WO2024017702A1 - Process for preparing a catalyst comprising a group viii metal and a support in the form of a monolith or a foam coated with alpha alumina - Google Patents
Process for preparing a catalyst comprising a group viii metal and a support in the form of a monolith or a foam coated with alpha alumina Download PDFInfo
- Publication number
- WO2024017702A1 WO2024017702A1 PCT/EP2023/069133 EP2023069133W WO2024017702A1 WO 2024017702 A1 WO2024017702 A1 WO 2024017702A1 EP 2023069133 W EP2023069133 W EP 2023069133W WO 2024017702 A1 WO2024017702 A1 WO 2024017702A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ceramic
- support
- monolith
- alumina
- catalyst
- Prior art date
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000006260 foam Substances 0.000 title claims description 40
- 239000000919 ceramic Substances 0.000 claims abstract description 74
- 239000006262 metallic foam Substances 0.000 claims abstract description 48
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- 229910052763 palladium Inorganic materials 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 10
- -1 nickel-chromium-aluminum Chemical compound 0.000 claims description 10
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
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- 239000010949 copper Substances 0.000 claims description 9
- 229910052878 cordierite Inorganic materials 0.000 claims description 9
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
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- 238000005119 centrifugation Methods 0.000 claims description 4
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 claims 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
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- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
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- 230000008021 deposition Effects 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/56—
-
- B01J35/60—
-
- B01J35/612—
-
- B01J35/615—
-
- B01J35/633—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
Definitions
- the subject of the invention is a process for preparing a selective hydrogenation catalyst comprising an active phase based on a Group VIII metal deposited on an alpha alumina and a support in the form of a monolith or a ceramic foam.
- the catalyst can be used in a process for the selective hydrogenation of polyunsaturated compounds in a hydrocarbon feed, in particular in C2-C5 steam cracking cuts and steam cracking gasolines.
- the monolith supports can be made of ceramic materials such as alumina or silicon carbide or zirconium or cordierite. Supports in the form of monoliths also exist with metallic materials, for example steel, stainless steel and many other types of metals.
- the foam supports can be made of ceramic materials, such as alumina or silicon carbide or zirconium. Foam supports also exist with metallic materials, for example nickel, aluminum, nickel-chrome, nickel-chrome-aluminum, and many other types of metals.
- Metallic or ceramic monoliths can be used in various catalytic applications, notably in the treatment of exhaust gases (US1969/3441381, US1971/35971653) or as a NO X reduction catalyst (Tomasic, V. 2007), or still in selective hydrogenation of hydrocarbon feeds comprising polyunsaturated compounds.
- Catalysts whose support is in the form of a monolith have a layer thickness of the active phase of 18 ⁇ m or 20 ⁇ m.
- This document discloses the use of a monolith support impregnated directly with PdCh on the walls of the monolith, the active phase obtained based on palladium having a thickness of 200 ⁇ m.
- the Applicant has developed a new process for preparing a catalyst comprising an active phase based on a group VIII metal deposited on an alpha alumina, and a support in the form of a monolith or a ceramic or metallic foam, said method comprising a step of bringing a gamma alumina powder into contact with a support in the form of a monolith or a ceramic or metallic foam, followed by a calcination step at high temperature in order to transform the gamma alumina into an alpha alumina, and finally a step of impregnation of the precursor of the active phase on the calcined catalyst precursor comprising an alpha alumina.
- This particular preparation process allows good adhesion of the active phase on the walls of the support after coating with gamma alumina, making it possible to treat the monolith or foam at very high temperatures without the adhesion deteriorating, and this even for final catalysts comprising a very low specific surface area.
- the subject of the present invention is a process for preparing a selective hydrogenation catalyst comprising an active phase based on at least one metal from group VIII, deposited on an alpha alumina, and a support in the form of a monolith or a ceramic or metallic foam, which process comprises at least the following steps: a) a gamma alumina powder is supplied comprising a specific surface area of between 100 and 500 m 2 /g; b) said gamma alumina powder from step a) is brought into contact by coating with a support in the form of a monolith or a ceramic or metallic foam to obtain a catalyst precursor comprising a gamma alumina ; c) the catalyst precursor obtained at the end of step b) is calcined at a temperature between 900°C and 1300°C to obtain a calcined catalyst precursor comprising an alpha alumina; d) the calcined catalyst precursor obtained at the end of step c) is brought into contact with a solution comprising at least one
- said Group VIII metal is palladium.
- the palladium content is between 0.005 and 1% by weight of palladium element relative to the total weight of the catalyst.
- step b) comprises the following sub-steps: b1) the gamma alumina powder is dispersed in a solution based on nitric acid and water, then the dispersed catalyst precursor is ground so as to obtain a suspension; b2) the ceramic or metallic foam is coated with said suspension obtained at the end of step b1) by soaking-withdrawal; b3) we carry out:
- step b2) either a centrifugation step of the coated ceramic or metal foam obtained at the end of step b2);
- step b2) either a step of blowing the coated ceramic or metallic foam obtained at the end of step b2); b4) optionally, the coated ceramic or metallic foam obtained at the end of step b3) is dried at a temperature between 80°C and 220°C; b5) the coated ceramic or metallic foam obtained at the end of step b3), optionally at the end of step b4), is calcined at a temperature between 250°C and 550°C.
- said support is in the form of a metal foam chosen from nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium-aluminum, nickel-iron-chromium-aluminum foams , iron-chrome-aluminum, nickel-aluminum, stainless steel.
- said support is in the form of a ceramic foam chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO), zinc oxide, zirconium oxide (ZrC>2), cordierite (AI 3 Mg 2 AISi50i8).
- alumina AI2O3
- silica-alumina silicon carbide
- SiC silicon carbide
- phosphorus-alumina phosphorus-alumina
- MgO magnesia
- ZrC>2 zirconium oxide
- cordierite AI 3 Mg 2 AISi50i8.
- said catalyst comprises a geometric surface area of between 1000 and 7000 m 2 /m 3 . According to one or more embodiments, said catalyst comprises a pore diameter of between 0.2 and 1.5 mm.
- step b) when the support is in the form of a ceramic or metallic monolith, said step b) comprises the following sub-steps: b1 ') the gamma alumina powder is dispersed in a solution based on nitric acid and water, then the dispersed catalyst precursor is ground so as to obtain a suspension; b2') the support in the form of a ceramic or metallic monolith is coated with said suspension obtained at the end of step bT) by soaking-withdrawal; b3') a step is carried out of blowing the coated ceramic or metallic monolith obtained at the end of step b2'); b4') optionally, the coated ceramic or metallic monolith obtained at the end of step b3') is dried at a temperature between 80°C and 220°C; b5') the coated ceramic or metallic monolith obtained at the end of step b3'), optionally at the end of step b4'), is calcined at a temperature between 250°C and 550°
- said support is in the form of a metal monolith chosen from steel, stainless steel, nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium-aluminum, iron-chromium monoliths. -aluminum.
- said support is in the form of a ceramic monolith chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO), zinc oxide, zirconium oxide (ZrCh), cordierite (Ah / ⁇ AISisOis).
- alumina AI2O3
- silica-alumina silicon carbide
- SiC silicon carbide
- phosphorus-alumina phosphorus-alumina
- MgO magnesia
- ZrCh zirconium oxide
- cordierite Ah / ⁇ AISisOis
- said support comprises a number of channels per unit of length (CPSI) between 300 and 1200.
- CPSI channels per unit of length
- the geometric surface of said catalyst is between 1500 m 2 /m 3 and 5000 m 2 /m 3 .
- said support in the form of a monolith or a ceramic or metallic foam supplied in step d) is previously calcined in air at a temperature between 300°C and 800° C for a period of between 2 and 8 hours.
- group VIII (or VIIIB) according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IIIPAC classification.
- the total pore volume and the specific surface area (SBET) of the alumina are measured by mercury porosimetry according to the ASTM D4284-92 standard with a wetting angle of 140° using an Autopore® IV model device from the Microméritics brand. ®.
- Monolithic or foam supports are generally characterized by the density and size of the channels, more specifically by the number of channels per unit of length which is called CPSI (“Channels per square inch” according to English terminology). -Saxon). As its abbreviation indicates, it corresponds to the number of channels intercepted by a section of 1 x 1 inch (“inch” according to Anglo-Saxon terminology) or 2.54 x 2.54 cm.
- the monolithic or foam supports are characterized by the number of channels per unit length (CPSI). It should be noted that the CPSI value of a catalyst comprising such a monolith or foam support does not change, whatever the thickness of the layer of the active phase of the catalyst.
- the porosity of the foam or monolith can be calculated by the following formula: with: s: porosity or void ratio of the foam or monolith; p m : density of the foam or monolith;
- Pmat density of the foam or monolith material.
- the group VIII metal content is measured by X-ray fluorescence.
- the process for preparing a selective hydrogenation catalyst comprising an active phase based on at least one group VIII metal, deposited on an alpha alumina, and an support in the form of a monolith or a ceramic or metallic foam comprises at least the following steps: a) a gamma alumina powder is supplied comprising a specific surface area of between 100 and 500 m 2 / g; b) said gamma alumina powder from step a) is brought into contact by coating with a support in the form of a monolith or a ceramic or metallic foam to obtain a catalyst precursor comprising a gamma alumina ; c) the catalyst precursor obtained at the end of step b) is calcined at a temperature between 900°C and 1300°C to obtain a calcined catalyst precursor comprising an alpha alumina; d) the calcined catalyst precursor obtained at the end of step c) is brought into contact with a solution comprising at least one precursor of the active phase comprising at least one
- a gamma alumina is supplied comprising a specific surface area of between 100 and 500 m 2 /g, preferably between 120 and 450 m 2 /g, and even more preferably between 150 and 300 m 2 /g , said gamma alumina being in the form of a powder.
- Alumina may include impurities such as metal oxides of groups HA, 111 B, IVB, II B, II IA, I A according to the CAS classification, preferably silica, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide and calcium oxide, or alkali metals, preferably lithium, sodium or potassium, and/or alkaline earth metals, preferably magnesium, calcium , strontium or barium or even sulfur.
- impurities such as metal oxides of groups HA, 111 B, IVB, II B, II IA, I A according to the CAS classification, preferably silica, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide and calcium oxide, or alkali metals, preferably lithium, sodium or potassium, and/or alkaline earth metals, preferably magnesium, calcium , strontium or barium or even sulfur.
- the alumina is in the form of a powder comprising a median diameter less than or equal to 250 pm, preferably between 10 and 250 pm, and even more preferably between 50 and 150 pm.
- the term "median diameter” here designates the diameter of an equivalent sphere such that 50% of the particles, by volume, have a greater diameter and 50% a smaller diameter.
- the alumina can be formed into powder by any technique well known to those skilled in the art, for example by grinding and sieving.
- the total porous volume of the alumina is between 0.1 and 1.5 cm 3 /g, preferably between 0.35 and 1.2 cm 3 /g, and even more preferably between 0.4 and 1.0 cm 3 /g, and even more preferably between 0.45 and 0.9 cm 3 /g.
- step b) the gamma alumina powder supplied in step a) is brought into contact with a support in the form of a monolith or a ceramic or metallic foam.
- the support in the form of a monolith or a ceramic or metallic foam used in step b) is previously calcined in air at a temperature between 300°C and 800°C for a period advantageously included between 2 and 8 hours in order to promote adhesion of the alumina powder to said support.
- a step b) is carried out of bringing the gamma alumina powder from step a) into contact with a support in the form of a ceramic or metallic foam.
- step b) advantageously comprises the following sub-steps: b1) the gamma alumina powder is dispersed in a solution based on nitric acid and water, then the precursor of catalyst dispersed so as to obtain a suspension (“slurry” according to Anglo-Saxon terminology) advantageously by means of a ball mill, for a period of preferably between 15 and 30 hours, more preferably between 18 and 28 hours, of so as to obtain a suspension advantageously comprising particles of calcined catalyst precursor having an average size of less than 1 ⁇ m; b2) the ceramic or metallic foam is coated with said suspension obtained at the end of step b1) by soaking-withdrawal; b3) we carry out:
- step b2 either a centrifugation step (“spin-coating” according to Anglo-Saxon terminology) of the coated ceramic or metallic foam obtained at the end of step b2) in order to remove the excess slurry, preferably at a speed between 4000 and 8500 rpm, preferably between 4500 and 8000 rpm;
- step b2 either a step of blowing the coated ceramic or metallic foam obtained at the end of step b2), advantageously using an inert gas or under air.
- the blowing technique is well known to those skilled in the art.
- a centrifugation step is carried out on the coated ceramic or metallic foam obtained at the end of step b2) in order to remove the excess slurry, preferably at a speed of between 4000 and 8500 rpm, preferably between 4500 and 8000 rpm; b4) optionally, the coated ceramic or metallic foam obtained at the end of step b3) is dried at a temperature between 80°C and 220°C, preferably between 90°C and 150°C, for a period advantageously between 6 and 30 hours, preferably between 8 and 24 hours; b5) the coated ceramic or metallic foam obtained at the end of step b3), optionally at the end of step b4), is calcined at a temperature between 250°C and 550°C, preferably between 320°C and 450°C, for a period advantageously between 1 and 6 hours, preferably between 2 and 4 hours.
- said foam is preferably chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO) foams. , zinc oxide, zirconium oxide (ZrCh), cordierite (AL / ⁇ AISisOis).
- said ceramic foam is made of alumina (AI2O3), silica-alumina, phosphorus-alumina, or silicon carbide (SiC).
- said foam is preferably chosen from nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium-aluminum, nickel-iron-chromium-foams. aluminum, iron-chrome-aluminum, nickel-aluminum, stainless steel (316L, 310SS).
- said metal foam is chosen from aluminum, nickel, nickel-chrome, nickel-chrome-aluminum foams. These foams can include additives such as molybdenum, manganese or even phosphorus.
- step b) of bringing the gamma alumina powder from step a) into contact with a support in the form of a ceramic or metallic monolith is carried out.
- step b) advantageously comprises the following substeps: b1 ') the gamma alumina powder is dispersed in a solution based on nitric acid and water, then the dispersed catalyst precursor is ground so as to obtain a suspension (“slurry” according to Anglo-Saxon terminology) advantageously by means of a ball mill, for a period preferably between 15 and 30 hours, more preferably between 18 and 28 hours, so as to obtain a suspension advantageously comprising particles of calcined catalyst precursor comprising a lower average size at 1 p.m.; b2') the ceramic or metallic monolith is coated with said suspension obtained at the end of step b1') by soaking-shrinkage; b3') a step of blowing the coated ceramic or metallic monolith obtained at the end
- the coated ceramic or metallic monolith obtained at the end of step b3') is dried at a temperature between 80°C and 220°C, preferably between 90°C and 150°C, for a duration advantageously between 6 and 30 hours, preferably between 8 and 24 hours;
- the coated ceramic or metallic foam obtained at the end of step b3'), optionally at the end of step b4'), is calcined at a temperature between 250°C and 550°C, preferably between 320°C and 450°C, for a period advantageously between 1 and 6 hours, preferably between 2 and 4 hours.
- said monolith is preferably chosen from monoliths made of steel, stainless steel (316L, 310SS), nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium -aluminum, iron-chrome-aluminum.
- said monolith is preferably chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO) monoliths. , zinc oxide, zirconium oxide (ZrCh), cordierite (Ah / ⁇ AISisOis).
- said ceramic monolith is made of alumina (AI2O3), silica-alumina, phosphorus-alumina, or silicon carbide (SiC).
- the support in the form of a monolith or a ceramic or metallic foam is coated with a layer of gamma alumina.
- the thickness of the layer depends on the number of coating steps carried out.
- Step b) can be repeated several times depending on the thickness of the desired gamma alumina layer.
- this preparation route makes it possible to obtain a layer of gamma alumina on the walls of the support comprised between 10 pm and 150 pm, preferably between 20 pm and 100 pm and even more preferably between 30 pm and 90 pm.
- the catalyst precursor comprising a gamma alumina obtained at the end of step b) is calcined, preferably under combustion air, and more preferably methane combustion air, comprising between 40 and 80 grams of water per kg of air, an oxygen level between 5% and 15% volume and a CO2 level between 4% and 10% volume.
- the calcination temperature is between 900°C and 1300°C, preferably between 1000°C and 1250°C, and even more preferably between 1000°C and 1150°C.
- the calcination of the support is carried out at high temperature in order to transform the gamma alumina into an alpha alumina.
- the calcination time is generally between 0.25 hours and 10 hours. Longer durations are not excluded, but do not necessarily bring improvement.
- step d) the calcined catalyst precursor comprising an alpha alumina obtained at the end of step c) is brought into contact with a solution comprising at least one precursor of the active phase comprising at least one metal from the group VIII to obtain a catalyst precursor.
- the deposition of the precursor of the active phase comprising at least one group VIII metal can be carried out by any method well known to those skilled in the art.
- said step d) can be carried out by impregnation, dry or in excess, or by deposition - precipitation, according to methods well known to those skilled in the art.
- Said step d) is preferably carried out by impregnation consisting for example of bringing the calcined catalyst precursor obtained at the end of step c) into contact with at least one solution, aqueous or organic (for example methanol or ethanol or phenol or acetone or toluene or dimethyl sulfoxide (DMSO)) or consisting of a mixture of water and at least one organic solvent, containing at least one precursor of the active phase comprising at least one group VIII metal at least partially in the dissolved state, or else by bringing the calcined catalyst precursor obtained at the end of step c) into contact with at least one colloidal solution of at least one precursor of the active phase comprising at least one metal from group VIII, in oxidized form or in reduced form.
- the solution is aqueous.
- the pH of this solution can be modified by the possible addition of an acid or a base.
- said step d) is carried out by dry impregnation, which consists of bringing the calcined catalyst precursor obtained at the end of step c) into contact with a solution, containing at least one active phase precursor comprising at least one group VIII metal, the volume of the solution of which is between 0.3 and 1.5 times the pore volume of the support to be impregnated.
- the Group VIII metal of the active phase is preferably chosen from nickel, platinum and palladium.
- the Group VIII metal is palladium or platinum and more preferably palladium.
