Classifications

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  • 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
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/755—Nickel
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/882—Molybdenum and cobalt
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/883—Molybdenum and nickel
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  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
  • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
  • B01J27/19—Molybdenum
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  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/24—Nitrogen compounds
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/638—Pore volume more than 1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/651—50-500 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/66—Pore distribution
  • B01J35/69—Pore distribution bimodal
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • 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
  • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/04—Mixing
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/20—Sulfiding
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
  • C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
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  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
  • C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
  • C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
• • 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
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
• • 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
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten 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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
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  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
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  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/205—Metal content

Definitions

• the invention relates to hydrotreatment catalysts, especially residues, and relates to the preparation of comalaxed active phase hydrotreating catalysts having a texture and a formulation that are favorable for the hydrotreatment of residues, in particular for hydrodemetallization.
• the preparation process according to the invention also makes it possible to avoid the impregnation step usually carried out on a previously shaped support.
• the invention consists of the use of active phase catalysts comalaxed in an aluminum oxide matrix comprising at least one element of group VIB, optionally at least one group VIII element, and optionally the phosphorus element.
• the fixed bed residue hydrotreating processes (commonly called "Residual Desulfurization” unit or RDS) lead to high refining performance: typically they can produce a boiling temperature cut above 370 ° C. containing less than 0 ° C. , 5% by weight of sulfur and less than 20 ppm of metals from fillers containing up to 5% by weight of sulfur and up to 250 ppm of metals (Ni + V).
• the different effluents thus obtained can serve as a basis for the production of good quality heavy fuel oils and / or pretreated feedstocks for other units such as catalytic cracking ("Fluid Catalytic Cracking").
• the hydroconversion of the residue in slices lighter than the atmospheric residue is generally low, typically of the order of 10 to 20% by weight.
• the feed, premixed with hydrogen circulates through a plurality of fixed bed reactors arranged in series and filled with catalysts.
• the total pressure is typically between 100 and 200 bar (10 and 20 MPa) and the temperatures between 340 and 420 ° C.
• the effluents withdrawn from the last reactor are sent to a fractionation section.
• the fixed bed hydrotreating process consists of at least two steps (or sections).
• the first so-called hydrodemetallation (HDM) stage is mainly aimed at eliminating the majority of metals from the feedstock by using one or more hydrodemetallization catalysts.
• This stage mainly includes vanadium and nickel removal operations and, to a lesser extent, iron.
• the second step or so-called hydrodesulfurization (HDS) section, consists in passing the product of the first step over one or more hydrodesulfurization catalysts, which are more active in terms of hydrodesulphurization and hydrogenation of the feedstock, but less tolerant to metals.
• hydrodesulfurization catalysts which are more active in terms of hydrodesulphurization and hydrogenation of the feedstock, but less tolerant to metals.
• the patent application WO 2010/002699 teaches in particular that it is advantageous to use a catalyst whose support has a median pore diameter of between 10 and 14 nm and whose distribution is narrow. It specifies that less than 5% of the pore volume must be developed in pores larger than 21 nm and in the same way, less than 10% of the volume must be observed in small pores smaller than 9 nm.
• US Patent 5,968,348 confirms that it is preferable to use a support whose mesoporosity remains close to 1 1 to 13 nm, possibly with the presence of macropores and a high BET surface, here at least 175 m 2 / g.
• US Pat. Nos. 4,976,848 and 5,089,463 disclose a heavy-charge hydrodemetallation and hydrodesulfurization catalyst comprising a hydrogenating active phase based on Group VI and VIII metals and an inorganic refractory oxide support, the catalyst having precisely between 5 and 1 1% of its pore volume in the form of macropores and has mesopores with a median diameter greater than 16.5 nm.
• US Pat. No. 7,169,294 describes a heavy-weight hydroconversion catalyst comprising between 7 and 20% of Group VI metal and between 0.5 and 6% by weight of Group VIII metal on an aluminum support.
• the catalyst has a specific surface area of between 100 and 180 m 2 / g, a total pore volume greater than or equal to 0.55 ml / g, and at least 50% of the total pore volume is included in pores larger than 20 nm.
• At least 5% of the total pore volume is included in pores larger than 100 nm, at least 85% of the total pore volume being included in pores between 10 and 120 nm, less than 2% of the total pore volume being contained in pores with a diameter greater than 400 nm, and less than 1% of the total pore volume being contained in pores with a diameter greater than 1000 nm.
• Numerous developments include the optimization of the porous distribution of the catalyst or catalyst mixtures by optimizing the catalyst support.
• US Pat. No. 6,589,908 describes, for example, a process for preparing an alumina characterized by the absence of macropores, less than 5% of the total pore volume constituted by pores with a diameter of greater than 35 nm, and a high pore volume greater than 0.8 ml / g, and a bimodal mesopore distribution in which the two modes are separated by 1 to 20 nm and the primary porous mode being larger than the porous median diameter.
• the method of preparation described implements two stages of precipitation of alumina precursors under well-controlled conditions of temperature, pH and flow rates. The first step operates at a temperature between 25 and 60 ° C, a pH between 3 and 10.
• the suspension is then heated to a temperature between 50 and 90 ° C.
• Reagents are again added to the slurry, which is then washed, dried, shaped and calcined to form a catalyst support.
• Said support is then impregnated with an active phase solution to obtain a hydrotreatment catalyst; a catalyst for hydrotreating residues on a mesoporous monomodal support of porous median diameter around 20 nm is described.
• US Pat. No. 7,790,652 discloses hydroconversion catalysts obtainable by coprecipitation of an alumina gel, then introduction of the metals onto the support obtained by any method known to those skilled in the art, in particular by impregnation.
• the obtained catalyst has a mesoporous monomodal distribution with a mesoporous median diameter of between 11 and 12.6 nm and a porous distribution width of less than 3.3 nm.