- the concentration of palladium in solution is adjusted according to the pore volume of the support still available so as to obtain on the final catalyst a palladium content generally between 0.005 and 1% by weight of said element relative to to the total weight of the catalyst, preferably between 0.01 and 0.7% by weight, and even more preferably between 0.02 and 0.5% by weight, even more preferably between 0.025 and 0.3% by weight.
- a precursor is advantageously used in the form of nitrate, carbonate, chloride, sulfate, etc. hydroxide, hydroxycarbonate, formate, acetate, oxalate, complexes formed with acetylacetonates, or even tetrammine or hexammine complexes, or any other inorganic derivative soluble in aqueous solution, which is brought into contact with said support.
- the precursor is selected from sodium chloropalladate and palladium nitrate.
- a colloidal suspension of metal oxide from Group VIII or d is prepared.
- Group VIII metal hydroxide preferably palladium oxide or palladium hydroxide, in aqueous phase by mixing an aqueous solution (I) comprising at least one hydroxide selected from the group consisting of hydroxides of group VIII alkalis and alkaline earth hydroxides and an aqueous solution (II) comprising at least one active phase precursor of palladium.
- said colloidal suspension is generally obtained by hydrolysis of the metal cation, preferably palladium, in an aqueous medium, which leads to the formation of particles of metal oxide or hydroxide, preferably palladium, in suspension.
- the aqueous solution of alkali hydroxide or alkaline earth hydroxide is generally selected from the group consisting of aqueous solutions of sodium hydroxide, aqueous solutions of magnesium hydroxide.
- the aqueous solution is an aqueous solution of sodium hydroxide.
- the catalyst precursor obtained is generally matured in the wet state for 5 minutes to 12 hours, preferably for 5 minutes to 6 hours, preferably at a temperature between 15° C and 45°C. Longer durations are not excluded, but do not necessarily bring improvement.
- the material obtained at the end of step d) is dried at a temperature below 250°C, more preferably between 30°C and 220°C, more preferably between 90°C and 180°C.
- the drying time is advantageously between 0.5 hour and 20 hours. Longer durations are not excluded, but do not necessarily bring improvement.
- Drying is generally carried out under combustion air of a hydrocarbon, preferably methane, or under heated air comprising between 0 and 80 grams of water per kilogram of combustion air, an oxygen level of between 5% and 25% volume and a carbon dioxide level of between 0% and 10% volume.
- a hydrocarbon preferably methane
- heated air comprising between 0 and 80 grams of water per kilogram of combustion air, an oxygen level of between 5% and 25% volume and a carbon dioxide level of between 0% and 10% volume.
- the dried material is calcined, preferably under combustion air, and more preferably methane combustion air, comprising between 40 and 80 grams of water per kg of air, an oxygen level of between 5% and 15% volume and a CO2 rate of between 4% and 10% volume.
- the calcination temperature is between 250°C and 550°C, preferably between 300°C and 480°C, and even more preferably between 320°C and 450°C.
- the calcination time is generally between 0.25 hours and 10 hours. Longer durations are not excluded, but do not necessarily bring improvement.
- Step f) (optional step)
- the catalyst obtained at the end of step e) generally undergoes a reduction step.
- This step is preferably carried out in the presence of a reducing gas, either in-situ, that is to say in the reactor where the catalytic transformation is carried out, or ex-situ.
- this step is carried out at a temperature between 80°C and 450°C, even more preferably between 100°C and 400°C.
- the reduction is carried out in the presence of a reducing gas preferably comprising between 25 vol% and 100 vol% of hydrogen, for example 100 vol% of hydrogen.
- a reducing gas preferably comprising between 25 vol% and 100 vol% of hydrogen, for example 100 vol% of hydrogen.
- the hydrogen is optionally supplemented by an inert gas for reduction, preferably argon, nitrogen or methane.
- the reduction generally includes a temperature rise phase then a plateau.
- the duration of the reduction stage is generally between 1 hour and 40 hours, preferably between 2 hours and 20 hours.
- the Volumetric Hourly Speed (VVH) is generally between 150 and 3000, preferably between 300 and 1500 liters of reducing gas per hour and per liter of catalyst.
- the catalyst obtained by the preparation process according to the invention comprises an active phase based on at least one metal from group VIII and a support in the form of a monolith or a ceramic or metallic foam coated with an alpha alumina.
- the Group VIII metal of the active phase is preferably chosen from nickel, platinum and palladium.
- the Group VIII metal is palladium or platinum, and more preferably platinum.
- the palladium content is generally between 0.005 and 1% by weight of said element relative to the total weight of the catalyst, preferably between 0.01 and 0.7% by weight, and even more preferably between 0.02 and 0.5% by weight, even more preferably between 0.025 and 0.3% by weight.
- the catalyst may further comprise, as active phase, a group IB element, preferably chosen from silver and copper.
- a group IB element preferably chosen from silver and copper.
- the element of group IB is money.
- the group IB element content is preferably between 0.01 and 0.3% by weight relative to the total weight of the catalyst, more preferably between 0.015 and 0.2% by weight.
- the support comes in the form of a monolith or ceramic or metallic foam. i) Ceramic or metallic monolith
- said support When the support is in the form of a ceramic or metallic monolith, said support comprises a number of channels per unit length (CPSI) between 300 and 1200.
- CPSI channels per unit length
- the number of channels per unit length (CPSI) of said support is between 300 and 1200, preferably between 350 and 1000, more preferably between 400 and 700, and even more preferably between 450 and 750.
- the geometric surface of said catalyst is between 1500 m 2 /m 3 and 5000 m 2 /m 3 , preferably between 1500 m 2 /m 3 and 4000 m 2 /m 3 , and even more preferably between 2000 m 2 /m 3 and 4000 m 2 /m 3 .
- the thickness of the catalyst wall is between 0.08 mm and 0.5 mm, more preferably between 0.1 mm and 0.4 mm.
- the porosity rate of said catalyst is between 15% and 90%, preferably between 20% and 90%, and more preferably between 20% and 70%.
- the active phase is in the form of a layer on the walls of said support, the thickness of said layer of active phase being between 30 pm and 150 pm, preferably between 60 pm and 100 pm, and again more preferably between 60 pm and 90 pm.
- the catalyst support is in the form of a metal monolith, said monolith is preferably chosen from monoliths made of steel, stainless steel (316L, 310SS), nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium -aluminum, iron-chrome-aluminum.
- said monolith is preferably chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO) monoliths. , zinc oxide, zirconium oxide (ZrCh), cordierite (Ah / ⁇ AISisOis).
- said ceramic monolith is made of alumina (AI2O3), silica-alumina, phosphorus-alumina, or silicon carbide (SiC).
- said catalyst comprises a geometric surface area of between 1000 and 7000 m 2 /m 3 and a pore diameter of between 0.2 and 1.5 mm.
- the geometric surface of said catalyst is between 2000 and 5000 m 2 /m 3 , and even more preferably between 2000 and 4000 m 2 /m 3 .
- the diameter of the pores of said catalyst is between 0.3 and 1.5 mm, and even more preferably between 0.5 and 1.5 mm.
- the porosity rate of said catalyst is between 75 and 90% when the support is a ceramic foam.
- the porosity rate of said catalyst is between 75 and 95% when the support is a metal foam.
- said foam is preferably chosen from nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium-aluminum, nickel-iron-chromium-foams. aluminum, iron-chrome-aluminum, nickel-aluminum, stainless steel (316L, 310SS).
- said metal foam is chosen from aluminum, nickel, nickel-chrome, nickel-chrome-aluminum foams. These foams can include additives such as molybdenum, manganese or even phosphorus.
- said foam is preferably chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO) foams. , zinc oxide, zirconium oxide (Zr ⁇ 2), cordierite (AI 3 Mg 2 AISi50i8).
- said ceramic foam is made of alumina (AI2O3), silica-alumina, phosphorus-alumina, or silicon carbide (SiC).
- the active phase is in the form of a layer on the walls of said support, the thickness of said layer of active phase being between 10 pm and 150 pm, preferably between 20 pm and 100 pm and even more preferably between 30 p.m. and 90 p.m.
- the catalyst obtained by the process according to the invention can be used in a process for the selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule, such as diolefins and/or acetylenes and/or alkenylaromatics, contained in a hydrocarbon feed having a final boiling point less than or equal to 300°C, which process being carried out at a temperature between 0 and 300°C, at a pressure between 0.1 and 10 MPa, at a ratio molar hydrogen/(polyunsaturated compounds to be hydrogenated) of between 0.1 and 10 and at an hourly volume rate (VVH) of between 0.1 and 200 h -1 when the process is carried out in the liquid phase, or at a molar hydrogen ratio /(polyunsaturated compounds to be hydrogenated) between 0.5 and 1000 and at an hourly volume rate between 100 and 40,000 h -1 when the process is carried out in the gas phase.
- Monounsaturated organic compounds such as ethylene and propylene, are the source of the manufacturing of polymers, plastics and other value-added chemicals. These compounds are obtained from natural gas, naphtha or diesel which have been treated by steam cracking or catalytic cracking processes.
- Selective hydrogenation is the primary treatment developed to specifically remove unwanted polyunsaturated compounds from these hydrocarbon feedstocks. It allows the conversion of polyunsaturated compounds to the corresponding alkenes or aromatics while avoiding their total saturation and therefore the formation of the corresponding alkanes or naphthenes. In the case of steam cracking gasolines used as feedstock, selective hydrogenation also makes it possible to selectively hydrogenate the alkenyl aromatics into aromatics while avoiding the hydrogenation of the aromatic nuclei.
- the hydrocarbon feedstock treated in the selective hydrogenation process has a final boiling point of 300°C or less and contains at least 2 carbon atoms per molecule and includes at least one polyunsaturated compound.
- polyunsaturated compounds means compounds comprising at least one acetylenic function and/or at least one diene function and/or at least one alkenyl aromatic function.
- the feed is selected from the group consisting of a C2 steam cracking cut, a C2-C3 steam cracking cut, a C3 steam cracking cut, a C4 steam cracking cut, a C5 steam cracking cut and a steam cracking gasoline also called pyrolysis gasoline or C5+ cut.
- the C2 steam cracking cut advantageously used for implementing the selective hydrogenation process according to the invention, has for example the following composition: between 40 and 95% by weight of ethylene, of the order of 0.1 to 5% by weight of acetylene, the remainder being essentially ethane and methane.
- ethylene of the order of 0.1 to 5% by weight of acetylene
- the remainder being essentially ethane and methane.
- C3 compounds may also be present.
- the C3 steam cracking cut advantageously used for implementing the selective hydrogenation process according to the invention, has for example the following average composition: of the order of 90% by weight of propylene, of the order of 1 to 8% by weight of propadiene and methylacetylene, the remainder being essentially propane. In some C3 cuts, between 0.1 and 2% by weight of C2 compounds and C4 compounds may also be present.
- a C2 - C3 cut can also be advantageously used for implementing the selective hydrogenation process according to the invention. It has, for example, the following composition: of the order of 0.1 to 5% by weight of acetylene, of the order of 0.1 to 3% by weight of propadiene and methylacetylene, of the order of 30% by weight of ethylene, of the order of 5% by weight of propylene, the remainder being essentially methane, ethane and propane.
- This filler can also contain between 0.1 and 2% by weight of C4 compounds.
- the C4 steam cracking cut advantageously used for implementing the selective hydrogenation process according to the invention, has for example the following average mass composition: 1% by weight of butane, 46.5% by weight of butene, 51% by weight of butadiene, 1.3% by weight of vinylacetylene and 0.2% by weight of butyne. In some C4 cuts, between 0.1 and 2% by weight of C3 compounds and C5 compounds may also be present.
- the C5 steam cracking cut advantageously used for implementing the selective hydrogenation process according to the invention, has for example the following composition: 21% by weight of pentanes, 45% by weight of pentenes, 34% by weight of pentadienes.
- the steam cracking gasoline or pyrolysis gasoline corresponds to a hydrocarbon cut whose boiling temperature is generally between 0 and 300 ° C, of preferably between 10 and 250°C.
- Polyunsaturated hydrocarbons to be hydrogenated present in said steam cracking gasoline are in particular diolefinic compounds (butadiene, isoprene, cyclopentadiene, etc.), styrenic compounds (styrene, alpha-methylstyrene, etc.) and indene compounds (indene, etc.).
- Steam cracked gasoline generally includes the C5-C12 cut with traces of C3, C4, C13, C14, C15 (for example between 0.1 and 3% by weight for each of these cuts).
- a charge formed from pyrolysis gasoline generally has the following composition: 5 to 30% by weight of saturated compounds (paraffins and naphthenes), 40 to 80% by weight of aromatic compounds, 5 to 20% by weight of mono-olefins, 5 to 40% by weight of diolefins, 1 to 20% by weight of alkenyl aromatic compounds, all of the compounds forming 100%. It also contains from 0 to 1000 ppm by weight of sulfur, preferably from 0 to 500 ppm by weight of sulfur.
- the polyunsaturated hydrocarbon feedstock treated in accordance with the selective hydrogenation process according to the invention is a C2 steam cracking cut, or a C2-C3 steam cracking cut, or a steam cracking gasoline.
- the selective hydrogenation process according to the invention aims to eliminate said polyunsaturated hydrocarbons present in said feed to be hydrogenated without hydrogenating the monounsaturated hydrocarbons.
- the selective hydrogenation process aims to selectively hydrogenate acetylene.
- the selective hydrogenation process aims to selectively hydrogenate propadiene and methylacetylene.
- a C4 cut we aim to eliminate butadiene, vinylacetylene (VAC) and butyne
- VAC vinylacetylene
- butyne in the case of a C5 cut, we aim to eliminate pentadienes.
- the selective hydrogenation process aims to selectively hydrogenate said polyunsaturated hydrocarbons present in said feedstock to be treated so that the diolefinic compounds are partially hydrogenated into mono-olefins and that the styrenic and indenic compounds are partially hydrogenated into corresponding aromatic compounds while avoiding the hydrogenation of the aromatic nuclei.
- the technological implementation of the selective hydrogenation process is for example carried out by injection, in an ascending or descending current, of the polyunsaturated hydrocarbon feed and the hydrogen into at least one fixed bed reactor.
- Said reactor can be of the isothermal type or of the adiabatic type.
- An adiabatic reactor is preferred.
- the polyunsaturated hydrocarbon feed can advantageously be diluted by one or more reinjections) of the effluent, coming from said reactor where the selective hydrogenation reaction occurs, at various points of the reactor, located between the inlet and outlet of the reactor in order to limit the temperature gradient in the reactor.
- the technological implementation of the selective hydrogenation process according to the invention can also be advantageously carried out by the implantation of at least said supported catalyst in a reactive distillation column or in reactors - exchangers or in a slurry type reactor .
- the flow of hydrogen can be introduced at the same time as the feed to be hydrogenated and/or at one or more different points in the reactor.
- the selective hydrogenation of the C2, C2-C3, C3, C4, C5 and C5+ steam cracking cuts can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase for the C3, C4, C5 and C5+ cuts and in the gaseous for cuts C2 and C2-C3.
- a reaction in the liquid phase makes it possible to lower the energy cost and increase the cycle time of the catalyst.
- the selective hydrogenation of a hydrocarbon feed containing polyunsaturated compounds containing at least 2 carbon atoms per molecule and having a final boiling point less than or equal to 300°C is carried out at a temperature between 0 and 300°C, at a pressure between 0.1 and 10 MPa, at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio between 0.1 and 10 and at an hourly volume velocity VVH (defined as the ratio of the volume flow rate of charge to the volume of the catalyst) of between 0.1 and 200 h -1 for a process carried out in the liquid phase, or at a molar ratio of hydrogen/(polyunsaturated compounds to be hydrogenated) of between 0.5 and 1000 and at an hourly volume speed VVH of between 100 and 40000 h -1 for a process carried out in the gas phase.
- VVH defined as the ratio of the volume flow rate of charge to the volume of the catalyst
- the molar ratio (hydrogen)/(polyunsaturated compounds to be hydrogenated) is generally understood between 0.5 and 10, preferably between 0.7 and 5.0 and even more preferably between 1.0 and 2.0, the temperature is between 0 and 200°C, preferably between 20 and 200° C and even more preferably between 30 and 180°C, the hourly volume velocity (VVH) is generally between 0.5 and 100 h'1 , preferably between 1 and 50 h'1 and the pressure is generally between 0.3 and 8.0 MPa, preferably between 1.0 and 7.0 MPa and even more preferably between 1.5 and 4.0 MPa.
- a selective hydrogenation process is carried out in which the feedstock is a steam cracking gasoline comprising polyunsaturated compounds, the hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio is between 0.7 and 5.0, the temperature is between 20 and 200°C, the hourly volume velocity (VVH) is generally between 1 and 50 h -1 and the pressure is between 1.0 and 7.0 MPa.
- the feedstock is a steam cracking gasoline comprising polyunsaturated compounds
- the hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio is between 0.7 and 5.0
- the temperature is between 20 and 200°C
- the hourly volume velocity (VVH) is generally between 1 and 50 h -1
- the pressure is between 1.0 and 7.0 MPa.
- a selective hydrogenation process is carried out in which the feedstock is a steam cracking gasoline comprising polyunsaturated compounds, the hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio is between 1.0 and 2.0, the temperature is between 30 and 180°C, the hourly volume velocity (VVH) is generally between 1 and 50 h'1 and the pressure is between 1.5 and 4.0 MPa.
- the flow rate of hydrogen is adjusted in order to have a sufficient quantity to theoretically hydrogenate all the polyunsaturated compounds and to maintain an excess of hydrogen at the reactor outlet.
- the molar ratio ( hydrogen)/(polyunsaturated compounds to be hydrogenated) is generally between 0.5 and 1000, preferably between 0.7 and 800, the temperature is between 0 and 300°C, preferably between 15 and 280°C, the speed hourly volume (VVH) is generally between 100 and 40,000 h -1 , preferably between 500 and 30,000 h -1 and the pressure is generally between 0.1 and 6.0 MPa, preferably between 0.2 and 5, 0 MPa.
- Example 1 Pd catalyst on NiCr metal foam support
- the support is a NiCr metal foam (RECEMAT® supplier) pretreated at 600°C to eliminate organic contaminants and promote adhesion of the catalyst precursor to the support.