• Alternative approaches to the conventional introduction of metals onto aluminum supports have also been developed, such as the incorporation of catalyst fines into the support.
• patent application WO2012 / 021386 discloses hydrotreatment catalysts comprising a porous refractory oxide support shaped from alumina powder and from 5% to 45% by weight of catalyst fines.
• the support including the fines is then dried, calcined.
• the support obtained has a specific surface area of between 50 m 2 / g and 450 m 2 / g, a mean pore diameter of between 50 and 200 A (5 to 20 nm), and a total pore volume exceeding 0.55 cm 3 / boy Wut.
• the support thus comprises metal incorporated thanks to the metals contained in the catalyst fines.
• the resulting support can be treated with a chelating agent.
• the pore volume may be partially filled by means of a polar additive, and may be impregnated with a metal impregnating solution.
• a catalyst prepared from an alumina resulting from the calcination of a specific alumina gel having a low dispersibility, by comalaxing a hydro-dehydrogenating active phase with the alumina calcined had a porous structure particularly interesting for the hydrotreatment of heavy loads, while having a suitable active phase content.
• the invention relates to a hydroconversion / hydrotreating residue catalyst having an optimized porous distribution and an active phase comalaxed in a calcined aluminic matrix.
• the invention also relates to a catalyst preparation process suitable for the hydroconversion / hydrotreatment of residues by comalaxing the active phase with a particular alumina.
• the invention finally relates to the use of the catalyst in hydrotreating processes, in particular the hydrotreatment of heavy feedstocks. Summary of the invention
• the invention relates to a process for the preparation of a comalaxed active phase catalyst, comprising at least one metal of group VI B of the periodic table of elements, optionally at least one metal of group VIII of the periodic table of elements, optionally of phosphorus and a predominantly aluminum oxide matrix, comprising the following steps:
• step d) a step of drying said alumina gel obtained in step d) to obtain a powder
• step f) a step of heat treatment of the powder obtained at the end of step e) between 500 and 1000 ° C, for a period of between 2 and 10 h, in the presence or absence of a flow of air containing up to 60% water volume to obtain a calcined aluminous porous oxide;
• the rate of advance of the first precipitation step a) is advantageously between 6 and 12%.
• the rate of advance of the first precipitation step a) is very preferably between 7 and 1 1%.
• the acidic precursor is advantageously chosen from aluminum sulphate, aluminum chloride and aluminum nitrate, preferably aluminum sulphate.
• the basic precursor is advantageously chosen from sodium aluminate and potassium aluminate, preferably sodium aluminate.
• the aqueous reaction medium is water and said steps operate with stirring, in the absence of organic additive.
• the invention also relates to a mesoporous and macroporous hydroconversion catalyst comprising:
• hydro-dehydrogenating active phase comprising at least one Group VIB metal of the periodic table of the elements, optionally at least one metal of the group
• said active phase being at least partially comalaxed within said calcined aluminum oxide matrix
• said catalyst having a surface area S B ET greater than 100 m 2 / g, a mesoporous median diameter by volume between 12 nm and 25 nm, inclusive, a median macroporous volume diameter between 50 and 250 nm, limits included, a mesoporous volume as measured by mercury porosimeter intrusion greater than or equal to 0.65 ml / g and a total pore volume measured by mercury porosimetry greater than or equal to 0.75 ml / g.
• said catalyst has a mesoporous median diameter in volume determined by mercury porosimeter intrusion of between 13 and 17 nm, limits included.
• said catalyst has a macroporous volume of between 15 and 35% of the total pore volume.
• the mesoporous volume is between 0.65 and 0.75 ml / g.
• the catalyst does not have micropores.
• the group VI B metal content is between 2 and 10% by weight of trioxide of at least Group VI B metal relative to the total mass of the catalyst
• the Group VIII metal content is between 0.0 and 3.6% by weight of the oxide of at least Group VIII metal relative to the total mass of the catalyst
• the content of phosphorus element is between 0 and 5% by weight of phosphorus pentoxide relative to the total mass of the catalyst.
• the hydro-dehydrogenating active phase may be composed of molybdenum (Mo), or nickel and molybdenum (NiMo), or cobalt and molybdenum (CoMo).
• the hydrodehydrogenating active phase preferably also comprises phosphorus.
• the hydro-dehydrogenating active phase is fully comalaxed.
• part of the hydro-dehydrogenating active phase may be impregnated on the predominantly aluminum oxide matrix.
• the invention also relates to a process for the hydrotreatment of a heavy hydrocarbon feedstock chosen from atmospheric residues, vacuum residues resulting from direct distillation, deasphalted oils, residues resulting from conversion processes such as, for example, those originating from coking, hydroconversion fixed bed, bubbling bed or moving bed, taken alone or in mixture, said hydrotreatment process comprising contacting said feedstock with hydrogen and a catalyst capable of being prepared according to the invention or a catalyst as described above.
• the process may be carried out partly in a bubbling bed at a temperature of between 320 ° and 450 ° C., under a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity advantageously between 0.1 and 10 vol. charge per volume of catalyst per hour, and with a hydrogen gas ratio on a hydrocarbon liquid charge advantageously between 100 and 3000 normal cubic meters per cubic meter.
• the process may be carried out at least in part in a fixed bed at a temperature of between 320 ° C. and 450 ° C., at a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity of between 0.05 and 5. volume of charge per volume of catalyst per hour, and with a hydrogen gas ratio on a hydrocarbon liquid charge of between 200 and 5000 normal cubic meters per cubic meter.
• the process may be a heavy hydrocarbon feedstock hydrotreatment process of the fixed bed residues type comprising at least:
• said catalyst is used in at least one of said steps a) and b).
• a catalyst which simultaneously has a high total pore volume (greater than or equal to 0.75 ml / g), a mesoporous volume (greater than or equal to 0.65 ml / g), a high median diameter of the mesopores high (between 12 and 25 nm), a median macroporous diameter between 50 and 250 nm, but also active phase characteristics favorable to hydrotreatment.