- a suspension based on a gamma alumina powder with a specific surface area of 212 m 2 /g (SDA 500, Sasol) is prepared by dispersing the alumina powder in a nitric acid + water solution. This suspension is placed in a ball mill for 24 hours to homogenize and reduce the size of the alumina particles ( ⁇ 1 pm).
- the catalyst precursor obtained is calcined in a muffle furnace at 1100°C for 13 hours under a static atmosphere with a temperature rise ramp of 10°C/min.
- a colloidal solution of palladium oxide particles is prepared with a concentration of 0.23% by weight of the element palladium in the presence of sodium hydroxide.
- Adhesion test - Protocol in order to check the good adhesion of the active phase on the support, each catalyst sample is dried, weighed, then placed in petroleum ether then sonicated for 30 minutes at room temperature. Then, the petroleum ether is evaporated at room temperature and the catalysts are dried at a temperature of 150°C to be weighed again.
- the preparation process according to the invention makes it possible to obtain catalysts whose active palladium phase has good adhesion to the walls of the support in the form of a NiCr metal foam, because the loss in mass after testing remains lower at 2%.
- a suspension based on a gamma alumina powder with a specific surface area of 212 m 2 /g (SDA 500, Sasol) is prepared by dispersing the alumina powder in a nitric acid + water solution. This suspension is placed in a ball mill for 24 hours to homogenize and reduce the size of the alumina particles ( ⁇ 1 pm).
- the catalyst precursor obtained is calcined in a muffle furnace at 1100°C for 10 hours under a static atmosphere with a temperature rise ramp of 10°C/min.
- a colloidal solution of palladium oxide particles is prepared with a concentration of 0.20% by weight of the element palladium in the presence of sodium hydroxide.
- the catalyst is tested via an adhesion test under the same operating conditions as Example 1.
- the test was carried out on 4 different samples in order to check the repeatability of the preparation process. The results are presented in Table 2 below. Table 2
- the preparation process according to the invention makes it possible to obtain catalysts whose active palladium phase has good adhesion to the walls of the support in the form of a metallic FeCrAI monolith because the loss in mass after testing remains less than 1.5%.
Abstract
Process for preparing a selective hydrogenation catalyst comprising an active phase based on at least one group VIII metal, deposited on an alpha alumina, and a support in the form of a ceramic or metal foam or monolith, which process comprises at least the following steps: - supplying a gamma alumina powder comprising a specific surface area of between 100 and 500 m²/g; - bringing into contact, by coating, the gamma alumina powder and a support in the form of a ceramic or metal foam or monolith; - calcining at a temperature of between 900°C and 1300°C; - bringing the calcined catalyst precursor into contact with a solution comprising a precursor of the active phase comprising a group VIII metal; - drying and then calcining the material.
Description
PROCEDE DE PREPARATION D’UN CATALYSEUR COMPRENANT UN METAL DU GROUPE VIII ET UN SUPPORT SOUS LA FORME D’UN MONOLITHE OU D’UNE MOUSSE ENDUIT D’ALUMINE ALPHA METHOD FOR PREPARING A CATALYST COMPRISING A GROUP VIII METAL AND A SUPPORT IN THE FORM OF A MONOLITH OR A FOAM COATED WITH ALPHA ALUMINA
Domaine technique Technical area
L'invention a pour objet un procédé de préparation d’un catalyseur d’hydrogénation sélective comprenant une phase active à base d’un métal du groupe VIII déposé sur une alumine alpha et un support se présentant sous la forme d’un monolithe ou d’une mousse céramique. Le catalyseur peut être utilisé dans un procédé d’hydrogénation sélective de composés polyinsaturés dans une charge hydrocarbonée, notamment dans les coupes C2-C5 de vapocraquage et les essences de vapocraquage. The subject of the invention is a process for preparing a selective hydrogenation catalyst comprising an active phase based on a Group VIII metal deposited on an alpha alumina and a support in the form of a monolith or a ceramic foam. The catalyst can be used in a process for the selective hydrogenation of polyunsaturated compounds in a hydrocarbon feed, in particular in C2-C5 steam cracking cuts and steam cracking gasolines.
Etat de la technique State of the art
De nombreux catalyseurs comprenant un support en forme de monolithe ou de mousse ont été développés et fabriqués ces dernières années avec différentes techniques de fabrication. Les supports en monolithe peuvent être en matériaux céramiques comme par exemple de l’alumine ou du carbure du silicium ou du zirconium ou de la cordiérite. Les supports se présentant sous la forme de monolithe existent aussi avec des matériaux métalliques, par exemple en acier, acier inox et bien d’autres types de métaux. Les supports en mousse peuvent être en matériaux céramiques, comme par exemple de l’alumine ou du carbure du silicium ou du zirconium. Les supports mousses existent aussi avec des matériaux métalliques, par exemple en nickel, aluminium, nickel-chrome, nickel-chrome-aluminium, et bien d’autres types de métaux. Many catalysts comprising a support in the form of a monolith or foam have been developed and manufactured in recent years with different manufacturing techniques. The monolith supports can be made of ceramic materials such as alumina or silicon carbide or zirconium or cordierite. Supports in the form of monoliths also exist with metallic materials, for example steel, stainless steel and many other types of metals. The foam supports can be made of ceramic materials, such as alumina or silicon carbide or zirconium. Foam supports also exist with metallic materials, for example nickel, aluminum, nickel-chrome, nickel-chrome-aluminum, and many other types of metals.
Les monolithes métalliques ou céramiques peuvent être utilisés dans diverses applications catalytiques, notamment dans le traitement des gaz d’échappement (US1969/3441381 , US1971/35971653) ou en tant que catalyseur de réduction des NOX (Tomasic, V. 2007), ou encore en hydrogénation sélective de charges hydrocarbonées comprenant des composés polyinsaturés. Metallic or ceramic monoliths can be used in various catalytic applications, notably in the treatment of exhaust gases (US1969/3441381, US1971/35971653) or as a NO X reduction catalyst (Tomasic, V. 2007), or still in selective hydrogenation of hydrocarbon feeds comprising polyunsaturated compounds.
L’article de revue "Selective hydrogenation of 1 ,3-butadiene in the presence of 1-butene under liquid phase conditions using structured catalysts" de F.J. Méndeza et al. publié dans Catalysis Today 289 (2017) 151-161 s’intéresse à l’utilisation d’un support de catalyseur sous la forme de mousses ou de monolithes métalliques pour l’hydrogénation sélective du 1 ,3-butadiène. Ce document divulgue que l’utilisation d’un support en mousse ou en monolithe enduit de phase active de NiPd/(CeO2-AI2O3) donne des bons résultats en matière de conversion et en matière de sélectivité en hydrogénation sélective du 1 ,3-butadiène. Les catalyseurs dont le support se présente sous la forme d’un monolithe ont une épaisseur de couche de la phase active de 18 pm ou 20 pm.
L’article “Catalyst deactivation in liquid- and gas-phase hydrogenation acetylene using a monolithic catalyst reactor” de Asplud et al. publié dans Catalysis Today, vol. 24 (181-187) 1995, s’intéresse à l’utilisation d’un support de catalyseur sous la forme de monolithe céramique en alumine-a pour l’hydrogénation sélective de l’acétylène. Ce document divulgue l’utilisation d’un support en monolithe imprégné directement avec du PdCh sur les parois du monolithe, la phase active obtenue à base de palladium ayant une épaisseur de 200 pm. The review article "Selective hydrogenation of 1,3-butadiene in the presence of 1-butene under liquid phase conditions using structured catalysts" by FJ Méndeza et al. published in Catalysis Today 289 (2017) 151-161 focuses on the use of a catalyst support in the form of foams or metal monoliths for the selective hydrogenation of 1,3-butadiene. This document discloses that the use of a foam or monolith support coated with active phase of NiPd/(CeO2-Al 2 O3) gives good results in terms of conversion and in terms of selectivity in selective hydrogenation of 1,3 -butadiene. Catalysts whose support is in the form of a monolith have a layer thickness of the active phase of 18 μm or 20 μm. The article “Catalyst deactivation in liquid- and gas-phase hydrogenation acetylene using a monolithic catalyst reactor” by Asplud et al. published in Catalysis Today, vol. 24 (181-187) 1995, focuses on the use of a catalyst support in the form of a ceramic alumina monolith for the selective hydrogenation of acetylene. This document discloses the use of a monolith support impregnated directly with PdCh on the walls of the monolith, the active phase obtained based on palladium having a thickness of 200 μm.
La Demanderesse a mis au point un nouveau procédé de préparation d’un catalyseur comprenant une phase active à base d’un métal du groupe VIII déposée sur une alumine alpha, et un support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique, ledit procédé comprenant une étape de mise en contact d’une poudre d’alumine gamma avec un support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique, suivie d’une étape de calcination à haute température afin de transformer l’alumine gamma en une alumine alpha, et enfin une étape d’imprégnation du précurseur de la phase active sur le précurseur de catalyseur calciné comprenant une alumine alpha. Ce procédé de préparation particulier permet une bonne accroche de la phase active sur les parois du support après une enduction de l’alumine gamma, permettant alors de traiter à de très haute température le monolithe ou la mousse sans que l’accroche se détériore, et cela même pour des catalyseurs finaux comprenant une surface spécifique très faible. The Applicant has developed a new process for preparing a catalyst comprising an active phase based on a group VIII metal deposited on an alpha alumina, and a support in the form of a monolith or a ceramic or metallic foam, said method comprising a step of bringing a gamma alumina powder into contact with a support in the form of a monolith or a ceramic or metallic foam, followed by a calcination step at high temperature in order to transform the gamma alumina into an alpha alumina, and finally a step of impregnation of the precursor of the active phase on the calcined catalyst precursor comprising an alpha alumina. This particular preparation process allows good adhesion of the active phase on the walls of the support after coating with gamma alumina, making it possible to treat the monolith or foam at very high temperatures without the adhesion deteriorating, and this even for final catalysts comprising a very low specific surface area.
Objets de l’invention Objects of the invention
La présente invention a pour objet un procédé de préparation d’un catalyseur d’hydrogénation sélective comprenant une phase active à base d’au moins un métal du groupe VIII, déposée sur une alumine alpha, et un support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique, lequel procédé comprend au moins les étapes suivantes : a) on approvisionne une poudre d’alumine gamma comprenant une surface spécifique comprise entre 100 et 500 m2/g ; b) on met en contact par enduction ladite poudre d’alumine gamma de l’étape a) avec un support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique pour obtenir un précurseur de catalyseur comprenant une alumine gamma ; c) on calcine le précurseur de catalyseur obtenu à l’issue de l’étape b) à une température comprise entre 900°C et 1300°C pour obtenir un précurseur de catalyseur calciné comprenant une alumine alpha ; d) on met en contact le précurseur de catalyseur calciné obtenu à l’issue de l’étape c) avec une solution comprenant au moins un précurseur de la phase active comprenant au moins un métal du groupe VIII pour obtenir un matériau ;
e) on sèche le matériau obtenu à l’issue de l’étape d) à une température inférieure à 250°C puis on calcine le matériau séché à une température comprise entre 250°C et 550°C. The subject of the present invention is a process for preparing a selective hydrogenation catalyst comprising an active phase based on at least one metal from group VIII, deposited on an alpha alumina, and a support in the form of a monolith or a ceramic or metallic foam, which process comprises at least the following steps: a) a gamma alumina powder is supplied comprising a specific surface area of between 100 and 500 m 2 /g; b) said gamma alumina powder from step a) is brought into contact by coating with a support in the form of a monolith or a ceramic or metallic foam to obtain a catalyst precursor comprising a gamma alumina ; c) the catalyst precursor obtained at the end of step b) is calcined at a temperature between 900°C and 1300°C to obtain a calcined catalyst precursor comprising an alpha alumina; d) the calcined catalyst precursor obtained at the end of step c) is brought into contact with a solution comprising at least one precursor of the active phase comprising at least one metal from group VIII to obtain a material; e) the material obtained at the end of step d) is dried at a temperature below 250°C and then the dried material is calcined at a temperature between 250°C and 550°C.
Selon un ou plusieurs modes de réalisation, ledit métal du groupe VIII est le palladium. According to one or more embodiments, said Group VIII metal is palladium.
Selon un ou plusieurs modes de réalisation, la teneur en palladium est comprise entre 0,005 et 1 % poids en élément palladium par rapport au poids total du catalyseur. According to one or more embodiments, the palladium content is between 0.005 and 1% by weight of palladium element relative to the total weight of the catalyst.
Dans un mode de réalisation selon l’invention, lorsque le support se présente sous la forme d’une mousse céramique ou métallique, ladite étape b) comprend les sous-étapes suivantes : b1) on disperse la poudre d’alumine gamma dans une solution à base d’acide nitrique et d’eau, puis on broie le précurseur de catalyseur dispersé de manière à obtenir une suspension ; b2) on enduit la mousse céramique ou métallique de ladite suspension obtenue à l’issue de l’étape b1) par trempage-retrait ; b3) on réalise : In one embodiment according to the invention, when the support is in the form of a ceramic or metallic foam, said step b) comprises the following sub-steps: b1) the gamma alumina powder is dispersed in a solution based on nitric acid and water, then the dispersed catalyst precursor is ground so as to obtain a suspension; b2) the ceramic or metallic foam is coated with said suspension obtained at the end of step b1) by soaking-withdrawal; b3) we carry out:
- soit une étape de centrifugation de la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b2) ; - either a centrifugation step of the coated ceramic or metal foam obtained at the end of step b2);
- soit une étape de soufflage de la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b2) ; b4) optionnellement, on sèche la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b3) à une température comprise entre 80°C et 220°C ; b5) on calcine la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b3), optionnellement à l’issue de l’étape b4), à une température comprise entre 250°C et 550°C. - either a step of blowing the coated ceramic or metallic foam obtained at the end of step b2); b4) optionally, the coated ceramic or metallic foam obtained at the end of step b3) is dried at a temperature between 80°C and 220°C; b5) the coated ceramic or metallic foam obtained at the end of step b3), optionally at the end of step b4), is calcined at a temperature between 250°C and 550°C.
Selon un ou plusieurs modes de réalisation, ledit support se présente sous la forme d’une mousse métallique choisie parmi les mousses en nickel, aluminium, fer, cuivre, nickel-chrome, nickel-chrome-aluminium, nickel-fer-chrome-aluminium, fer-chrome-aluminium, nickel- aluminium, inox. According to one or more embodiments, said support is in the form of a metal foam chosen from nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium-aluminum, nickel-iron-chromium-aluminum foams , iron-chrome-aluminum, nickel-aluminum, stainless steel.
Selon un ou plusieurs modes de réalisation, ledit support se présente sous la forme d’une mousse céramique choisie parmi les mousses en alumine (AI2O3), silice-alumine, carbure de silicium (SiC), phosphore-alumine, magnésie (MgO), oxyde de zinc, oxyde de zirconium (ZrC>2), cordiérite (AI3Mg2AISi50i8). According to one or more embodiments, said support is in the form of a ceramic foam chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO), zinc oxide, zirconium oxide (ZrC>2), cordierite (AI 3 Mg 2 AISi50i8).
Selon un ou plusieurs modes de réalisation, ledit catalyseur comprend une surface géométrique comprise entre 1000 et 7000 m2/m3.
Selon un ou plusieurs modes de réalisation, ledit catalyseur comprend un diamètre des pores compris entre 0,2 et 1 ,5 mm. According to one or more embodiments, said catalyst comprises a geometric surface area of between 1000 and 7000 m 2 /m 3 . According to one or more embodiments, said catalyst comprises a pore diameter of between 0.2 and 1.5 mm.
Dans un mode de réalisation selon l’invention, lorsque le support se présente sous la forme d’un monolithe céramique ou métallique, ladite étape b) comprend les sous-étapes suivantes : b1 ’) on disperse la poudre d’alumine gamma dans une solution à base d’acide nitrique et d’eau, puis on broie le précurseur de catalyseur dispersé de manière à obtenir une suspension ; b2’) on enduit le support se présentant sous la forme d’un monolithe céramique ou métallique de ladite suspension obtenue à l’issue de l’étape bT) par trempage-retrait ; b3’) on réalise une étape de soufflage du monolithe céramique ou métallique enduit obtenu à l’issue de l’étape b2’); b4’) optionnellement, on sèche du monolithe céramique ou métallique enduit obtenu à l’issue de l’étape b3’) à une température comprise entre 80°C et 220°C ; b5’) on calcine du monolithe céramique ou métallique enduit obtenue à l’issue de l’étape b3’), optionnellement à l’issue de l’étape b4’), à une température comprise entre 250°C et 550°C. In one embodiment according to the invention, when the support is in the form of a ceramic or metallic monolith, said step b) comprises the following sub-steps: b1 ') the gamma alumina powder is dispersed in a solution based on nitric acid and water, then the dispersed catalyst precursor is ground so as to obtain a suspension; b2') the support in the form of a ceramic or metallic monolith is coated with said suspension obtained at the end of step bT) by soaking-withdrawal; b3') a step is carried out of blowing the coated ceramic or metallic monolith obtained at the end of step b2'); b4') optionally, the coated ceramic or metallic monolith obtained at the end of step b3') is dried at a temperature between 80°C and 220°C; b5') the coated ceramic or metallic monolith obtained at the end of step b3'), optionally at the end of step b4'), is calcined at a temperature between 250°C and 550°C.
Selon un ou plusieurs modes de réalisation, ledit support se présente sous la forme d’un monolithe métallique choisi parmi les monolithes en acier, inox, nickel, aluminium, fer, cuivre, nickel-chrome, nickel-chrome-aluminium, fer-chrome-aluminium. According to one or more embodiments, said support is in the form of a metal monolith chosen from steel, stainless steel, nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium-aluminum, iron-chromium monoliths. -aluminum.
Selon un ou plusieurs modes de réalisation, ledit support se présente sous la forme d’un monolithe céramique choisi parmi les monolithes en alumine (AI2O3), silice-alumine, carbure de silicium (SiC), phosphore-alumine, magnésie (MgO), oxyde de zinc, oxyde de zirconium (ZrCh), cordiérite (Ah /^AISisOis). According to one or more embodiments, said support is in the form of a ceramic monolith chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO), zinc oxide, zirconium oxide (ZrCh), cordierite (Ah /^AISisOis).
Selon un ou plusieurs modes de réalisation, ledit support comprend un nombre de canaux par unité de longueur (CPSI) entre 300 et 1200. According to one or more embodiments, said support comprises a number of channels per unit of length (CPSI) between 300 and 1200.
Selon un ou plusieurs modes de réalisation, la surface géométrique dudit catalyseur est comprise entre 1500 m2/m3 et 5000 m2/m3. According to one or more embodiments, the geometric surface of said catalyst is between 1500 m 2 /m 3 and 5000 m 2 /m 3 .
Selon un ou plusieurs modes de réalisation, ledit support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique approvisionné à l’étape d) est préalablement calciné sous air à une température comprise entre 300°C et 800°C pendant une durée comprise entre 2 et 8 heures.
Description détaillée According to one or more embodiments, said support in the form of a monolith or a ceramic or metallic foam supplied in step d) is previously calcined in air at a temperature between 300°C and 800° C for a period of between 2 and 8 hours. detailed description
Définitions Definitions
Dans la suite, les groupes d'éléments chimiques sont donnés selon la classification CAS (CRC Handbook of Chemistry and Physics, éditeur CRC press, rédacteur en chef D.R. Lide, 81ème édition, 2000-2001). Par exemple, le groupe VIII (ou VIIIB) selon la classification CAS correspond aux métaux des colonnes 8, 9 et 10 selon la nouvelle classification IIIPAC. In the following, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief DR Lide, 81st edition, 2000-2001). For example, group VIII (or VIIIB) according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IIIPAC classification.
Le volume poreux total et la surface spécifique (SBET) de l’alumine sont mesurés par porosimétrie au mercure selon la norme ASTM D4284-92 avec un angle de mouillage de 140° au moyen d'un appareil modèle Autopore® IV de la marque Microméritics®. The total pore volume and the specific surface area (SBET) of the alumina are measured by mercury porosimetry according to the ASTM D4284-92 standard with a wetting angle of 140° using an Autopore® IV model device from the Microméritics brand. ®.
Les supports monolithes ou mousses (céramiques ou métalliques) sont généralement caractérisés par la densité et la taille des canaux, plus spécifiquement par le nombre de canaux par unité de longueur que l’on appelle CPSI («Channels per square inch » selon la terminologie anglo-saxonne). Comme son abréviation l’indique, il correspond au nombre de canaux interceptés par une section de 1 x 1 pouce (« inch » selon la terminologie anglo- saxonne) soit 2,54 x 2,54 cm. Dans la présente demande, les supports monolithes ou mousses (céramiques ou métalliques) sont caractérisés par le nombre de canaux par unité de longueur (CPSI). Il est à noter que la valeur du CPSI d’un catalyseur comprenant un tel support en monolithe ou en mousse ne change pas, quelle que soit l’épaisseur de la couche de la phase active du catalyseur. Monolithic or foam supports (ceramic or metallic) are generally characterized by the density and size of the channels, more specifically by the number of channels per unit of length which is called CPSI (“Channels per square inch” according to English terminology). -Saxon). As its abbreviation indicates, it corresponds to the number of channels intercepted by a section of 1 x 1 inch (“inch” according to Anglo-Saxon terminology) or 2.54 x 2.54 cm. In the present application, the monolithic or foam supports (ceramic or metallic) are characterized by the number of channels per unit length (CPSI). It should be noted that the CPSI value of a catalyst comprising such a monolith or foam support does not change, whatever the thickness of the layer of the active phase of the catalyst.
La porosité de la mousse ou du monolithe peut être calculée par la formule suivante :
avec : s : porosité ou taux de vide de la mousse ou du monolithe ; pm : densité de la mousse ou du monolithe ; The porosity of the foam or monolith can be calculated by the following formula: with: s: porosity or void ratio of the foam or monolith; p m : density of the foam or monolith;
Pmat : densité du matériau de la mousse ou du monolithe. Pmat: density of the foam or monolith material.
La teneur en métal du groupe VIII est mesurée par fluorescence X. The group VIII metal content is measured by X-ray fluorescence.
Procédé de préparation Preparation process
Le procédé de préparation d’un catalyseur d’hydrogénation sélective comprenant une phase active à base d’au moins un métal du groupe VIII, déposée sur une alumine alpha, et un
support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique, lequel procédé comprend au moins les étapes suivantes : a) on approvisionne une poudre d’alumine gamma comprenant une surface spécifique comprise entre 100 et 500 m2/g ; b) on met en contact par enduction ladite poudre d’alumine gamma de l’étape a) avec un support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique pour obtenir un précurseur de catalyseur comprenant une alumine gamma ; c) on calcine le précurseur de catalyseur obtenu à l’issue de l’étape b) à une température comprise entre 900°C et 1300°C pour obtenir un précurseur de catalyseur calciné comprenant une alumine alpha ; d) on met en contact le précurseur de catalyseur calciné obtenu à l’issue de l’étape c) avec une solution comprenant au moins un précurseur de la phase active comprenant au moins un métal du groupe VIII pour obtenir un matériau ; e) on sèche le matériau obtenu à l’issue de l’étape d) à une température inférieure à 250°C puis on calcine le matériau séché à une température comprise entre 250°C et 550°C ; f) optionnellement, on réalise une étape de réduction du catalyseur obtenu à l’issue de l’étape e) en présence d'un gaz réducteur à une température comprise entre 80°C et 450°C. The process for preparing a selective hydrogenation catalyst comprising an active phase based on at least one group VIII metal, deposited on an alpha alumina, and an support in the form of a monolith or a ceramic or metallic foam, which process comprises at least the following steps: a) a gamma alumina powder is supplied comprising a specific surface area of between 100 and 500 m 2 / g; b) said gamma alumina powder from step a) is brought into contact by coating with a support in the form of a monolith or a ceramic or metallic foam to obtain a catalyst precursor comprising a gamma alumina ; c) the catalyst precursor obtained at the end of step b) is calcined at a temperature between 900°C and 1300°C to obtain a calcined catalyst precursor comprising an alpha alumina; d) the calcined catalyst precursor obtained at the end of step c) is brought into contact with a solution comprising at least one precursor of the active phase comprising at least one metal from group VIII to obtain a material; e) the material obtained at the end of step d) is dried at a temperature below 250°C then the dried material is calcined at a temperature between 250°C and 550°C; f) optionally, a step of reduction of the catalyst obtained at the end of step e) is carried out in the presence of a reducing gas at a temperature between 80°C and 450°C.
Les étapes dudit procédé de préparation sont décrites en détail ci-après. The steps of said preparation process are described in detail below.
Etape a) Step a)
Selon l’étape a), on approvisionne une alumine gamma comprenant une surface spécifique comprise entre 100 et 500 m2/g, de préférence comprise entre 120 et 450 m2/g, et encore plus préférentiellement entre 150 et 300 m2/g, ladite alumine gamma se présentant sous la forme d’une poudre. According to step a), a gamma alumina is supplied comprising a specific surface area of between 100 and 500 m 2 /g, preferably between 120 and 450 m 2 /g, and even more preferably between 150 and 300 m 2 /g , said gamma alumina being in the form of a powder.
L’alumine, peut comprendre des impuretés telles que les oxydes de métaux des groupes HA, 111 B, IVB, Il B, Il IA, I A selon la classification CAS, de préférence la silice, le dioxyde de titane, le dioxyde de zirconium, l'oxyde de zinc, l'oxyde de magnésium et l'oxyde de calcium, ou encore des métaux alcalins, de préférence le lithium, le sodium ou le potassium, et/ou les alcalino-terreux, de préférence le magnésium, le calcium, le strontium ou le baryum ou encore du soufre. Alumina may include impurities such as metal oxides of groups HA, 111 B, IVB, II B, II IA, I A according to the CAS classification, preferably silica, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide and calcium oxide, or alkali metals, preferably lithium, sodium or potassium, and/or alkaline earth metals, preferably magnesium, calcium , strontium or barium or even sulfur.
Selon l’étape a), l’alumine se présente sous la forme d’une poudre comprenant un diamètre médian inférieur ou égal à 250 pm, de préférence comprise entre 10 et 250 pm, et encore plus préférentiellement entre 50 et 150 pm. Le terme "diamètre médian" désigne ici le diamètre d'une sphère équivalente tel que 50 % des particules, en volume, ont un diamètre supérieur
et 50 % un diamètre inférieur. L’alumine peut être mise en forme de poudre par toute technique bien connue de l’Homme du métier, par exemple par broyage et tamisage. According to step a), the alumina is in the form of a powder comprising a median diameter less than or equal to 250 pm, preferably between 10 and 250 pm, and even more preferably between 50 and 150 pm. The term "median diameter" here designates the diameter of an equivalent sphere such that 50% of the particles, by volume, have a greater diameter and 50% a smaller diameter. The alumina can be formed into powder by any technique well known to those skilled in the art, for example by grinding and sieving.
Avantageusement, le volume total poreux de l’alumine est compris entre 0,1 et 1 ,5 cm3/g, de préférence compris entre 0,35 et 1 ,2 cm3/g, et encore plus préférentiellement compris entre 0,4 et 1 ,0 cm3/g, et encore plus préférentiellement entre 0,45 et 0,9 cm3/g. Advantageously, the total porous volume of the alumina is between 0.1 and 1.5 cm 3 /g, preferably between 0.35 and 1.2 cm 3 /g, and even more preferably between 0.4 and 1.0 cm 3 /g, and even more preferably between 0.45 and 0.9 cm 3 /g.
Etape b) Step b)
Selon l’étape b), on met en contact la poudre d’alumine gamma approvisionné à l’étape a) avec un support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique. According to step b), the gamma alumina powder supplied in step a) is brought into contact with a support in the form of a monolith or a ceramic or metallic foam.
Avantageusement, le support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique utilisé à l’étape b) est préalablement calciné sous air à une température comprise entre 300°C et 800 °C pendant une durée comprise avantageusement entre 2 et 8 heures afin de favoriser l’accroche de la poudre d’alumine sur ledit support. Advantageously, the support in the form of a monolith or a ceramic or metallic foam used in step b) is previously calcined in air at a temperature between 300°C and 800°C for a period advantageously included between 2 and 8 hours in order to promote adhesion of the alumina powder to said support.
La mise en contact de la poudre d’alumine gamma avec le support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique est réalisée par enduction (« washcoat » selon la terminologie anglo-saxonne). Bringing the gamma alumina powder into contact with the support in the form of a monolith or a ceramic or metallic foam is carried out by coating (“washcoat” according to Anglo-Saxon terminology).
Dans un mode de réalisation selon l’invention, on réalise une étape b) de mise en contact de la poudre d’alumine gamma de l’étape a) avec un support se présentant sous la forme d’une mousse céramique ou métallique. Dans ce mode de réalisation particulier, l’étape b) comprend avantageusement les sous-étapes suivantes : b1) on disperse la poudre d’alumine gamma dans une solution à base d’acide nitrique et d’eau, puis on broie le précurseur de catalyseur dispersé de manière à obtenir une suspension (« slurry » selon la terminologie anglo-saxonne) avantageusement au moyen d’un broyeur à billes, pendant une durée de préférence comprise entre 15 et 30 heures, plus préférentiellement entre 18 et 28 heures, de manière à obtenir une suspension comprenant avantageusement des particules de précurseur de catalyseur calciné comprenant une taille moyenne inférieure à 1 pm ; b2) on enduit la mousse céramique ou métallique de ladite suspension obtenue à l’issue de l’étape b1) par trempage-retrait ; b3) on réalise : In one embodiment according to the invention, a step b) is carried out of bringing the gamma alumina powder from step a) into contact with a support in the form of a ceramic or metallic foam. In this particular embodiment, step b) advantageously comprises the following sub-steps: b1) the gamma alumina powder is dispersed in a solution based on nitric acid and water, then the precursor of catalyst dispersed so as to obtain a suspension (“slurry” according to Anglo-Saxon terminology) advantageously by means of a ball mill, for a period of preferably between 15 and 30 hours, more preferably between 18 and 28 hours, of so as to obtain a suspension advantageously comprising particles of calcined catalyst precursor having an average size of less than 1 μm; b2) the ceramic or metallic foam is coated with said suspension obtained at the end of step b1) by soaking-withdrawal; b3) we carry out:
- soit une étape de centrifugation (« spin-coating » selon la terminologie anglo-saxonne) de la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b2) afin de retirer l’excès
de slurry, de préférence à une vitesse comprise entre 4000 et 8500 tours/minute, de préférence entre 4500 et 8000 tours/minute ; - either a centrifugation step (“spin-coating” according to Anglo-Saxon terminology) of the coated ceramic or metallic foam obtained at the end of step b2) in order to remove the excess slurry, preferably at a speed between 4000 and 8500 rpm, preferably between 4500 and 8000 rpm;
- soit une étape de soufflage de la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b2) avantageusement au moyen d’un gaz inerte ou sous air. La technique de soufflage est bien connue de l’Homme du métier. - either a step of blowing the coated ceramic or metallic foam obtained at the end of step b2), advantageously using an inert gas or under air. The blowing technique is well known to those skilled in the art.
De préférence, on réalise une étape de centrifugation de la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b2) afin de retirer l’excès de slurry, de préférence à une vitesse comprise entre 4000 et 8500 tours/minute, de préférence entre 4500 et 8000 tours/minute ; b4) optionnellement, on sèche la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b3) à une température comprise entre 80°C et 220°C, de préférence entre 90°C et 150°C, pendant une durée comprise avantageusement entre 6 et 30 heures, de préférence entre 8 et 24 heures ; b5) on calcine la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b3), optionnellement à l’issue de l’étape b4), à une température comprise entre 250°C et 550°C, de préférence entre 320°C et 450°C, pendant une durée comprise avantageusement entre 1 et 6 heures, de préférence entre 2 et 4 heures. Preferably, a centrifugation step is carried out on the coated ceramic or metallic foam obtained at the end of step b2) in order to remove the excess slurry, preferably at a speed of between 4000 and 8500 rpm, preferably between 4500 and 8000 rpm; b4) optionally, the coated ceramic or metallic foam obtained at the end of step b3) is dried at a temperature between 80°C and 220°C, preferably between 90°C and 150°C, for a period advantageously between 6 and 30 hours, preferably between 8 and 24 hours; b5) the coated ceramic or metallic foam obtained at the end of step b3), optionally at the end of step b4), is calcined at a temperature between 250°C and 550°C, preferably between 320°C and 450°C, for a period advantageously between 1 and 6 hours, preferably between 2 and 4 hours.
Lorsque le support du catalyseur se présente sous la forme d’une mousse céramique, ladite mousse est de préférence choisie parmi les mousses en alumine (AI2O3), silice-alumine, carbure de silicium (SiC), phosphore-alumine, magnésie (MgO), oxyde de zinc, oxyde de zirconium (ZrCh), cordiérite (AL /^AISisOis). De préférence, ladite mousse céramique est en alumine (AI2O3), silice-alumine, phosphore-alumine, ou carbure de silicium (SiC). When the catalyst support is in the form of a ceramic foam, said foam is preferably chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO) foams. , zinc oxide, zirconium oxide (ZrCh), cordierite (AL /^AISisOis). Preferably, said ceramic foam is made of alumina (AI2O3), silica-alumina, phosphorus-alumina, or silicon carbide (SiC).
Lorsque le support du catalyseur se présente sous la forme d’une mousse métallique, ladite mousse est de préférence choisie parmi les mousses en nickel, aluminium, fer, cuivre, nickel- chrome, nickel-chrome-aluminium, nickel-fer-chrome-aluminium, fer-chrome-aluminium, nickel-aluminium, inox (316L, 310SS). De préférence, ladite mousse métallique est choisie parmi les mousses en aluminium, nickel, nickel-chrome, nickel-chrome-aluminium. Ces mousses peuvent inclure des additifs tels que le molybdène, le manganèse ou encore le phosphore. When the catalyst support is in the form of a metal foam, said foam is preferably chosen from nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium-aluminum, nickel-iron-chromium-foams. aluminum, iron-chrome-aluminum, nickel-aluminum, stainless steel (316L, 310SS). Preferably, said metal foam is chosen from aluminum, nickel, nickel-chrome, nickel-chrome-aluminum foams. These foams can include additives such as molybdenum, manganese or even phosphorus.
Dans un autre mode de réalisation selon l’invention, on réalise une étape b) de mise en contact de la poudre d’alumine gamma de l’étape a) avec un support se présentant sous la forme d’un monolithe céramique ou métallique. Dans ce mode de réalisation particulier, l’étape b) comprend avantageusement les sous-étapes suivantes :
b1 ’) on disperse la poudre d’alumine gamma dans une solution à base d’acide nitrique et d’eau, puis on broie le précurseur de catalyseur dispersé de manière à obtenir une suspension (« slurry » selon la terminologie anglo-saxonne) avantageusement au moyen d’un broyeur à billes, pendant une durée de préférence comprise entre 15 et 30 heures, plus préférentiellement entre 18 et 28 heures, de manière à obtenir une suspension comprenant avantageusement des particules de précurseur de catalyseur calciné comprenant une taille moyenne inférieure à 1 pm ; b2’) on enduit le monolithe céramique ou métallique de ladite suspension obtenue à l’issue de l’étape b1’) par trempage-retrait ; b3’) on réalise une étape de soufflage du monolithe céramique ou métallique enduit obtenu à l’issue de l’étape b2’) avantageusement au moyen d’un gaz inerte. La technique de soufflage est bien connue de l’Homme du métier ; b4’) optionnellement, on sèche le monolithe céramique ou métallique enduite obtenue à l’issue de l’étape b3’) à une température comprise entre 80°C et 220°C, de préférence entre 90°C et 150°C, pendant une durée comprise avantageusement entre 6 et 30 heures, de préférence entre 8 et 24 heures ; b5’) on calcine la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b3’), optionnellement à l’issue de l’étape b4’), à une température comprise entre 250°C et 550°C, de préférence entre 320°C et 450°C, pendant une durée comprise avantageusement entre 1 et 6 heures, de préférence entre 2 et 4 heures. In another embodiment according to the invention, a step b) of bringing the gamma alumina powder from step a) into contact with a support in the form of a ceramic or metallic monolith is carried out. In this particular embodiment, step b) advantageously comprises the following substeps: b1 ') the gamma alumina powder is dispersed in a solution based on nitric acid and water, then the dispersed catalyst precursor is ground so as to obtain a suspension (“slurry” according to Anglo-Saxon terminology) advantageously by means of a ball mill, for a period preferably between 15 and 30 hours, more preferably between 18 and 28 hours, so as to obtain a suspension advantageously comprising particles of calcined catalyst precursor comprising a lower average size at 1 p.m.; b2') the ceramic or metallic monolith is coated with said suspension obtained at the end of step b1') by soaking-shrinkage; b3') a step of blowing the coated ceramic or metallic monolith obtained at the end of step b2') is carried out advantageously using an inert gas. The blowing technique is well known to those skilled in the art; b4') optionally, the coated ceramic or metallic monolith obtained at the end of step b3') is dried at a temperature between 80°C and 220°C, preferably between 90°C and 150°C, for a duration advantageously between 6 and 30 hours, preferably between 8 and 24 hours; b5') the coated ceramic or metallic foam obtained at the end of step b3'), optionally at the end of step b4'), is calcined at a temperature between 250°C and 550°C, preferably between 320°C and 450°C, for a period advantageously between 1 and 6 hours, preferably between 2 and 4 hours.