• the advantage of a comparison compared to an impregnation is that it avoids any risk of partial blockage of the porosity of the support during the deposit of the active phase and therefore the appearance of problems of limitations.
• such a catalyst In addition to being able to be synthesized at a lower cost, such a catalyst has a significant gain in hydrodemetallation compared to other comalaxed catalysts of the prior art, and therefore requires a lower operating temperature than these to reach the same level of conversion of metallated compounds.
• said catalyst according to the invention at the beginning of complete chaining to a fixed bed, ie a hydrodemetallation section (HDM) and then a hydrodesulfurization section (HDS), the overall performances of the sequence are improved. .
• HDM hydrodemetallation section
• HDS hydrodesulfurization section
• dispersibility is defined as the weight of solid or gel of peptised alumina that can not be dispersed by centrifugation in a 3600G polypropylene tube for 3 min.
• the catalyst of the present invention has a specific porous distribution, where the macroporous and mesoporous volumes are measured by mercury intrusion and the microporous volume is measured by nitrogen adsorption.
• Macropores means pores whose opening is greater than 50 nm.
• pores is meant pores whose opening is between 2 nm and 50 nm, limits included.
• micropores pores whose opening is less than 2 nm.
• specific surface means the specific surface B.E.T. determined by nitrogen adsorption according to ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the journal "The Journal of the American Society", 60, 309, (1938).
• total pore volume of the alumina or the predominantly aluminum matrix or catalyst means the volume measured by mercury porosimeter intrusion according to ASTM D4284-83 at a pressure of maximum of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °.
• the angle of anchorage was taken equal to 140 ° following the recommendations of the book “Techniques of the engineer, treated analysis and characterization", p.1050-5, written by Jean Charpin and Bernard Rasneur.
• the value of the total pore volume in ml / g given in the following text corresponds to the value of the total mercury volume (total pore volume measured by mercury porosimeter intrusion) in ml / g measured on the sample minus the mercury volume value in ml / g measured on the same sample for a pressure corresponding to 30 psi (approximately 0.2 MPa).
• the volume of macropores and mesopores is measured by mercury intrusion porosimetry according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °.
• the value at which mercury fills all the intergranular voids is fixed at 0.2 MPa, and it is considered that beyond this mercury enters the pores of the sample.
• the macroporous volume of the catalyst is defined as the cumulative volume of mercury introduced at a pressure of between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores with an apparent diameter greater than 50 nm.
• the mesoporous volume of the catalyst is defined as the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores with an apparent diameter of between 2 and 50 nm.
• micropore volume is measured by nitrogen porosimetry.
• the quantitative analysis of the microporosity is carried out using the "t" method (Lippens-De Boer method, 1965) which corresponds to a transformation of the starting adsorption isotherm as described in the book “Adsorption by powders and porous solids. Principles, methodology and applications "written by F. Rouquérol, J. Rouquérol and K. Sing, Académie Press, 1999.
• the mesoporous median diameter is also defined as a diameter such that all pores smaller than this diameter constitute 50% total mesoporous volume determined by mercury porosimeter intrusion.
• Macroporous median diameter is also defined as a diameter such that all pores smaller than this diameter constitute 50% of the total macroporous volume determined by mercury porosimeter intrusion.
• group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
• the invention relates to a comalaxed active phase hydroconversion catalyst comprising at least one Group VI B metal of the Periodic Table of Elements, optionally at least one Group VIII metal of the Periodic Table of Elements, optionally phosphorus and a predominantly calcined aluminum oxide matrix, its method of preparation and its use in a hydrotreating process of heavy hydrocarbon feedstocks such as petroleum residues (atmospheric or vacuum).
• the catalyst according to the invention is in the form of a matrix comprising for the most part a calcined porous refractory oxide in which the metals of the active phase are distributed.
• the invention also relates to the process for preparing the catalyst which is carried out by comalaxing a particular alumina with a metal solution of formulation adapted to the target metal target for the final catalyst.
• the Group VI B metals are advantageously selected from molybdenum and tungsten, and preferably said Group VI B metal is molybdenum.
• Group VIII metals are preferably selected from iron, nickel or cobalt and nickel or cobalt, or a combination of both, is preferred.
• the respective quantities of group VI B metal and of group VIII metal are advantageously such that the atomic ratio metal (aux) of group VIII on group VI B metal (aux) (VI 11: VI B) is between 0, 0: 1 and 0.7: 1, preferably between 0.1: 1 and 0.6: 1 and more preferably between 0.2: 1 and 0.5: 1. This ratio can in particular be adjusted according to the type of load and the process used.
• the respective amounts of group VI B metal and phosphorus are such that the atomic phosphorus to metal group (A) ratio of group VI B (P / VI B) is between 0.2: 1 and 1.0: 1, preferably between 0.4: 1 and 0.9: 1 and even more preferably between 0.5: 1.0 and 0.85: 1.
• the metal content of group VI B is advantageously between 2 and 10% by weight of trioxide of at least Group VI B metal relative to the total mass of the catalyst, preferably between 3 and 8%, and still more preferably more preferred between 4 and 7% weight.
• the metal content of group VIII is advantageously between 0.0 and 3.6% by weight of the oxide of at least one group VIII metal relative to the total mass of the catalyst, preferably between 0.4 and 2.5% and even more preferably between 0.7 and 1.8% by weight.
• the content of phosphorus element is advantageously between 0.0 and 5% by weight of phosphorus pentoxide relative to the total mass of the catalyst, preferably between 0.6 and 3.5% by weight and even more preferably between 1 and 5% by weight. , 0 and 3.0% weight.
• the predominantly calcined aluminum matrix of said catalyst according to the invention comprises an alumina content of greater than or equal to 90% and a silica content of at most 10% by weight of Si0 2 equivalent relative to the mass of the matrix, preferably silica content of less than 5% by weight, very preferably less than 2% by weight.
• the silica may be introduced, by any technique known to those skilled in the art, during the synthesis of the alumina gel or at the time of the comalaxing.
• the aluminic matrix contains nothing other than alumina.
• the said co-axial phase active catalyst according to the invention is generally presented in all the forms known to those skilled in the art.
• it consists of extrudates of diameter generally between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and very preferably between 1.0 and 2.5 mm.
• This may advantageously be in the form of extruded cylindrical, trilobed or quadrilobed.
• its shape will be trilobed or quadrilobed.
• the shape of the lobes can be adjusted according to all known methods of the prior art.
• the comalaxed catalyst according to the invention has particular textural properties.
• the catalyst according to the invention has a total pore volume (VPT) of at least 0.75 ml / g and preferably at least 0.80 ml / g. In a preferred embodiment, the catalyst has a total pore volume of from 0.80 to 1.05 ml / g.
• the catalyst used according to the invention advantageously has a macroporous volume, Vmacro or V 50 nm, defined as the pore volume with a diameter greater than 50 nm, between 15 and 35% of the total pore volume, and preferably between 15 and 30. % of the total pore volume. In a very preferred embodiment, the macroporous volume represents between 20 and 30% of the total pore volume.
• the mesoporous volume (Vmeso) of the catalyst is at least 0.65 ml / g, preferably between 0.65 and 0.80 ml / g. In a preferred embodiment, the mesoporous volume of the catalyst is between 0.65 ml / g and 0.75 ml / g.
• the mesoporous median diameter (D pmoiso ) is between 12 nm and 25 nm, limits included, and preferably between 12 and 18 nm, limits included. Very preferably, the median mesoporous diameter is between 13 and 17 nm, inclusive.
• the catalyst advantageously has a macroporous median diameter (D pma cro) of between 50 and 250 nm, preferably between 80 and 200 nm, even more preferably between 80 and 150 nm. Very preferably, the macroporous median diameter is between 90 and 130 nm.
• the catalyst according to the present invention has a BET (S B ET) specific surface area of at least 100 m 2 / g, preferably at least 120 m 2 / g and even more preferably between 150 and 250 m 2 /boy Wut.
• the catalyst has a low microporosity, very preferably no microporosity is detectable in nitrogen porosimetry.
• the catalyst according to the invention differs structurally from a catalyst obtained by simply impregnating a metal precursor on an alumina support in which the alumina forms the support and the active phase is introduced into the pores of this support.
• the process for preparing the catalyst according to the invention by comalaxing a particular aluminous porous oxide with one or more precursors of metals makes it possible to obtain a composite in which the metals and the The alumina is intimately mixed thereby forming the catalyst structure with porosity and active phase content at the desired reactions.
• the catalyst according to the invention is prepared by co-mixing a calcined porous aluminum oxide obtained from a specific alumina gel and the precursor (s) of metals.
• the process for preparing the catalyst according to the invention comprises the following steps: a) to e): Synthesis of the precursor gel of the porous oxide
• step g) of comalaxing The solid obtained at the end of steps a) to f) undergoes a step g) of comalaxing. It is then shaped in a step h), then can then simply be dried at a temperature of less than or equal to 200 ° C (step i) or dried, and then subjected to a new calcination heat treatment in a step j) optional.
• the catalyst Prior to its use in a hydrotreatment process, the catalyst is usually subjected to a final sulfurization step.
• This step consists in activating the catalyst by transforming, at least in part, the oxide phase in a sulpho-reducing medium.
• This activation treatment by sulphurisation is well known to those skilled in the art and can be performed by any previously known method already described in the literature.
• a sulphidation method Conventional well known to those skilled in the art consists in heating the mixture of solids under a stream of a mixture of hydrogen and hydrogen sulfide or under a stream of a mixture of hydrogen and hydrocarbons containing sulfur molecules at a temperature of between 150 ° C. and 800 ° C, preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.
• the comalaxed active phase catalyst according to the invention is prepared from a specific alumina gel, which is dried and calcined, before comalaxing with the active phase, and then shaped.
• said method for preparing the alumina gel comprises a first step a) of precipitation, a step b) of heating, a step c) of second precipitation, a step d) of filtration, a step e) drying.
• the rate of progress for each of the precipitation stages is defined as the proportion of alumina formed in Al 2 0 3 equivalent during said first or second precipitation stage relative to the total amount of alumina formed in Al 2 equivalent. 0 3 at the end of the two precipitation steps and more generally at the end of the steps of preparation of the alumina gel and in particular at the end of step c) of the preparation process according to the invention.
• This step consists in bringing into contact, in an aqueous reaction medium, at least one basic precursor chosen from sodium aluminate, potassium aluminate, aqueous ammonia, sodium hydroxide and potassium hydroxide. and at least one acid precursor selected from aluminum sulfate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, wherein at least one of one of the basic precursors or acid comprises aluminum, the relative flow rate of acidic and basic precursors is chosen in such a way as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the acidic and basic precursor (s) containing aluminum is adjusted so as to obtain a degree of progress.
• at least one basic precursor chosen from sodium aluminate, potassium aluminate, aqueous ammonia, sodium hydroxide and potassium hydroxide.
• the mixture in the aqueous reaction medium of at least one basic precursor and at least one acidic precursor requires that at least one of the acidic or basic precursors comprises aluminum. It is also possible that at least two of the basic and acidic precursors comprise aluminum.
• Basic precursors comprising aluminum are sodium aluminate and potassium aluminate.
• the preferred basic precursor is sodium aluminate.
• Acidic precursors comprising aluminum are aluminum sulphate, aluminum chloride and aluminum nitrate.
• the preferred acidic precursor is aluminum sulphate.
• the aqueous reaction medium is water.
• said step a) operates with stirring.