Lorsque le support du catalyseur se présente sous la forme d’un monolithe métallique, ledit monolithe est de préférence choisi parmi les monolithes en acier, inox (316L, 310SS), nickel, aluminium, fer, cuivre, nickel-chrome, nickel-chrome-aluminium, fer-chrome-aluminium. When the catalyst support is in the form of a metal monolith, said monolith is preferably chosen from monoliths made of steel, stainless steel (316L, 310SS), nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium -aluminum, iron-chrome-aluminum.
Lorsque le support du catalyseur se présente sous la forme d’un monolithe céramique, ledit monolithe est de préférence choisi parmi les monolithes en alumine (AI2O3), silice-alumine, carbure de silicium (SiC), phosphore-alumine, magnésie (MgO), oxyde de zinc, oxyde de zirconium (ZrCh), cordiérite (Ah /^AISisOis). De préférence, ledit monolithe céramique est en alumine (AI2O3), silice-alumine, phosphore-alumine, ou carbure de silicium (SiC). When the catalyst support is in the form of a ceramic monolith, said monolith is preferably chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO) monoliths. , zinc oxide, zirconium oxide (ZrCh), cordierite (Ah /^AISisOis). Preferably, said ceramic monolith is made of alumina (AI2O3), silica-alumina, phosphorus-alumina, or silicon carbide (SiC).
A l’issue de l’étape b), le support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique est enduit d’une couche d’alumine gamma. L’épaisseur de la couche dépend du nombre d’étapes d’enduction réalisée. L’étape b) peut être répétée plusieurs fois selon l’épaisseur de la couche d’alumine gamma voulue. Avantageusement, cette voie de préparation permet d’obtenir une couche d’alumine gamma sur les parois du support comprise
entre 10 pm et 150 pm, préférentiellement entre 20 pm et 100 pm et encore plus préférentiellement entre 30 pm et 90 pm. At the end of step b), the support in the form of a monolith or a ceramic or metallic foam is coated with a layer of gamma alumina. The thickness of the layer depends on the number of coating steps carried out. Step b) can be repeated several times depending on the thickness of the desired gamma alumina layer. Advantageously, this preparation route makes it possible to obtain a layer of gamma alumina on the walls of the support comprised between 10 pm and 150 pm, preferably between 20 pm and 100 pm and even more preferably between 30 pm and 90 pm.
Etape c) Step c)
Selon l’étape c), le précurseur de catalyseur comprenant une alumine gamma obtenu à l’issue de l’étape b) est calciné, de préférence sous air de combustion, et plus préférentiellement un air de combustion du méthane, comprenant entre 40 et 80 grammes d'eau par kg d'air, un taux d'oxygène compris entre 5% et 15% volume et un taux de CO2 compris entre 4% et 10% volume. La température de calcination est comprise entre 900°C et 1300°C, de préférence entre 1000°C et 1250°C, et encore plus préférentiellement entre 1000°C et 1150°C. La calcination du support est réalisée à haute température afin de transformer l’alumine gamma en une alumine alpha. According to step c), the catalyst precursor comprising a gamma alumina obtained at the end of step b) is calcined, preferably under combustion air, and more preferably methane combustion air, comprising between 40 and 80 grams of water per kg of air, an oxygen level between 5% and 15% volume and a CO2 level between 4% and 10% volume. The calcination temperature is between 900°C and 1300°C, preferably between 1000°C and 1250°C, and even more preferably between 1000°C and 1150°C. The calcination of the support is carried out at high temperature in order to transform the gamma alumina into an alpha alumina.
La durée de calcination est généralement comprise entre 0,25 heure et 10 heures. Des durées plus longues ne sont pas exclues, mais n’apportent pas nécessairement d’amélioration. The calcination time is generally between 0.25 hours and 10 hours. Longer durations are not excluded, but do not necessarily bring improvement.
Etape d) Step d)
Selon l’étape d), on met en contact le précurseur de catalyseur calciné comprenant une alumine alpha obtenu à l’issue de l’étape c) avec une solution comprenant au moins un précurseur de la phase active comprenant au moins un métal du groupe VIII pour obtenir un précurseur de catalyseur. Le dépôt du précurseur de la phase active comprenant au moins un métal du groupe VIII peut être réalisé par toute méthode bien connue de l'Homme du métier. En particulier, ladite étape d) peut être réalisée par imprégnation, à sec ou en excès, ou encore par dépôt - précipitation, selon des méthodes bien connues de l'Homme du métier. According to step d), the calcined catalyst precursor comprising an alpha alumina obtained at the end of step c) is brought into contact with a solution comprising at least one precursor of the active phase comprising at least one metal from the group VIII to obtain a catalyst precursor. The deposition of the precursor of the active phase comprising at least one group VIII metal can be carried out by any method well known to those skilled in the art. In particular, said step d) can be carried out by impregnation, dry or in excess, or by deposition - precipitation, according to methods well known to those skilled in the art.
Ladite étape d) est préférentiellement réalisée par imprégnation consistant par exemple en la mise en contact du précurseur de catalyseur calciné obtenu à l’issue de l’étape c) avec au moins une solution, aqueuse ou organique (par exemple le méthanol ou l'éthanol ou le phénol ou l’acétone ou le toluène ou le diméthylsulfoxyde (DMSO)) ou bien constituée d'un mélange d'eau et d'au moins un solvant organique, contenant au moins un précurseur de la phase active comprenant au moins un métal du groupe VIII au moins partiellement à l'état dissous, ou encore en la mise en contact du précurseur de catalyseur calciné obtenu à l’issue de l’étape c) avec au moins une solution colloïdale d'au moins un précurseur de la phase active comprenant au moins un métal du groupe VIII, sous forme oxydée ou sous forme réduite. De préférence, la solution est aqueuse. Le pH de cette solution pourra être modifié par l'ajout éventuel d'un acide ou d’une base. Said step d) is preferably carried out by impregnation consisting for example of bringing the calcined catalyst precursor obtained at the end of step c) into contact with at least one solution, aqueous or organic (for example methanol or ethanol or phenol or acetone or toluene or dimethyl sulfoxide (DMSO)) or consisting of a mixture of water and at least one organic solvent, containing at least one precursor of the active phase comprising at least one group VIII metal at least partially in the dissolved state, or else by bringing the calcined catalyst precursor obtained at the end of step c) into contact with at least one colloidal solution of at least one precursor of the active phase comprising at least one metal from group VIII, in oxidized form or in reduced form. Preferably, the solution is aqueous. The pH of this solution can be modified by the possible addition of an acid or a base.
De manière préférée, ladite étape d) est réalisée par imprégnation à sec, laquelle consiste à mettre en contact le précurseur de catalyseur calciné obtenu à l’issue de l’étape c) avec une
solution, contenant au moins un précurseur de phase active comprenant au moins un métal du groupe VIII, dont le volume de la solution est compris entre 0,3 et 1 ,5 fois le volume poreux du support à imprégner. Preferably, said step d) is carried out by dry impregnation, which consists of bringing the calcined catalyst precursor obtained at the end of step c) into contact with a solution, containing at least one active phase precursor comprising at least one group VIII metal, the volume of the solution of which is between 0.3 and 1.5 times the pore volume of the support to be impregnated.
Le métal du groupe VIII de la phase active est de préférence choisi parmi le nickel, le platine, le palladium. De préférence, le métal du groupe VIII est le palladium ou le platine et plus préférentiellement le palladium. The Group VIII metal of the active phase is preferably chosen from nickel, platinum and palladium. Preferably, the Group VIII metal is palladium or platinum and more preferably palladium.
Lorsque le métal du groupe VIII est le palladium, la concentration en palladium en solution est ajustée selon le volume poreux du support encore disponible de façon à obtenir sur le catalyseur final une teneur en palladium généralement comprise entre 0,005 et 1 % poids dudit élément par rapport au poids total du catalyseur, de préférence compris entre 0,01 et 0,7% poids, et encore plus préférentiellement compris entre 0,02 et 0,5% poids, de manière encore plus préférée entre 0,025 et 0,3% poids. When the metal of group VIII is palladium, the concentration of palladium in solution is adjusted according to the pore volume of the support still available so as to obtain on the final catalyst a palladium content generally between 0.005 and 1% by weight of said element relative to to the total weight of the catalyst, preferably between 0.01 and 0.7% by weight, and even more preferably between 0.02 and 0.5% by weight, even more preferably between 0.025 and 0.3% by weight.
Lorsque le précurseur de la phase active à base d’au moins un métal du groupe VIII, de préférence le palladium, est introduit en solution aqueuse, on utilise avantageusement un précurseur sous forme de nitrate, de carbonate, de chlorure, de sulfate, d’hydroxyde, d’hydroxycarbonate, de formiate, d'acétate, d’oxalate, de complexes formés avec les acétylacétonates, ou encore de complexes tétrammine ou hexammine, ou de tout autre dérivé inorganique soluble en solution aqueuse, laquelle est mise en contact avec ledit support. De préférence, le précurseur est sélectionné parmi le chloropalladate de sodium et le nitrate de palladium. When the precursor of the active phase based on at least one metal from group VIII, preferably palladium, is introduced into an aqueous solution, a precursor is advantageously used in the form of nitrate, carbonate, chloride, sulfate, etc. hydroxide, hydroxycarbonate, formate, acetate, oxalate, complexes formed with acetylacetonates, or even tetrammine or hexammine complexes, or any other inorganic derivative soluble in aqueous solution, which is brought into contact with said support. Preferably, the precursor is selected from sodium chloropalladate and palladium nitrate.
Lorsque le précurseur de la phase active à base d’au moins un métal du groupe VIII, de manière préférée le palladium, est introduit sous forme d’une suspension colloïdale, on prépare une suspension colloïdale d'oxyde de métal du groupe VIII ou d'hydroxyde de métal du groupe VIII, de manière préférée d'oxyde de palladium ou d'hydroxyde de palladium, en phase aqueuse par mélange d’une solution aqueuse (I) comprenant au moins un hydroxyde sélectionné dans le groupe constitué par les hydroxydes d’alcalins et les hydroxydes d’alcalino-terreux et d’une solution aqueuse (II) comprenant au moins un précurseur de phase active de palladium. De préférence, ladite suspension colloïdale est généralement obtenue par hydrolyse du cation métallique, de préférence palladium, en milieu aqueux, ce qui conduit à la formation de particules d'oxyde ou d'hydroxyde métallique, de préférence de palladium, en suspension. La solution aqueuse d'hydroxyde d'alcalins ou d'hydroxyde alcalino-terreux est généralement sélectionnée dans le groupe constitué par les solutions aqueuses d’hydroxyde de sodium, les solutions aqueuses d'hydroxyde de magnésium. De manière préférée, de préférence la solution aqueuse est une solution aqueuse d’hydroxyde de sodium.
A l’issue de l’étape d), le précurseur de catalyseur obtenu est généralement maturé à l'état humide pendant 5 minutes à 12 heures, de manière préférée pendant 5 minutes à 6 heures, de préférence à une température comprise entre 15°C et 45°C. Des durées plus longues ne sont pas exclues, mais n’apportent pas nécessairement d’amélioration. When the precursor of the active phase based on at least one metal from Group VIII, preferably palladium, is introduced in the form of a colloidal suspension, a colloidal suspension of metal oxide from Group VIII or d is prepared. Group VIII metal hydroxide, preferably palladium oxide or palladium hydroxide, in aqueous phase by mixing an aqueous solution (I) comprising at least one hydroxide selected from the group consisting of hydroxides of group VIII alkalis and alkaline earth hydroxides and an aqueous solution (II) comprising at least one active phase precursor of palladium. Preferably, said colloidal suspension is generally obtained by hydrolysis of the metal cation, preferably palladium, in an aqueous medium, which leads to the formation of particles of metal oxide or hydroxide, preferably palladium, in suspension. The aqueous solution of alkali hydroxide or alkaline earth hydroxide is generally selected from the group consisting of aqueous solutions of sodium hydroxide, aqueous solutions of magnesium hydroxide. Preferably, preferably the aqueous solution is an aqueous solution of sodium hydroxide. At the end of step d), the catalyst precursor obtained is generally matured in the wet state for 5 minutes to 12 hours, preferably for 5 minutes to 6 hours, preferably at a temperature between 15° C and 45°C. Longer durations are not excluded, but do not necessarily bring improvement.
Etape e) Step e)
Le matériau obtenu à l’issue de l’étape d) est séché à une température inférieure à 250°C, de manière plus préférée entre 30°C et 220°C, de manière plus préférée entre 90°C et 180°C. La durée du séchage est avantageusement comprise entre 0,5 heure et 20 heures. Des durées plus longues ne sont pas exclues, mais n’apportent pas nécessairement d’amélioration.The material obtained at the end of step d) is dried at a temperature below 250°C, more preferably between 30°C and 220°C, more preferably between 90°C and 180°C. The drying time is advantageously between 0.5 hour and 20 hours. Longer durations are not excluded, but do not necessarily bring improvement.
Le séchage est généralement effectué sous air de combustion d'un hydrocarbure, de préférence du méthane, ou sous air chauffé comprenant entre 0 et 80 grammes d'eau par kilogramme d'air de combustion, un taux d'oxygène compris entre 5% et 25% volume et un taux de dioxyde de carbone compris entre 0% et 10% volume. Drying is generally carried out under combustion air of a hydrocarbon, preferably methane, or under heated air comprising between 0 and 80 grams of water per kilogram of combustion air, an oxygen level of between 5% and 25% volume and a carbon dioxide level of between 0% and 10% volume.
Après séchage, le matériau séché est calciné, de préférence sous air de combustion, et plus préférentiellement un air de combustion du méthane, comprenant entre 40 et 80 grammes d'eau par kg d'air, un taux d'oxygène compris entre 5% et 15% volume et un taux de CO2 compris entre 4% et 10% volume. La température de calcination est comprise entre 250°C et 550°C, de préférence entre 300°C et 480°C, et encore plus préférentiellement entre 320°C et 450°C. La durée de calcination est généralement comprise entre 0,25 heure et 10 heures. Des durées plus longues ne sont pas exclues, mais n’apportent pas nécessairement d’amélioration. After drying, the dried material is calcined, preferably under combustion air, and more preferably methane combustion air, comprising between 40 and 80 grams of water per kg of air, an oxygen level of between 5% and 15% volume and a CO2 rate of between 4% and 10% volume. The calcination temperature is between 250°C and 550°C, preferably between 300°C and 480°C, and even more preferably between 320°C and 450°C. The calcination time is generally between 0.25 hours and 10 hours. Longer durations are not excluded, but do not necessarily bring improvement.
Etape f) (étape optionnelle) Step f) (optional step)
Le catalyseur obtenu à l’issue de l’étape e) subit généralement une étape de réduction. Cette étape est de préférence réalisée en présence d'un gaz réducteur, soit in-situ, c'est-à-dire dans le réacteur où est réalisée la transformation catalytique, soit ex-situ. De manière préférée, cette étape est effectuée à une température comprise entre 80°C et 450°C, de manière encore plus préférée entre 100°C et 400°C. The catalyst obtained at the end of step e) generally undergoes a reduction step. This step is preferably carried out in the presence of a reducing gas, either in-situ, that is to say in the reactor where the catalytic transformation is carried out, or ex-situ. Preferably, this step is carried out at a temperature between 80°C and 450°C, even more preferably between 100°C and 400°C.
La réduction est réalisée en présence d'un gaz réducteur comprenant de préférence entre 25 vol% et 100 vol% d'hydrogène, par exemple 100% volume d'hydrogène. L'hydrogène est éventuellement complété par un gaz inerte pour la réduction, de préférence de l'argon, de l'azote ou du méthane. The reduction is carried out in the presence of a reducing gas preferably comprising between 25 vol% and 100 vol% of hydrogen, for example 100 vol% of hydrogen. The hydrogen is optionally supplemented by an inert gas for reduction, preferably argon, nitrogen or methane.
La réduction comprend généralement une phase de montée en température puis un palier.The reduction generally includes a temperature rise phase then a plateau.
La durée du palier de réduction est généralement comprise entre 1 heure et 40 heures, de préférence entre 2 heures et 20 heures.
La Vitesse Volumétrique Horaire (V.V.H) est généralement comprise entre 150 et 3000, de préférence entre 300 et 1500 litres de gaz réducteur par heure et par litre de catalyseur. The duration of the reduction stage is generally between 1 hour and 40 hours, preferably between 2 hours and 20 hours. The Volumetric Hourly Speed (VVH) is generally between 150 and 3000, preferably between 300 and 1500 liters of reducing gas per hour and per liter of catalyst.
Catalyseur Catalyst
Le catalyseur obtenu par le procédé de préparation selon l’invention comprend une phase active à base d’au moins un métal du groupe VIII et un support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique enduit d’une alumine alpha. The catalyst obtained by the preparation process according to the invention comprises an active phase based on at least one metal from group VIII and a support in the form of a monolith or a ceramic or metallic foam coated with an alpha alumina.