• said step a) is carried out in the absence of organic additive.
• the acidic and basic precursors, whether they contain aluminum or not, are mixed, preferably in solution, in the aqueous reaction medium, in such proportions that the pH of the resulting suspension is between 8.5 and 10. 5.
• the alumina acid precursors and the basic alumina precursors can be used alone or as a mixture in the precipitation step.
• the relative flow rate of the acidic and basic precursors they contain aluminum or not is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5.
• the mass ratio of said basic precursor to said acidic precursor is advantageously between 1.60 and 2.05.
• the base / acid mass ratios are established by a curve of neutralization of the base by the acid. Such a curve is easily obtained by those skilled in the art.
• said precipitation step a) is carried out at a pH of between 8.5 and 10.0 and very preferably between 8.7 and 9.9.
• the first precipitation step a) is carried out at a temperature of between 20 and 90 ° C, preferably between 20 and 70 ° C and more preferably between 30 and 50 ° C.
• the first step a) of precipitation is carried out for a duration of between 2 and 30 minutes, preferably between 5 and 20 minutes, and very preferably between 5 and 15 minutes.
• the rate of progress of said first precipitation step a) is between 5 and 13%, preferably between 6 and 12% and very preferably between 7 and 11%.
• the acidic and basic precursors containing aluminum are therefore introduced in amounts which make it possible to obtain a suspension containing the desired quantity of alumina, as a function of the final concentration of alumina to be reached.
• said step a) makes it possible to obtain 5 to 13% by weight of alumina with respect to the total amount of alumina formed in Al 2 O 3 equivalent at the end of stage c) of the preparation process.
• said preparation method comprises a step b) of heating the suspension obtained at the end of the first step a) of precipitation.
• a heating step of the suspension obtained at the end of the precipitation step a) is carried out between the two precipitation stages.
• Said step of heating the suspension obtained at the end of step a), carried out between said first precipitation step a) and the second precipitation step c) operates at a temperature between 40 and 90 ° C, preferably between 40 and 80 ° C, very preferably between 40 and 70 ° C and even more preferably between 40 and 65 ° C.
• Said heating step is carried out for a period of between 7 and 45 minutes and preferably between 7 and 35 minutes.
• Said heating step is advantageously carried out according to all the heating methods known to those skilled in the art.
• said preparation method comprises a second step of precipitation of the heated suspension obtained at the end of the heating step b), said second stage operating by adding to said suspension at least one chosen basic precursor among sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, in which at least one of the basic or acidic precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the acidic and basic precursor (s) containing aluminum is adjusted so as to obtain a progress rate of the second stage comprised between 87 and 95%, the ta advancement rate being defined as the proportion of alumina formed in Al 2 0 3 equivalent at said second precipitation step relative to the total amount of alumina formed in Al 2 0 3 equivalent at the end of step
• the basic precursor (s) and acid (s) are added in the said second co-precipitation step in aqueous solution.
• the addition to the heated suspension of at least one basic precursor and at least one acidic precursor requires that at least one of the basic or acid precursors comprises aluminum. It is also possible that at least two of the basic and acidic precursors comprise aluminum.
• Basic precursors comprising aluminum are sodium aluminate and potassium aluminate.
• the preferred basic precursor is sodium aluminate.
• Acidic precursors comprising aluminum are aluminum sulphate, aluminum chloride and aluminum nitrate.
• the preferred acidic precursor is aluminum sulphate.
• said second precipitation step operates with stirring.
• said second step is carried out in the absence of organic additive.
• the acidic and basic precursors, whether they contain aluminum or not, are mixed, preferably in solution, in the suspension, in such proportions that the pH of the resulting suspension is between 8.5 and 10.5. .
• the relative flow rate of the acidic and basic precursors, whether they contain aluminum or not is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10. , 5, preferably between 8.5 and 10, even more preferably between 8.7 and 9.9.
• the mass ratio of said basic precursor to said acidic precursor is advantageously between 1.60 and 2.05.
• the base / acid mass ratio is established by a curve of neutralization of the base by the acid. Such a curve is easily obtained by those skilled in the art.
• the aluminum precursors are also mixed in amounts to obtain a suspension containing the desired amount of alumina, depending on the final concentration of alumina to be achieved.
• said second precipitation step makes it possible to obtain 87 to 95% by weight of alumina with respect to the total amount of alumina formed in Al 2 O 3 equivalent at the end of the two precipitation stages.
• step a) of precipitation it is the flow rate of the acidic and basic precursor (s) containing aluminum which is adjusted so as to obtain a progress rate of the second stage between 87 and 95 %, preferably between 88 and 94%, very preferably between 89 and 93%, the degree of progress being defined as the proportion of alumina formed in Al 2 0 3 equivalent during said second precipitation step relative to to the total amount of alumina formed in equivalent AI203 at the end of step c) of the preparation process.
• the amounts of aluminum to be provided by the acid precursors and / or basic are calculated and the Precursor flow rate is adjusted according to the concentration of said added aluminum precursors, the amount of water added to the reaction medium and the rate of progress required for each of the precipitation steps.
• the flow rates of the acid-containing precursor (s) and / or base (s) containing aluminum depend on the size of the reactor used and thus on the amount of water added to the reaction medium.
• the precursors of aluminas are sodium aluminate at a concentration of 155 g / l in Al 2 O 3 and aluminum sulphate at a concentration of 102 g / l in Al 2 O 3.
• the precipitation pH of the first step is set at 9.5 and the pH of the second step at 9.
• the amount of water added to the reactor is 620 ml.
• the flow rate of aluminum sulphate must be 2.1 ml / min and the flow rate of sodium aluminate is 2.6 ml / min .
• the weight ratio of sodium aluminate to aluminum sulfate is therefore 1.91.
• the aluminum sulfate flow rate should be 5.2 ml / min and the sodium aluminate flow rate is 6.3 ml / min.
• the weight ratio of sodium aluminate to aluminum sulfate is therefore 1.84.
• the second precipitation step is carried out at a temperature between 40 and 80 ° C, preferably between 45 and 70 ° C and very preferably between 50 and 70 ° C.
• the second precipitation step is carried out for a period of between 5 and 45 minutes, and preferably of 7 to 40 minutes.
• the second precipitation step generally makes it possible to obtain a suspension of alumina having an Al 2 O 3 concentration of between 20 and 100 g / l, preferably between 20 and 80 g / l, preferably between 20 and 50 g. / l.
• the process for preparing alumina according to the invention also comprises a step of filtering the suspension obtained at the end of the second precipitation step c). Said filtration step is carried out according to the methods known to those skilled in the art.
• the filterability of the suspension obtained at the end of the two precipitation steps is improved by the low dispersibility of the alumina gel obtained, which makes it possible to improve the productivity of the process according to the invention as well as to allow extrapolation of the process. at the industrial level.
• Said filtration step is advantageously followed by at least one washing step, preferably with water and preferably from one to three washing steps, with a quantity of water equal to the amount of filtered precipitate.
• the sequence of the first precipitation a), the heating b) and the second precipitation c) stages and the filtration stage d) makes it possible to obtain a specific alumina gel having a dispersibility ratio of less than 15%, preferably between 5 and 15% and preferably between 6 and 14%, very preferably between 7 and 13%, and even more preferably between 7 and 10% and a crystallite size between 1 and 35 nm and preferably between 2 to 35 nm.
• the alumina gel obtained also advantageously has a sulfur content, measured by the X-ray fluorescence method, of between 0.001 and 2% by weight and preferably between 0.01 and 0.2% by weight and a sodium content, measured by ICP. MS or inductively coupled plasma spectrometry between 0.001 and 2% by weight, and preferably between 0.01 and 0.1% by weight, the weight percentages being expressed relative to the total mass of alumina gel.
• the alumina gel or the boehmite in powder form according to the invention is composed of crystallites whose size, obtained by the Scherrer formula in X-ray diffraction according to the crystallographic directions [020] and [120] are respectively between 2 and 20 nm and between 2 and 35 nm.
• the alumina gel according to the invention has a crystallite size in the crystallographic direction [020] of between 1 to 15 nm and a crystallite size in the crystallographic direction [120] of between 1 to 35 nm.
• X-ray diffraction on alumina or boehmite gels was performed using the conventional powder method using a diffractometer.
• Scherrer's formula is a formula used in X-ray diffraction on powders or polycrystalline samples which connects the width at half height of the diffraction peaks to the size of the crystallites. It is described in detail in the reference: Appl. Cryst. (1978). 1 1, 102-1 13 "Scherrer after sixty years: A survey and some new results in the determination of crystallite size", J. I. Langford and A. J. C. Wilson.
• the low dispersibility rate of the gel thus prepared makes it possible to facilitate the step of shaping said gel according to all the methods known to those skilled in the art and in particular by extrusion kneading, by granulation and by the technique known as drop (draining) according to the English terminology. Step e): drying of the alumina gel
• the alumina gel obtained at the end of the second precipitation step c), followed by a filtration step d), is dried in a drying step e) to obtain a powder, said drying step being carried out by drying, for example by drying at a temperature between 20 and 200 ° C and for a period of time ranging from 8 hours to 15 hours, or by atomization or by any other known drying technique; skilled person.
• drying step e) is carried out by atomization
• the cake obtained at the end of the second precipitation step, followed by a filtration step is resuspended.
• Said suspension is then sprayed in fine droplets, in a vertical cylindrical chamber in contact with a stream of hot air to evaporate the water according to the principle well known to those skilled in the art.
• the powder obtained is driven by the heat flow to a cyclone or a bag filter that will separate the air from the powder.
• the powder obtained at the end of the drying step e) is subjected to a heat treatment step f) at a temperature of between 500 and 1000 ° C. for a duration of between 2 and 10 hours. h, with or without a flow of air containing up to 60% water volume.
• said heat treatment step f) operates at a temperature of between 540 ° C. and 850 ° C.
• said heat treatment step f) operates for a duration of between 2 h and 10 h.
• Said f) heat treatment step allows the transition of the boehmite to the final alumina.
• the heat treatment step may be preceded by drying at a temperature between 50 ° C and 120 ° C, according to any technique known to those skilled in the art.
• the powder obtained after drying step e), after heat treatment in a step f), is comalaxed with the metal precursor (s) of the active phase, in a step g) comalaxing allowing the contact or solutions containing the active phase to come into contact with the powder, and then shaping the resulting material to obtain the catalyst in a step h).
• the calcined aluminous porous oxide resulting from step f) is kneaded in the presence of the active phase in the form of a solution of the precursors of the metal (s) chosen from the group VIB elements, optionally the elements of group VIII and possibly phosphorus.
• the active phase is provided by one or more solutions containing at least one Group VIB metal, optionally at least one Group VIII metal and optionally the phosphorus element.
• the said solution (s) may be aqueous, consisting of an organic solvent or a mixture of water and at least one organic solvent (for example ethanol or toluene).
• the solution is aquo-organic and even more preferably aqueous-alcoholic.
• the pH of this solution may be modified by the possible addition of an acid.
• the compounds which can be introduced into the solution as sources of group VIII elements advantageously are: citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, sulphates, aluminates, molybdates, tungstates, oxides, nitrates, halides for example, chlorides, fluorides, bromides, acetates, or any mixture of the compounds set forth herein.
• the sources of the group VIB element which are well known to those skilled in the art, there are advantageously, for example, for molybdenum and tungsten: oxides, hydroxides, molybdic and tungstic acids and their salts, in particular sodium salts.
• ammonium, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts Oxides or ammonium salts such as ammonium molybdate, ammonium heptamolybdate or ammonium tungstate are preferably used.