Le métal du groupe VIII de la phase active est de préférence choisi parmi le nickel, le platine, le palladium. De préférence, le métal du groupe VIII est le palladium ou le platine, et plus préférentiellement le platine. The Group VIII metal of the active phase is preferably chosen from nickel, platinum and palladium. Preferably, the Group VIII metal is palladium or platinum, and more preferably platinum.
Lorsque le métal du groupe VIII est le palladium, la teneur en palladium est généralement comprise entre 0,005 et 1% poids dudit élément par rapport au poids total du catalyseur, de préférence compris entre 0,01 et 0,7% poids, et encore plus préférentiellement compris entre 0,02 et 0,5% poids, de manière encore plus préférée entre 0,025 et 0,3% poids. When the Group VIII metal is palladium, the palladium content is generally between 0.005 and 1% by weight of said element relative to the total weight of the catalyst, preferably between 0.01 and 0.7% by weight, and even more preferably between 0.02 and 0.5% by weight, even more preferably between 0.025 and 0.3% by weight.
Le catalyseur peut comprendre en outre en tant que phase active un élément du groupe IB, de préférence choisi parmi l’argent et le cuivre. De manière préférée, l’élément du groupe IB est l’argent. La teneur en élément du groupe IB est de préférence comprise entre 0,01 et 0,3% poids par rapport au poids total du catalyseur, plus préférentiellement comprise entre 0,015 et 0,2% poids. The catalyst may further comprise, as active phase, a group IB element, preferably chosen from silver and copper. Preferably, the element of group IB is money. The group IB element content is preferably between 0.01 and 0.3% by weight relative to the total weight of the catalyst, more preferably between 0.015 and 0.2% by weight.
Support Support
Le support se présente sous la forme d’un monolithe ou d’une mousse céramique ou métallique. i) Monolithe céramique ou métallique The support comes in the form of a monolith or ceramic or metallic foam. i) Ceramic or metallic monolith
Lorsque le support se présente sous la forme d’un monolithe céramique ou métallique, ledit support comprend un nombre de canaux par unité de longueur (CPSI) entre 300 et 1200.When the support is in the form of a ceramic or metallic monolith, said support comprises a number of channels per unit length (CPSI) between 300 and 1200.
De préférence, le nombre de canaux par unité de longueur (CPSI) dudit support est compris entre 300 et 1200, de préférence entre 350 et 1000, plus préférentiellement entre 400 et 700, et encore plus préférentiellement entre 450 et 750. Preferably, the number of channels per unit length (CPSI) of said support is between 300 and 1200, preferably between 350 and 1000, more preferably between 400 and 700, and even more preferably between 450 and 750.
De préférence, la surface géométrique dudit catalyseur est comprise entre 1500 m2/m3et 5000 m2/m3, de préférence entre 1500 m2/m3 et 4000 m2/m3, et encore plus préférentiellement entre 2000 m2/m3 et 4000 m2/m3. Preferably, the geometric surface of said catalyst is between 1500 m 2 /m 3 and 5000 m 2 /m 3 , preferably between 1500 m 2 /m 3 and 4000 m 2 /m 3 , and even more preferably between 2000 m 2 /m 3 and 4000 m 2 /m 3 .
De préférence, l’épaisseur de la paroi du catalyseur est comprise entre 0,08 mm et 0,5 mm, plus préférentiellement entre 0,1 mm et 0,4 mm. Preferably, the thickness of the catalyst wall is between 0.08 mm and 0.5 mm, more preferably between 0.1 mm and 0.4 mm.
De préférence, le taux de porosité dudit catalyseur est compris entre 15% et 90%, de préférence entre 20% et 90%, et plus préférentiellement compris entre 20% et 70%.
De préférence, la phase active se présente sous la forme d’une couche sur les parois dudit support, l’épaisseur de ladite couche de phase active étant compris entre 30 pm et 150 pm, de préférence entre 60 pm et 100 pm, et encore plus préférentiellement entre 60 pm et 90 pm. Lorsque le support du catalyseur se présente sous la forme d’un monolithe métallique, ledit monolithe est de préférence choisi parmi les monolithes en acier, inox (316L, 310SS), nickel, aluminium, fer, cuivre, nickel-chrome, nickel-chrome-aluminium, fer-chrome-aluminium. Preferably, the porosity rate of said catalyst is between 15% and 90%, preferably between 20% and 90%, and more preferably between 20% and 70%. Preferably, the active phase is in the form of a layer on the walls of said support, the thickness of said layer of active phase being between 30 pm and 150 pm, preferably between 60 pm and 100 pm, and again more preferably between 60 pm and 90 pm. When the catalyst support is in the form of a metal monolith, said monolith is preferably chosen from monoliths made of steel, stainless steel (316L, 310SS), nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium -aluminum, iron-chrome-aluminum.
Lorsque le support du catalyseur se présente sous la forme d’un monolithe céramique, ledit monolithe est de préférence choisi parmi les monolithes en alumine (AI2O3), silice-alumine, carbure de silicium (SiC), phosphore-alumine, magnésie (MgO), oxyde de zinc, oxyde de zirconium (ZrCh), cordiérite (Ah /^AISisOis). De préférence, ledit monolithe céramique est en alumine (AI2O3), silice-alumine, phosphore-alumine, ou carbure de silicium (SiC). ii) Mousse métallique ou céramique When the catalyst support is in the form of a ceramic monolith, said monolith is preferably chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO) monoliths. , zinc oxide, zirconium oxide (ZrCh), cordierite (Ah /^AISisOis). Preferably, said ceramic monolith is made of alumina (AI2O3), silica-alumina, phosphorus-alumina, or silicon carbide (SiC). ii) Metallic or ceramic foam
Lorsque le support se présente sous la forme d’une mousse métallique ou céramique, ledit catalyseur comprend une surface géométrique comprise entre 1000 et 7000 m2/m3 et un diamètre des pores compris entre 0,2 et 1 ,5 mm. When the support is in the form of a metal or ceramic foam, said catalyst comprises a geometric surface area of between 1000 and 7000 m 2 /m 3 and a pore diameter of between 0.2 and 1.5 mm.
De préférence, la surface géométrique dudit catalyseur est comprise entre 2000 et 5000 m2/m3, et encore plus préférentiellement entre 2000 et 4000 m2/m3. Preferably, the geometric surface of said catalyst is between 2000 and 5000 m 2 /m 3 , and even more preferably between 2000 and 4000 m 2 /m 3 .
De préférence, le diamètre des pores dudit catalyseur est compris entre 0,3 et 1 ,5 mm, et encore plus préférentiellement entre 0,5 et 1 ,5 mm. Preferably, the diameter of the pores of said catalyst is between 0.3 and 1.5 mm, and even more preferably between 0.5 and 1.5 mm.
De préférence, le taux de porosité dudit catalyseur est compris entre 75 et 90% lorsque le support est une mousse céramique. Preferably, the porosity rate of said catalyst is between 75 and 90% when the support is a ceramic foam.
De préférence, le taux de porosité dudit catalyseur est compris entre 75 et 95% lorsque le support est une mousse métallique. Preferably, the porosity rate of said catalyst is between 75 and 95% when the support is a metal foam.
Lorsque le support du catalyseur se présente sous la forme d’une mousse métallique, ladite mousse est de préférence choisie parmi les mousses en nickel, aluminium, fer, cuivre, nickel- chrome, nickel-chrome-aluminium, nickel-fer-chrome-aluminium, fer-chrome-aluminium, nickel-aluminium, inox (316L, 310SS). De préférence, ladite mousse métallique est choisie parmi les mousses en aluminium, nickel, nickel-chrome, nickel-chrome-aluminium. Ces mousses peuvent inclure des additifs tels que le molybdène, le manganèse ou encore le phosphore. When the catalyst support is in the form of a metal foam, said foam is preferably chosen from nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium-aluminum, nickel-iron-chromium-foams. aluminum, iron-chrome-aluminum, nickel-aluminum, stainless steel (316L, 310SS). Preferably, said metal foam is chosen from aluminum, nickel, nickel-chrome, nickel-chrome-aluminum foams. These foams can include additives such as molybdenum, manganese or even phosphorus.
Lorsque le support du catalyseur se présente sous la forme d’une mousse céramique, ladite mousse est de préférence choisie parmi les mousses en alumine (AI2O3), silice-alumine, carbure de silicium (SiC), phosphore-alumine, magnésie (MgO), oxyde de zinc, oxyde de zirconium (ZrÛ2), cordiérite (AI3Mg2AISi50i8). De préférence, ladite mousse céramique est en alumine (AI2O3), silice-alumine, phosphore-alumine, ou carbure de silicium (SiC).
De préférence, la phase active se présente sous la forme d’une couche sur les parois dudit support, l’épaisseur de ladite couche de phase active étant compris entre 10 pm et 150 pm, préférentiellement entre 20 pm et 100 pm et encore plus préférentiellement entre 30 pm et 90 pm. When the catalyst support is in the form of a ceramic foam, said foam is preferably chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina, magnesia (MgO) foams. , zinc oxide, zirconium oxide (ZrÛ2), cordierite (AI 3 Mg 2 AISi50i8). Preferably, said ceramic foam is made of alumina (AI2O3), silica-alumina, phosphorus-alumina, or silicon carbide (SiC). Preferably, the active phase is in the form of a layer on the walls of said support, the thickness of said layer of active phase being between 10 pm and 150 pm, preferably between 20 pm and 100 pm and even more preferably between 30 p.m. and 90 p.m.
Utilisation du catalyseur Use of the catalyst
Le catalyseur obtenu par le procédé selon l’invention peut être utilisé dans un procédé d’hydrogénation sélective de composés polyinsaturés contenant au moins 2 atomes de carbone par molécule, tels que les dioléfines et/ou les acétyléniques et/ou les alcénylaromatiques, contenus dans une charge d’hydrocarbures ayant un point d'ébullition final inférieur ou égal à 300°C, lequel procédé étant réalisé à une température comprise entre 0 et 300°C, à une pression comprise entre 0,1 et 10 MPa, à un ratio molaire hydrogène/(composés polyinsaturés à hydrogéner) compris entre 0,1 et 10 et à une vitesse volumique horaire (V.V.H.) comprise entre 0,1 et 200 h-1 lorsque le procédé est réalisé en phase liquide, ou à un ratio molaire hydrogène/(composés polyinsaturés à hydrogéner) compris entre 0,5 et 1000 et à une vitesse volumique horaire entre 100 et 40000 h-1 lorsque le procédé est réalisé en phase gazeuse. The catalyst obtained by the process according to the invention can be used in a process for the selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule, such as diolefins and/or acetylenes and/or alkenylaromatics, contained in a hydrocarbon feed having a final boiling point less than or equal to 300°C, which process being carried out at a temperature between 0 and 300°C, at a pressure between 0.1 and 10 MPa, at a ratio molar hydrogen/(polyunsaturated compounds to be hydrogenated) of between 0.1 and 10 and at an hourly volume rate (VVH) of between 0.1 and 200 h -1 when the process is carried out in the liquid phase, or at a molar hydrogen ratio /(polyunsaturated compounds to be hydrogenated) between 0.5 and 1000 and at an hourly volume rate between 100 and 40,000 h -1 when the process is carried out in the gas phase.
Les composés organiques mono-insaturés tels que par exemple l’éthylène et le propylène, sont à la source de la fabrication de polymères, de matières plastiques et d'autres produits chimiques à valeur ajoutée. Ces composés sont obtenus à partir du gaz naturel, du naphta ou du gazole qui ont été traités par des procédés de vapocraquage ou de craquage catalytique. Ces procédés sont opérés à haute température et produisent, en plus des composés mono- insaturés recherchés, des composés organiques polyinsaturés tels que l'acétylène, le propadiène et le méthylacétylène (ou propyne), le 1-2-butadiène et le 1-3-butadiène, le vinylacétylène et l'éthylacétylène, et d’autres composés polyinsaturés dont le point d’ébullition correspond à la coupe C5+ (composés hydrocarbonés ayant au moins 5 atomes de carbone), en particulier des composés dioléfiniques ou styréniques ou indéniques. Ces composés polyinsaturés sont très réactifs et conduisent à des réactions parasites dans les unités de polymérisation. Il est donc nécessaire de les éliminer avant de valoriser ces coupes. Monounsaturated organic compounds, such as ethylene and propylene, are the source of the manufacturing of polymers, plastics and other value-added chemicals. These compounds are obtained from natural gas, naphtha or diesel which have been treated by steam cracking or catalytic cracking processes. These processes are operated at high temperature and produce, in addition to the desired monounsaturated compounds, polyunsaturated organic compounds such as acetylene, propadiene and methylacetylene (or propyne), 1-2-butadiene and 1-3 -butadiene, vinylacetylene and ethylacetylene, and other polyunsaturated compounds whose boiling point corresponds to the C5+ cut (hydrocarbon compounds having at least 5 carbon atoms), in particular diolefinic or styrenic or indenic compounds. These polyunsaturated compounds are very reactive and lead to parasitic reactions in the polymerization units. It is therefore necessary to eliminate them before valorizing these cuts.
L'hydrogénation sélective est le principal traitement développé pour éliminer spécifiquement les composés polyinsaturés indésirables de ces charges d'hydrocarbures. Elle permet la conversion des composés polyinsaturés vers les alcènes ou aromatiques correspondants en évitant leur saturation totale et donc la formation des alcanes ou naphtènes correspondants. Dans le cas d'essences de vapocraquage utilisées comme charge, l'hydrogénation sélective permet également d'hydrogéner sélectivement les alcénylaromatiques en aromatiques en évitant l’hydrogénation des noyaux aromatiques.
La charge d'hydrocarbures traitée dans le procédé d’hydrogénation sélective a un point d'ébullition final inférieur ou égal à 300°C et contient au moins 2 atomes de carbone par molécule et comprend au moins un composé polyinsaturé. On entend par « composés polyinsaturés » des composés comportant au moins une fonction acétylénique et/ou au moins une fonction diénique et/ou au moins une fonction alcénylaromatique. Selective hydrogenation is the primary treatment developed to specifically remove unwanted polyunsaturated compounds from these hydrocarbon feedstocks. It allows the conversion of polyunsaturated compounds to the corresponding alkenes or aromatics while avoiding their total saturation and therefore the formation of the corresponding alkanes or naphthenes. In the case of steam cracking gasolines used as feedstock, selective hydrogenation also makes it possible to selectively hydrogenate the alkenyl aromatics into aromatics while avoiding the hydrogenation of the aromatic nuclei. The hydrocarbon feedstock treated in the selective hydrogenation process has a final boiling point of 300°C or less and contains at least 2 carbon atoms per molecule and includes at least one polyunsaturated compound. The term “polyunsaturated compounds” means compounds comprising at least one acetylenic function and/or at least one diene function and/or at least one alkenyl aromatic function.
Plus particulièrement, la charge est sélectionnée dans le groupe constitué par une coupe C2 de vapocraquage, une coupe C2-C3 de vapocraquage, une coupe C3 de vapocraquage, une coupe C4 de vapocraquage, une coupe C5 de vapocraquage et une essence de vapocraquage encore appelée essence de pyrolyse ou coupe C5+. More particularly, the feed is selected from the group consisting of a C2 steam cracking cut, a C2-C3 steam cracking cut, a C3 steam cracking cut, a C4 steam cracking cut, a C5 steam cracking cut and a steam cracking gasoline also called pyrolysis gasoline or C5+ cut.
La coupe C2 de vapocraquage, avantageusement utilisée pour la mise en œuvre du procédé d'hydrogénation sélective selon l'invention, présente par exemple la composition suivante : entre 40 et 95 % poids d'éthylène, de l'ordre de 0,1 à 5 % poids d'acétylène, le reste étant essentiellement de l'éthane et du méthane. Dans certaines coupes C2 de vapocraquage, entre 0,1 et 1 % poids de composés en C3 peut aussi être présent. The C2 steam cracking cut, advantageously used for implementing the selective hydrogenation process according to the invention, has for example the following composition: between 40 and 95% by weight of ethylene, of the order of 0.1 to 5% by weight of acetylene, the remainder being essentially ethane and methane. In certain steam cracked C2 cuts, between 0.1 and 1% by weight of C3 compounds may also be present.
La coupe C3 de vapocraquage, avantageusement utilisée pour la mise en œuvre du procédé d'hydrogénation sélective selon l'invention, présente par exemple la composition moyenne suivante : de l’ordre de 90 % poids de propylène, de l’ordre de 1 à 8 % poids de propadiène et de méthylacétylène, le reste étant essentiellement du propane. Dans certaines coupes C3, entre 0,1 et 2 % poids de composés en C2 et de composés en C4 peut aussi être présent.The C3 steam cracking cut, advantageously used for implementing the selective hydrogenation process according to the invention, has for example the following average composition: of the order of 90% by weight of propylene, of the order of 1 to 8% by weight of propadiene and methylacetylene, the remainder being essentially propane. In some C3 cuts, between 0.1 and 2% by weight of C2 compounds and C4 compounds may also be present.
Une coupe C2 - C3 peut aussi être avantageusement utilisée pour la mise en œuvre du procédé d'hydrogénation sélective selon l'invention. Elle présente par exemple la composition suivante : de l'ordre de 0,1 à 5 % poids d'acétylène, de l’ordre de 0,1 à 3 % poids de propadiène et de méthylacétylène, de l’ordre de 30 % poids d'éthylène, de l’ordre de 5 % poids de propylène, le reste étant essentiellement du méthane, de l’éthane et du propane. Cette charge peut aussi contenir entre 0,1 et 2 % poids de composés en C4. A C2 - C3 cut can also be advantageously used for implementing the selective hydrogenation process according to the invention. It has, for example, the following composition: of the order of 0.1 to 5% by weight of acetylene, of the order of 0.1 to 3% by weight of propadiene and methylacetylene, of the order of 30% by weight of ethylene, of the order of 5% by weight of propylene, the remainder being essentially methane, ethane and propane. This filler can also contain between 0.1 and 2% by weight of C4 compounds.
La coupe C4 de vapocraquage, avantageusement utilisée pour la mise en œuvre du procédé d'hydrogénation sélective selon l'invention, présente par exemple la composition massique moyenne suivante : 1 % poids de butane, 46,5 % poids de butène, 51 % poids de butadiène, 1 ,3 % poids de vinylacétylène et 0,2 % poids de butyne. Dans certaines coupes C4, entre 0,1 et 2 % poids de composés en C3 et de composés en C5 peut aussi être présent. The C4 steam cracking cut, advantageously used for implementing the selective hydrogenation process according to the invention, has for example the following average mass composition: 1% by weight of butane, 46.5% by weight of butene, 51% by weight of butadiene, 1.3% by weight of vinylacetylene and 0.2% by weight of butyne. In some C4 cuts, between 0.1 and 2% by weight of C3 compounds and C5 compounds may also be present.
La coupe C5 de vapocraquage, avantageusement utilisée pour la mise en œuvre du procédé d'hydrogénation sélective selon l'invention, présente par exemple la composition suivante : 21 % poids de pentanes, 45 % poids de pentènes, 34 % poids de pentadiènes. The C5 steam cracking cut, advantageously used for implementing the selective hydrogenation process according to the invention, has for example the following composition: 21% by weight of pentanes, 45% by weight of pentenes, 34% by weight of pentadienes.
L'essence de vapocraquage ou essence de pyrolyse, avantageusement utilisée pour la mise en œuvre du procédé d'hydrogénation sélective selon l'invention, correspond à une coupe hydrocarbonée dont la température d'ébullition est généralement comprise entre 0 et 300°C, de préférence entre 10 et250°C. Les hydrocarbures polyinsaturés à hydrogéner présents dans
ladite essence de vapocraquage sont en particulier des composés dioléfiniques (butadiène, isoprène, cyclopentadiène...), des composés styréniques (styrène, alpha-méthylstyrène...) et des composés indéniques (indène...). L'essence de vapocraquage comprend généralement la coupe C5-C12 avec des traces de C3, C4, C13, C14, C15 (par exemple entre 0,1 et 3% poids pour chacune de ces coupes). Par exemple, une charge formée d'essence de pyrolyse a généralement une composition suivante : 5 à 30 % poids de composés saturés (paraffines et naphtènes), 40 à 80 % poids de composés aromatiques, 5 à 20 % poids de mono-oléfines, 5 à 40 % poids de dioléfines, 1 à 20 % poids de composés alcénylaromatiques, l'ensemble des composés formant 100 %. Elle contient également de 0 à 1000 ppm poids de soufre, de préférence de 0 à 500 ppm poids de soufre. The steam cracking gasoline or pyrolysis gasoline, advantageously used for the implementation of the selective hydrogenation process according to the invention, corresponds to a hydrocarbon cut whose boiling temperature is generally between 0 and 300 ° C, of preferably between 10 and 250°C. Polyunsaturated hydrocarbons to be hydrogenated present in said steam cracking gasoline are in particular diolefinic compounds (butadiene, isoprene, cyclopentadiene, etc.), styrenic compounds (styrene, alpha-methylstyrene, etc.) and indene compounds (indene, etc.). Steam cracked gasoline generally includes the C5-C12 cut with traces of C3, C4, C13, C14, C15 (for example between 0.1 and 3% by weight for each of these cuts). For example, a charge formed from pyrolysis gasoline generally has the following composition: 5 to 30% by weight of saturated compounds (paraffins and naphthenes), 40 to 80% by weight of aromatic compounds, 5 to 20% by weight of mono-olefins, 5 to 40% by weight of diolefins, 1 to 20% by weight of alkenyl aromatic compounds, all of the compounds forming 100%. It also contains from 0 to 1000 ppm by weight of sulfur, preferably from 0 to 500 ppm by weight of sulfur.
De manière préférée, la charge d'hydrocarbures polyinsaturés traitée conformément au procédé d'hydrogénation sélective selon l'invention est une coupe C2 de vapocraquage, ou une coupe C2-C3 de vapocraquage, ou une essence de vapocraquage. Preferably, the polyunsaturated hydrocarbon feedstock treated in accordance with the selective hydrogenation process according to the invention is a C2 steam cracking cut, or a C2-C3 steam cracking cut, or a steam cracking gasoline.
Le procédé d'hydrogénation sélective selon l'invention vise à éliminer lesdits hydrocarbures polyinsaturés présents dans ladite charge à hydrogéner sans hydrogéner les hydrocarbures monoinsaturés. Par exemple, lorsque ladite charge est une coupe C2, le procédé d'hydrogénation sélective vise à hydrogéner sélectivement l'acétylène. Lorsque ladite charge est une coupe C3, le procédé d'hydrogénation sélective vise à hydrogéner sélectivement le propadiène et le méthylacétylène. Dans le cas d'une coupe C4, on vise à éliminer le butadiène, le vinylacétylène (VAC) et le butyne, dans le cas d'une coupe C5, on vise à éliminer les pentadiènes. Lorsque ladite charge est une essence de vapocraquage, le procédé d'hydrogénation sélective vise à hydrogéner sélectivement lesdits hydrocarbures polyinsaturés présents dans ladite charge à traiter de manière à ce que les composés dioléfiniques soient partiellement hydrogénés en mono-oléfines et que les composés styréniques et indéniques soient partiellement hydrogénés en composés aromatiques correspondants en évitant l’hydrogénation des noyaux aromatiques. The selective hydrogenation process according to the invention aims to eliminate said polyunsaturated hydrocarbons present in said feed to be hydrogenated without hydrogenating the monounsaturated hydrocarbons. For example, when said feedstock is a C2 cut, the selective hydrogenation process aims to selectively hydrogenate acetylene. When said feedstock is a C3 cut, the selective hydrogenation process aims to selectively hydrogenate propadiene and methylacetylene. In the case of a C4 cut, we aim to eliminate butadiene, vinylacetylene (VAC) and butyne, in the case of a C5 cut, we aim to eliminate pentadienes. When said feedstock is a steam cracking gasoline, the selective hydrogenation process aims to selectively hydrogenate said polyunsaturated hydrocarbons present in said feedstock to be treated so that the diolefinic compounds are partially hydrogenated into mono-olefins and that the styrenic and indenic compounds are partially hydrogenated into corresponding aromatic compounds while avoiding the hydrogenation of the aromatic nuclei.
La mise en œuvre technologique du procédé d’hydrogénation sélective est par exemple réalisée par injection, en courant ascendant ou descendant, de la charge d'hydrocarbures polyinsaturés et de l’hydrogène dans au moins un réacteur à lit fixe. Ledit réacteur peut être de type isotherme ou de type adiabatique. Un réacteur adiabatique est préféré. La charge d'hydrocarbures polyinsaturés peut avantageusement être diluée par une ou plusieurs réinjections) de l'effluent, issu dudit réacteur où se produit la réaction d'hydrogénation sélective, en divers points du réacteur, situés entre l'entrée et la sortie du réacteur afin de limiter le gradient de température dans le réacteur. La mise en œuvre technologique du procédé d’hydrogénation sélective selon l'invention peut également être avantageusement réalisée par l'implantation d’au moins dudit catalyseur supporté dans une colonne de distillation réactive ou dans des réacteurs - échangeurs ou dans un réacteur de type slurry. Le flux d'hydrogène
peut être introduit en même temps que la charge à hydrogéner et/ou en un ou plusieurs points différents du réacteur. The technological implementation of the selective hydrogenation process is for example carried out by injection, in an ascending or descending current, of the polyunsaturated hydrocarbon feed and the hydrogen into at least one fixed bed reactor. Said reactor can be of the isothermal type or of the adiabatic type. An adiabatic reactor is preferred. The polyunsaturated hydrocarbon feed can advantageously be diluted by one or more reinjections) of the effluent, coming from said reactor where the selective hydrogenation reaction occurs, at various points of the reactor, located between the inlet and outlet of the reactor in order to limit the temperature gradient in the reactor. The technological implementation of the selective hydrogenation process according to the invention can also be advantageously carried out by the implantation of at least said supported catalyst in a reactive distillation column or in reactors - exchangers or in a slurry type reactor . The flow of hydrogen can be introduced at the same time as the feed to be hydrogenated and/or at one or more different points in the reactor.
L'hydrogénation sélective des coupes C2, C2-C3, C3, C4, C5 et C5+ de vapocraquage peut être réalisée en phase gazeuse ou en phase liquide, de préférence en phase liquide pour les coupes C3, C4, C5 et C5+ et en phase gazeuse pour les coupes C2 et C2-C3. Une réaction en phase liquide permet d’abaisser le coût énergétique et d’augmenter la durée de cycle du catalyseur. The selective hydrogenation of the C2, C2-C3, C3, C4, C5 and C5+ steam cracking cuts can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase for the C3, C4, C5 and C5+ cuts and in the gaseous for cuts C2 and C2-C3. A reaction in the liquid phase makes it possible to lower the energy cost and increase the cycle time of the catalyst.
D'une manière générale, l'hydrogénation sélective d’une charge d'hydrocarbures contenant des composés polyinsaturés contenant au moins 2 atomes de carbone par molécule et ayant un point d'ébullition final inférieur ou égal à 300°C s'effectue à une température comprise entre 0 et 300°C, à une pression comprise entre 0,1 et 10 MPa, à un ratio molaire hydrogène/(composés polyinsaturés à hydrogéner) compris entre 0,1 et 10 et à une vitesse volumique horaire V.V.H. (définie comme le rapport du débit volumique de charge sur le volume du catalyseur) comprise entre 0,1 et 200 h-1 pour un procédé réalisé en phase liquide, ou à un ratio molaire hydrogène/(composés polyinsaturés à hydrogéner) compris entre 0,5 et 1000 et à une vitesse volumique horaire V.V.H. comprise entre 100 et 40000 h-1 pour un procédé réalisé en phase gazeuse. Generally speaking, the selective hydrogenation of a hydrocarbon feed containing polyunsaturated compounds containing at least 2 carbon atoms per molecule and having a final boiling point less than or equal to 300°C is carried out at a temperature between 0 and 300°C, at a pressure between 0.1 and 10 MPa, at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio between 0.1 and 10 and at an hourly volume velocity VVH (defined as the ratio of the volume flow rate of charge to the volume of the catalyst) of between 0.1 and 200 h -1 for a process carried out in the liquid phase, or at a molar ratio of hydrogen/(polyunsaturated compounds to be hydrogenated) of between 0.5 and 1000 and at an hourly volume speed VVH of between 100 and 40000 h -1 for a process carried out in the gas phase.
Dans un mode de réalisation selon l’invention, lorsqu’on effectue un procédé d'hydrogénation sélective dans lequel la charge est une essence de vapocraquage comportant des composés polyinsaturés, le ratio molaire (hydrogène)/(composés polyinsaturés à hydrogéner) est généralement compris entre 0,5 et 10, de préférence entre 0,7 et 5,0 et de manière encore plus préférée entre 1 ,0 et 2,0, la température est comprise entre 0 et 200°C, de préférence entre 20 et 200 °C et de manière encore plus préférée entre 30 et 180°C, la vitesse volumique horaire (V.V.H.) est comprise généralement entre 0,5 et 100 h'1, de préférence entre 1 et 50 h'1 et la pression est généralement comprise entre 0,3 et 8,0 MPa, de préférence entre 1 ,0 et 7,0 MPa et de manière encore plus préférée entre 1 ,5 et 4,0 MPa. In one embodiment according to the invention, when carrying out a selective hydrogenation process in which the feedstock is a steam cracking gasoline comprising polyunsaturated compounds, the molar ratio (hydrogen)/(polyunsaturated compounds to be hydrogenated) is generally understood between 0.5 and 10, preferably between 0.7 and 5.0 and even more preferably between 1.0 and 2.0, the temperature is between 0 and 200°C, preferably between 20 and 200° C and even more preferably between 30 and 180°C, the hourly volume velocity (VVH) is generally between 0.5 and 100 h'1 , preferably between 1 and 50 h'1 and the pressure is generally between 0.3 and 8.0 MPa, preferably between 1.0 and 7.0 MPa and even more preferably between 1.5 and 4.0 MPa.
Plus préférentiellement, on effectue un procédé d’hydrogénation sélective dans lequel la charge est une essence de vapocraquage comportant des composés polyinsaturés, le ratio molaire hydrogène/(composés polyinsaturés à hydrogéner) est compris entre 0,7 et 5,0, la température est comprise entre 20 et 200°C, la vitesse volumique horaire (V.V.H.) est comprise généralement entre 1 et 50 h-1 et la pression est comprise entre 1 ,0 et 7,0 MPa.More preferably, a selective hydrogenation process is carried out in which the feedstock is a steam cracking gasoline comprising polyunsaturated compounds, the hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio is between 0.7 and 5.0, the temperature is between 20 and 200°C, the hourly volume velocity (VVH) is generally between 1 and 50 h -1 and the pressure is between 1.0 and 7.0 MPa.
Encore plus préférentiellement, on effectue un procédé d’hydrogénation sélective dans lequel la charge est une essence de vapocraquage comportant des composés polyinsaturés, le ratio molaire hydrogène/(composés polyinsaturés à hydrogéner) est compris entre 1 ,0 et 2,0, la température est comprise entre 30 et 180°C, la vitesse volumique horaire (V.V.H.) est comprise généralement entre 1 et 50 h'1 et la pression est comprise entre 1 ,5 et 4,0 MPa.
Le débit d’hydrogène est ajusté afin d’en disposer en quantité suffisante pour hydrogéner théoriquement l’ensemble des composés polyinsaturés et de maintenir un excès d’hydrogène en sortie de réacteur. Even more preferably, a selective hydrogenation process is carried out in which the feedstock is a steam cracking gasoline comprising polyunsaturated compounds, the hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio is between 1.0 and 2.0, the temperature is between 30 and 180°C, the hourly volume velocity (VVH) is generally between 1 and 50 h'1 and the pressure is between 1.5 and 4.0 MPa. The flow rate of hydrogen is adjusted in order to have a sufficient quantity to theoretically hydrogenate all the polyunsaturated compounds and to maintain an excess of hydrogen at the reactor outlet.
Dans un autre mode de réalisation selon l’invention, lorsqu’on effectue un procédé d'hydrogénation sélective dans lequel la charge est une coupe C2 de vapocraquage et/ou une coupe C2-C3 de vapocraquage comportant des composés polyinsaturés, le ratio molaire (hydrogène)/(composés polyinsaturés à hydrogéner) est généralement compris entre 0,5 et 1000, de préférence entre 0,7 et 800, la température est comprise entre 0 et 300°C, de préférence entre 15 et 280 °C, la vitesse volumique horaire (V.V.H.) est comprise généralement entre 100 et 40000 h-1, de préférence entre 500 et 30000 h-1 et la pression est généralement comprise entre 0,1 et 6,0 MPa, de préférence entre 0,2 et 5,0 MPa. In another embodiment according to the invention, when carrying out a selective hydrogenation process in which the feed is a C2 steam cracking cut and/or a C2-C3 steam cracking cut comprising polyunsaturated compounds, the molar ratio ( hydrogen)/(polyunsaturated compounds to be hydrogenated) is generally between 0.5 and 1000, preferably between 0.7 and 800, the temperature is between 0 and 300°C, preferably between 15 and 280°C, the speed hourly volume (VVH) is generally between 100 and 40,000 h -1 , preferably between 500 and 30,000 h -1 and the pressure is generally between 0.1 and 6.0 MPa, preferably between 0.2 and 5, 0 MPa.
Exemple 1 : Catalyseur Pd sur support mousse métallique NiCr Example 1: Pd catalyst on NiCr metal foam support
Dans cet exemple, le support est une mousse métallique NiCr (fournisseur RECEMAT®) prétraitée à 600°C pour éliminer les contaminants organiques et favoriser l’accroche du précurseur de catalyseur sur le support. In this example, the support is a NiCr metal foam (RECEMAT® supplier) pretreated at 600°C to eliminate organic contaminants and promote adhesion of the catalyst precursor to the support.
Une suspension à base d’une poudre d’alumine gamma de surface spécifique de 212 m2/g (SDA 500, Sasol) est préparée en dispersant la poudre d’alumine dans une solution acide nitrique + eau. Cette suspension est placée dans un broyeur à billes pendant 24 heures pour homogénéiser et réduire la taille des particules d’alumine (< 1 pm). A suspension based on a gamma alumina powder with a specific surface area of 212 m 2 /g (SDA 500, Sasol) is prepared by dispersing the alumina powder in a nitric acid + water solution. This suspension is placed in a ball mill for 24 hours to homogenize and reduce the size of the alumina particles (<1 pm).
On réalise ensuite une étape d’enduction (en un ou plusieurs cycles d’enduction - cf. Tableau 1) via un protocole comprenant les sous-étapes suivantes : We then carry out a coating step (in one or more coating cycles - see Table 1) via a protocol comprising the following sub-steps:
- immersion de support dans le slurry (trempage-retrait) ; - immersion of support in the slurry (soaking-withdrawal);
- soufflage sous air pour favoriser un dépôt homogène et retirer l’excès de slurry ; - blowing under air to promote a homogeneous deposit and remove excess slurry;
- séchage à une température de 120°C pendant 12 heures ; - drying at a temperature of 120°C for 12 hours;
- calcination à 500°C pendant 2 heures. - calcination at 500°C for 2 hours.
Après l’étape d’enduction, le précurseur de catalyseur obtenu est calciné dans four à moufle à 1100°C pendant 13 heures sous atmosphère statique avec une rampe de montée en température de 10°C/min. After the coating step, the catalyst precursor obtained is calcined in a muffle furnace at 1100°C for 13 hours under a static atmosphere with a temperature rise ramp of 10°C/min.
Le catalyseur obtenu à l’issue de l’étape de calcination comprend les caractéristiques suivantes : The catalyst obtained at the end of the calcination step includes the following characteristics:
- surface spécifique, mesurée par porosimetrie mercure : 6 m2/gAI2O3
- volume poreux total, mesuré par porosimetrie au mercure : 0,65 ml/g AI2O3 (* Volume injecté à Pmax ~ 400 MPa soit dpOres ~ 3,6 nm). - specific surface area, measured by mercury porosimetry: 6 m 2 /gAI 2 O3 - total pore volume, measured by mercury porosimetry: 0.65 ml/g AI2O3 (* Volume injected at Pmax ~ 400 MPa or d pO res ~ 3.6 nm).