• the preferred phosphorus source is orthophosphoric acid, but its salts and esters such as alkaline phosphates, ammonium phosphate, gallium phosphate or alkyl phosphates are also suitable.
• Phosphorous acids for example hypophosphorous acid, phosphomolybdic acid and its salts, phosphotungstic acid and its salts can be advantageously used.
• An additive for example a chelating agent of organic nature, may advantageously be introduced into the solution if the person skilled in the art deems it necessary.
• any other element for example silica in the form of a solution or emulsion of silicic precursor, can be introduced into the mixing tank at the time of this step.
• Comalaxing is advantageously carried out in a kneader, for example a "Brabender" kneader, well known to those skilled in the art.
• the aluminous porous oxide in the form of calcined powder obtained in step f) and one or more additives or other possible elements are placed in the tank of the kneader.
• the solution of metal precursors for example nickel and molybdenum, and optionally deionized water are added to the syringe or any other means for a period of a few minutes, typically about 2 minutes at a given kneading speed.
• the kneading can be maintained for a few minutes, for example about 15 minutes at 50 rpm.
• the paste obtained at the end of the comalaxing step g) is then shaped according to any technique known to those skilled in the art, for example extrusion shaping methods, pelletizing, by the method of the drop of oil, or by granulation at the turntable.
• said support used according to the invention is shaped by extrusion in the form of extrudates of diameter generally between 0.5 and 10 mm and preferably 0.8 and 3.2 mm. In a preferred embodiment, it will be composed of trilobed or quadrilobed extrudates of size between 1.0 and 2.5 mm in diameter.
• said comalling step g) and said shaping step h) are combined in a single kneading-extruding step.
• the paste obtained after the mixing can be introduced into a piston extruder through a die having the desired diameter, typically between 0.5 and 10 mm.
• the catalyst obtained after the galting and shaping step h) h) undergoes drying i) at a temperature less than or equal to at 200 ° C, preferably below 150 ° C according to any technique known to those skilled in the art, for a period of typically between 2 and 12 hours.
• the catalyst thus dried can then undergo a complementary heat treatment or hydrothermal step j) at a temperature of between 200 and 1000 ° C., preferably between 300 and 800 ° C. and even more preferably between 350 and 550 ° C., while a duration typically between 2 and 10 h, in the presence or absence of a flow of air containing up to 60% by volume of water.
• a complementary heat treatment or hydrothermal step j) at a temperature of between 200 and 1000 ° C., preferably between 300 and 800 ° C. and even more preferably between 350 and 550 ° C., while a duration typically between 2 and 10 h, in the presence or absence of a flow of air containing up to 60% by volume of water.
• Several combined cycles of thermal or hydrothermal treatments can be carried out.
• the catalyst is only advantageously dried in step i).
• the contact with the steam can take place at atmospheric pressure (steaming) or autogenous pressure (autoclaving).
• steaming the water content is preferably between 150 and 900 grams per kilogram of dry air, and even more preferably between 250 and 650 grams per kilogram of dry air.
• a part of the metals may be introduced by impregnation of said catalyst from step i) or j), according to any known method of the A person skilled in the art, the most common being that of dry impregnation.
• all of the metal phase is introduced during the preparation by comalaxing the porous aluminum oxide and no additional impregnation step will therefore be necessary.
• the active phase of the catalyst is fully comalaxed within the calcined porous aluminum oxide. Description of the process for using the catalyst according to the invention
• the catalyst according to the invention can be used in hydrotreatment processes for converting heavy hydrocarbon feeds, containing sulfur impurities and metal impurities.
• One objective sought by the use of the catalysts of the present invention relates to an improvement of the performances, in particular in hydrodemetallation and hydrodesulphurization, while improving the ease of preparation with respect to the catalysts known from the prior art.
• the catalyst according to the invention makes it possible to improve the performances in hydrodemetallation and in hydrodesulphalate with respect to conventional catalysts, while having a high stability over time.
• the hydrotreatment processes for converting heavy hydrocarbon feeds, containing sulfur impurities and metal impurities operate at a temperature of between 320 and 450 ° C. under a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity advantageously between 0.05 and 10 volumes of filler per volume of catalyst and per hour, and with a hydrogen gas ratio on a hydrocarbon liquid feed advantageously between 100 and 5000 normal cubic meters per cubic meter . loads
• the feedstocks treated in the process according to the invention are advantageously chosen from atmospheric residues, vacuum residues resulting from direct distillation, deasphalted oils, residues resulting from conversion processes such as, for example, those originating from coking, from a hydroconversion in a fixed bed, in a bubbling bed, or in a moving bed, taken alone or as a mixture.
• fillers can advantageously be used as they are or else diluted by a hydrocarbon fraction or a mixture of hydrocarbon fractions which may be chosen from the products of the FCC process, a light cutting oil (LCO according to the initials of the English name of Light Cycle Oil), a heavy cutting oil (HCO according to the initials of the English name of Heavy Cycle Oil), a decanted oil (OD according to the initials of the English name of Decanted Oil), a slurry, or From the distillation, gas oil fractions including those obtained by vacuum distillation called according to the English terminology VGO (Vacuum Gas Oil). Heavy loads can advantageously include cuts from the process of liquefying coal, aromatic extracts, or any other hydrocarbon cut.
• a hydrocarbon fraction or a mixture of hydrocarbon fractions which may be chosen from the products of the FCC process, a light cutting oil (LCO according to the initials of the English name of Light Cycle Oil), a heavy cutting oil (HCO according to the initials of the English name of Heavy Cycle Oil), a decanted oil
• Said heavy charges generally have more than 1% by weight of molecules having a boiling point greater than 500 ° C., a Ni + V metals content of greater than 1 ppm by weight, preferably greater than 20 ppm by weight, and very preferably greater than 50 ppm by weight, an asphaltene content, precipitated in heptane, greater than 0.05% by weight, preferably greater than 1% by weight, very preferably greater than 2%.