Une solution colloïdale de particules d’oxyde de palladium est préparée avec une concentration de 0,23 % poids en élément palladium en présence d’hydroxyde de sodium.A colloidal solution of palladium oxide particles is prepared with a concentration of 0.23% by weight of the element palladium in the presence of sodium hydroxide.
Un volume correspondant au volume poreux total de l’alumine enduite sur le support (VPT = 0,65 ml/g) de la solution colloïdale est ensuite déposé en goutte à goutte sur toute la surface du support enduit. S’en suit une maturation de 30 minutes à température ambiante. Le matériau obtenu est ensuite séché dans une étuve à 45°C pendant 48 heures puis calciné en four tubulaire à 450°C pendant 2 heures. A volume corresponding to the total pore volume of the alumina coated on the support (VPT = 0.65 ml/g) of the colloidal solution is then deposited dropwise over the entire surface of the coated support. This is followed by maturation for 30 minutes at room temperature. The material obtained is then dried in an oven at 45°C for 48 hours then calcined in a tubular oven at 450°C for 2 hours.
Test d’accroche - Protocole : afin de vérifier la bonne accroche de la phase active sur le support, chaque échantillon de catalyseur est séché, pesé, puis placé dans de l’éther de pétrole puis mis aux ultrasons pendant 30 minutes à température ambiante. Ensuite, l’éther de pétrole est évaporé à température ambiante et les catalyseurs sont séchés à une température de 150°C pour être à nouveau pesés. Adhesion test - Protocol: in order to check the good adhesion of the active phase on the support, each catalyst sample is dried, weighed, then placed in petroleum ether then sonicated for 30 minutes at room temperature. Then, the petroleum ether is evaporated at room temperature and the catalysts are dried at a temperature of 150°C to be weighed again.
Le test a été réalisé sur 6 échantillons différents afin de vérifier la répétabilité du procédé de préparation. Les résultats sont présentés dans le tableau 1 ci-après. The test was carried out on 6 different samples in order to check the repeatability of the preparation process. The results are presented in Table 1 below.
Table 1
Table 1
Le procédé de préparation selon l’invention permet d’obtenir des catalyseurs dont la phase active de palladium présente une bonne accroche sur les parois du support se présentant sous la forme d’une mousse métallique NiCr, car la perte en masse après test reste inférieure à 2%. The preparation process according to the invention makes it possible to obtain catalysts whose active palladium phase has good adhesion to the walls of the support in the form of a NiCr metal foam, because the loss in mass after testing remains lower at 2%.
Exemple 2 : Catalyseur Pd sur support monolithe FeCrAI Example 2: Pd catalyst on FeCrAI monolith support
Dans cet exemple, le support est un monolithe en FeCrAI (fournisseur Bercy®, CPSI = 600, hauteur 2,5 cm) pré-traitée à 500°C pour éliminer les contaminants organiques et favoriser l’accroche du précurseur de catalyseur sur le support.
Une suspension à base d’une poudre d’alumine gamma de surface spécifique de 212 m2/g (SDA 500, Sasol) est préparée en dispersant la poudre d’alumine dans une solution acide nitrique + eau. Cette suspension est placée dans un broyeur à billes pendant 24 heures pour homogénéiser et réduire la taille des particules d’alumine (< 1 pm). In this example, the support is a FeCrAI monolith (supplier Bercy®, CPSI = 600, height 2.5 cm) pre-treated at 500°C to eliminate organic contaminants and promote adhesion of the catalyst precursor to the support . A suspension based on a gamma alumina powder with a specific surface area of 212 m 2 /g (SDA 500, Sasol) is prepared by dispersing the alumina powder in a nitric acid + water solution. This suspension is placed in a ball mill for 24 hours to homogenize and reduce the size of the alumina particles (<1 pm).
On réalise ensuite une étape d’enduction (en un ou plusieurs cycles d’enduction - cf. Tableau 2) via un protocole comprenant les sous-étapes suivantes : We then carry out a coating step (in one or more coating cycles - see Table 2) via a protocol comprising the following sub-steps:
- immersion de support dans le slurry (trempage-retrait) ; - immersion of support in the slurry (soaking-withdrawal);
- soufflage sous air pour favoriser un dépôt homogène et retirer l’excès de slurry ; - blowing under air to promote a homogeneous deposit and remove excess slurry;
- séchage à une température de 120°C pendant 12 heures ; - drying at a temperature of 120°C for 12 hours;
- calcination à 500°C pendant 2 heures. - calcination at 500°C for 2 hours.
Après l’étape d’enduction, le précurseur de catalyseur obtenu est calciné dans four à moufle à 1100°C pendant 10 heures sous atmosphère statique avec une rampe de montée en température de 10°C/min. After the coating step, the catalyst precursor obtained is calcined in a muffle furnace at 1100°C for 10 hours under a static atmosphere with a temperature rise ramp of 10°C/min.
Le catalyseur obtenu à l’issue de l’étape de calcination comprend les caractéristiques suivantes : The catalyst obtained at the end of the calcination step includes the following characteristics:
- surface spécifique, mesurée par porosimetrie mercure : 6 n gAfeOs - specific surface area, measured by mercury porosimetry: 6 n gAfeOs
- volume poreux total, mesuré par porosimetrie au mercure : 0,48 ml/g AI2O3 (* Volume injecté à Pmax ~ 400 MPa soit dpOres ~ 3,6 nm). - total pore volume, measured by mercury porosimetry: 0.48 ml/g AI2O3 (* Volume injected at Pmax ~ 400 MPa or d pO res ~ 3.6 nm).
Une solution colloïdale de particules d’oxyde de palladium est préparée avec une concentration de 0,20 % poids en élément palladium en présence d’hydroxyde de sodium.A colloidal solution of palladium oxide particles is prepared with a concentration of 0.20% by weight of the element palladium in the presence of sodium hydroxide.
Un volume correspondant au volume poreux total de l’alumine enduite sur le support (VPT = 0,65 ml/g) de la solution colloïdale est ensuite déposé en goutte à goutte sur toute la surface du support enduit. S’en suit une maturation de 30 minutes à température ambiante. Le matériau obtenu est ensuite séché dans une étuve à 45°C pendant 48 heures puis calciné en four tubulaire à 450°C pendant 2 heures. A volume corresponding to the total pore volume of the alumina coated on the support (VPT = 0.65 ml/g) of the colloidal solution is then deposited dropwise over the entire surface of the coated support. This is followed by maturation for 30 minutes at room temperature. The material obtained is then dried in an oven at 45°C for 48 hours then calcined in a tubular oven at 450°C for 2 hours.
Le catalyseur est testé via un test d’accroche dans les mêmes conditions opératoires que l’exemple 1. Le test a été réalisé sur 4 échantillons différents afin de vérifier la répétabilité du procédé de préparation. Les résultats sont présentés dans le tableau 2 ci-après.
Table 2
The catalyst is tested via an adhesion test under the same operating conditions as Example 1. The test was carried out on 4 different samples in order to check the repeatability of the preparation process. The results are presented in Table 2 below. Table 2
Le procédé de préparation selon l’invention permet d’obtenir des catalyseurs dont la phase active de palladium présente une bonne accroche sur les parois du support se présentant sous la forme d’un monolithe métallique FeCrAI car la perte en masse après test reste inférieure à 1,5%.
The preparation process according to the invention makes it possible to obtain catalysts whose active palladium phase has good adhesion to the walls of the support in the form of a metallic FeCrAI monolith because the loss in mass after testing remains less than 1.5%.
Claims
1. Procédé de préparation d’un catalyseur d’hydrogénation sélective comprenant une phase active à base d’au moins un métal du groupe VIII, déposée sur une alumine alpha, et un support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique, lequel procédé comprend au moins les étapes suivantes : a) on approvisionne une poudre d’alumine gamma comprenant une surface spécifique comprise entre 100 et 500 m2/g ; b) on met en contact par enduction ladite poudre d’alumine gamma de l’étape a) avec un support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique pour obtenir un précurseur de catalyseur comprenant une alumine gamma ; c) on calcine le précurseur de catalyseur obtenu à l’issue de l’étape b) à une température comprise entre 900°C et 1300°C pour obtenir un précurseur de catalyseur calciné comprenant une alumine alpha ; d) on met en contact le précurseur de catalyseur calciné obtenu à l’issue de l’étape c) avec une solution comprenant au moins un précurseur de la phase active comprenant au moins un métal du groupe VIII pour obtenir un matériau ; e) on sèche le matériau obtenu à l’issue de l’étape d) à une température inférieure à 250°C puis on calcine le matériau séché à une température comprise entre 250°C et 550°C. 1. Process for preparing a selective hydrogenation catalyst comprising an active phase based on at least one group VIII metal, deposited on an alpha alumina, and a support in the form of a monolith or a ceramic or metallic foam, which process comprises at least the following steps: a) a gamma alumina powder is supplied comprising a specific surface area of between 100 and 500 m 2 /g; b) said gamma alumina powder from step a) is brought into contact by coating with a support in the form of a monolith or a ceramic or metallic foam to obtain a catalyst precursor comprising a gamma alumina ; c) the catalyst precursor obtained at the end of step b) is calcined at a temperature between 900°C and 1300°C to obtain a calcined catalyst precursor comprising an alpha alumina; d) the calcined catalyst precursor obtained at the end of step c) is brought into contact with a solution comprising at least one precursor of the active phase comprising at least one metal from group VIII to obtain a material; e) the material obtained at the end of step d) is dried at a temperature below 250°C and then the dried material is calcined at a temperature between 250°C and 550°C.
2. Procédé selon la revendication 1 , dans lequel ledit métal du groupe VIII est le palladium. 2. Method according to claim 1, wherein said Group VIII metal is palladium.
3. Procédé selon la revendication 2, dans lequel la teneur en palladium est comprise entre 0,005 et 1% poids en élément palladium par rapport au poids total du catalyseur. 3. Method according to claim 2, in which the palladium content is between 0.005 and 1% by weight of palladium element relative to the total weight of the catalyst.
4. Procédé selon l’une quelconque des revendications 1 à 3, dans lequel lorsque le support se présente sous la forme d’une mousse céramique ou métallique, ladite étape b) comprend les sous-étapes suivantes : b1) on disperse la poudre d’alumine gamma dans une solution à base d’acide nitrique et d’eau, puis on broie le précurseur de catalyseur dispersé de manière à obtenir une suspension ; b2) on enduit la mousse céramique ou métallique de ladite suspension obtenue à l’issue de l’étape b1) par trempage-retrait ;
b3) on réalise : 4. Method according to any one of claims 1 to 3, in which when the support is in the form of a ceramic or metallic foam, said step b) comprises the following sub-steps: b1) the powder is dispersed gamma alumina in a solution based on nitric acid and water, then the dispersed catalyst precursor is ground so as to obtain a suspension; b2) the ceramic or metallic foam is coated with said suspension obtained at the end of step b1) by soaking-withdrawal; b3) we carry out:
- soit une étape de centrifugation de la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b2) ; - either a centrifugation step of the coated ceramic or metal foam obtained at the end of step b2);
- soit une étape de soufflage de la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b2) ; b4) optionnellement, on sèche la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b3) à une température comprise entre 80°C et 220°C ; b5) on calcine la mousse céramique ou métallique enduite obtenue à l’issue de l’étape b3), optionnellement à l’issue de l’étape b4), à une température comprise entre 250°C et 550°C. - either a step of blowing the coated ceramic or metallic foam obtained at the end of step b2); b4) optionally, the coated ceramic or metallic foam obtained at the end of step b3) is dried at a temperature between 80°C and 220°C; b5) the coated ceramic or metallic foam obtained at the end of step b3), optionally at the end of step b4), is calcined at a temperature between 250°C and 550°C.
5. Procédé selon la revendication 4, dans lequel ledit support se présente sous la forme d’une mousse métallique choisie parmi les mousses en nickel, aluminium, fer, cuivre, nickel-chrome, nickel-chrome-aluminium, nickel-fer-chrome-aluminium, fer-chrome-aluminium, nickel- aluminium, inox. 5. Method according to claim 4, in which said support is in the form of a metal foam chosen from nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium-aluminum, nickel-iron-chromium foams -aluminum, iron-chrome-aluminum, nickel-aluminum, stainless steel.
6. Procédé selon l’une des revendications 4, dans lequel ledit support se présente sous la forme d’une mousse céramique choisie parmi les mousses en alumine (AI2O3), silice-alumine, carbure de silicium (SiC), phosphore-alumine, magnésie (MgO), oxyde de zinc, oxyde de zirconium (ZrCh), cordiérite (AklV^AISisOis). 6. Method according to one of claims 4, in which said support is in the form of a ceramic foam chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina foams, magnesia (MgO), zinc oxide, zirconium oxide (ZrCh), cordierite (AklV^AISisOis).
7. Procédé selon l’une quelconque des revendications 4 à 6, dans lequel ledit catalyseur comprend une surface géométrique comprise entre 1000 et 7000 m2/m3. 7. Method according to any one of claims 4 to 6, wherein said catalyst comprises a geometric surface area of between 1000 and 7000 m 2 /m 3 .
8. Procédé selon l’une quelconque des revendications 4 à 7, dans lequel ledit catalyseur comprend un diamètre des pores compris entre 0,2 et 1 ,5 mm. 8. Method according to any one of claims 4 to 7, wherein said catalyst comprises a pore diameter of between 0.2 and 1.5 mm.
9. Procédé selon l’une quelconque des revendications 1 à 3, dans lequel lorsque le support se présente sous la forme d’un monolithe céramique ou métallique, ladite étape b) comprend les sous-étapes suivantes : b1 ’) on disperse la poudre d’alumine gamma dans une solution à base d’acide nitrique et d’eau, puis on broie le précurseur de catalyseur dispersé de manière à obtenir une suspension ; b2’) on enduit le support se présentant sous la forme d’un monolithe céramique ou métallique de ladite suspension obtenue à l’issue de l’étape bT) par trempage-retrait ;
b3’) on réalise une étape de soufflage du monolithe céramique ou métallique enduit obtenu à l’issue de l’étape b2’); b4’) optionnellement, on sèche du monolithe céramique ou métallique enduit obtenu à l’issue de l’étape b3’) à une température comprise entre 80°C et 220°C ; b5’) on calcine du monolithe céramique ou métallique enduit obtenue à l’issue de l’étape b3’), optionnellement à l’issue de l’étape b4’), à une température comprise entre 250°C et 550°C. 9. Method according to any one of claims 1 to 3, in which when the support is in the form of a ceramic or metallic monolith, said step b) comprises the following sub-steps: b1 ') the powder is dispersed of gamma alumina in a solution based on nitric acid and water, then the dispersed catalyst precursor is ground so as to obtain a suspension; b2') the support in the form of a ceramic or metallic monolith is coated with said suspension obtained at the end of step bT) by soaking-withdrawal; b3') a step is carried out of blowing the coated ceramic or metallic monolith obtained at the end of step b2');b4') optionally, the coated ceramic or metallic monolith obtained at the end of step b3') is dried at a temperature between 80°C and 220°C; b5') the coated ceramic or metallic monolith obtained at the end of step b3'), optionally at the end of step b4'), is calcined at a temperature between 250°C and 550°C.
10. Procédé selon la revendication 9, dans lequel ledit support se présente sous la forme d’un monolithe métallique choisi parmi les monolithes en acier, inox, nickel, aluminium, fer, cuivre, nickel-chrome, nickel-chrome-aluminium, fer-chrome-aluminium. 10. Method according to claim 9, in which said support is in the form of a metal monolith chosen from steel, stainless steel, nickel, aluminum, iron, copper, nickel-chromium, nickel-chromium-aluminum, iron monoliths -chrome-aluminum.
11. Procédé selon l’une des revendications 9, dans lequel ledit support se présente sous la forme d’un monolithe céramique choisi parmi les monolithes en alumine (AI2O3), silice-alumine, carbure de silicium (SiC), phosphore-alumine, magnésie (MgO), oxyde de zinc, oxyde de zirconium (ZrC>2), cordiérite (AI3Mg2AISi50i8). 11. Method according to one of claims 9, in which said support is in the form of a ceramic monolith chosen from alumina (AI2O3), silica-alumina, silicon carbide (SiC), phosphorus-alumina monoliths, magnesia (MgO), zinc oxide, zirconium oxide (ZrC>2), cordierite (AI 3 Mg 2 AISi50i8).
12. Procédé selon l’une quelconque des revendications 9 à 11 , dans lequel ledit support comprend un nombre de canaux par unité de longueur (CPSI) entre 300 et 1200. 12. Method according to any one of claims 9 to 11, wherein said support comprises a number of channels per unit length (CPSI) between 300 and 1200.
13. Procédé selon l’une quelconque des revendications 9 à 12, dans lequel la surface géométrique dudit catalyseur est comprise entre 1500 m2/m3 et 5000 m2/m3. 13. Method according to any one of claims 9 to 12, in which the geometric surface of said catalyst is between 1500 m 2 /m 3 and 5000 m 2 /m 3 .
14. Procédé selon l’une quelconque des revendications 1 à 13, dans lequel ledit support se présentant sous la forme d’un monolithe ou d’une mousse céramique ou métallique approvisionné à l’étape d) est préalablement calciné sous air à une température comprise entre 300°C et 800°C pendant une durée comprise entre 2 et 8 heures.
14. Method according to any one of claims 1 to 13, in which said support in the form of a monolith or a ceramic or metallic foam supplied in step d) is previously calcined in air at a temperature between 300°C and 800°C for a period of between 2 and 8 hours.
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| FR2207347A FR3137848A1 (en) | 2022-07-18 | 2022-07-18 | METHOD FOR PREPARING A CATALYST COMPRISING A GROUP VIII METAL AND A SUPPORT IN THE FORM OF A MONOLITH OR A FOAM COATED WITH ALPHA ALUMINA |
| FRFR2207347 | 2022-07-18 |
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| PCT/EP2023/069133 WO2024017702A1 (en) | 2022-07-18 | 2023-07-11 | Process for preparing a catalyst comprising a group viii metal and a support in the form of a monolith or a foam coated with alpha alumina |
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2022
- 2022-07-18 FR FR2207347A patent/FR3137848A1/en active Pending
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