• the heavy fillers can advantageously also be mixed with coal in the form of powder, this mixture being generally called slurry. These fillers can advantageously be by-products from the conversion of the coal and mixed again with fresh coal.
• the coal content in the heavy load is generally and preferably a 1 ⁇ 4 (Oil / Coal) ratio and may advantageously vary widely between 0.1 and 1.
• the coal may contain lignite, be a sub-bituminous coal (according to the English terminology), or bituminous. Any other type of coal is suitable for the use of the invention, both in fixed bed reactors and in bubbling bed reactors. Setting the catalyst according to the invention
• the comalaxed active phase catalyst is preferably used in the first catalytic beds of a process successively comprising at least one hydrodemetallization step and at least one hydrodesulfurization step.
• the process according to the invention is advantageously carried out in one to ten successive reactors, the catalyst (s) according to the invention can advantageously be charged in one or more reactors and / or in all or some of the reactors. .
• reactive reactors ie reactors operating alternately, in which hydrodemetallation catalysts according to the invention can preferably be implemented, can be used upstream of the unit. .
• the reactive reactors are then followed by series reactors, in which catalysts are used.
• hydrodesulfurization which can be prepared according to any method known to those skilled in the art.
• two permutable reactors are used upstream of the unit, preferably for the hydrodemetallation and containing one or more catalysts according to the invention. They are advantageously monitored by one to four reactors in series, advantageously used for hydrodesulfurization.
• the process according to the invention can advantageously be implemented in a fixed bed with the objective of eliminating metals and sulfur and lowering the average boiling point of the hydrocarbons.
• the operating temperature is advantageously between 320 ° C. and 450 ° C., preferably 350 ° C. to 410 ° C., under a partial pressure.
• in hydrogen advantageously between 3 MPa and 30 MPa, preferably between 10 and 20 MPa, at a space velocity advantageously between 0.05 and 5 volume of charge per volume of catalyst per hour, and with a gaseous hydrogen gas on charge ratio hydrocarbon liquid advantageously between 200 and 5000 normal cubic meters per cubic meter, preferably 500 to 1500 normal cubic meters per cubic meter.
• the process according to the invention can also advantageously be implemented partly in bubbling bed on the same charges.
• the catalyst is advantageously used at a temperature of between 320 and 450 ° C. under a hydrogen partial pressure of advantageously between 3 MPa and 30.degree. MPa, preferably between 10 and 20 MPa, at a space velocity advantageously between 0.1 and 10 volumes of filler per volume of catalyst and per hour, preferably between 0.5 and 2 volumes of filler by volume of catalyst and by hour, and with a gaseous hydrogen gas on hydrocarbon liquid charge advantageously between 100 and 3000 normal cubic meters per cubic meter, preferably between 200 to 1200 normal cubic meters per cubic meter.
• the method according to the invention is implemented in a fixed bed.
• the catalysts of the present invention are preferably subjected to a sulphurization treatment making it possible, at least in part, to convert the metal species into sulphide before they come into contact with the charge. treat.
• This activation treatment by sulphurisation is well known to those skilled in the art and can be performed by any previously known method already described in the literature.
• a conventional sulphurization method well known to those skilled in the art consists in heating the mixture of solids under a stream of a mixture of hydrogen and hydrogen sulphide or under a stream of a mixture of hydrogen and of hydrocarbons containing sulfur-containing molecules at a temperature of temperature between 150 and 800 ° C, preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.
• the sulfurization treatment can be carried out ex situ (before the introduction of the catalyst into the hydrotreatment / hydroconversion reactor) or in situ by means of an organosulfur precursor agent of H 2 S, for example DMDS (dimethyl disulphide).
• organosulfur precursor agent of H 2 S for example DMDS (dimethyl disulphide).
• the concentration of the precursor is: aluminum sulphate Al 2 (S0 4) 3 to 102g / L of Al 2 O 3 and NaAIOO sodium aluminate in 155g / L of Al 2 0 3 ..
• Alumina AI (A1) used according to the invention is manufactured according to the following steps:
• a first co-precipitation of aluminum sulphate Al 2 (SO 4 ) 3 and sodium aluminate NaAlOO at 30 ° C. and pH 9.1 in 8 min: the degree of progress is 10% .
• the rate of progress corresponds to the proportion of alumina formed during the first stage, ie a final concentration of alumina at 45 g / l. If working in a 5 L reactor and aiming for 4 l of alumina suspension with a final concentration of Al 2 O 3 of 45 g / l, with a targeted advancement rate of 10% for the first precipitation stage, % of the total alumina must be provided during the step a) of precipitation.
• the precipitation pH of the first step is set at 9.1 and the precipitation pH of the second step is 9.1.
• the amount of water initially present in the reactor is 1330 ml.
• the flow rate of aluminum sulfate should be 7.6 ml / min
• the flow rate of sodium aluminate is 9.1 ml / min
• the weight ratio of sodium aluminate to aluminum sulfate is therefore 1.91.
• the concentration of the precursor is: aluminum sulphate Al 2 (S0 4) 3 to 102g / l of Al 2 0 3 and NaAIOO sodium aluminate in 155g / l of Al 2 0 3.
• the precipitation pH of the first step is set at 9.1 and the precipitation pH of the second step is 9.1.
• the amount of water initially present in the reactor is 1330 ml.
• the flow rate of aluminum sulphate should be 6.1 ml / min, the flow rate of sodium aluminate is 7.6 ml / min and the water flow rate of 69.7 mL / min.
• the weight ratio of sodium aluminate to aluminum sulfate is therefore 1.91.
• the impregnation solutions A and B were respectively kneaded in the presence of the Al (A1) and Al (B1) aluminas prepared above to prepare the catalysts A1 and B1.
• the comalaxing takes place in a "Brabender" mixer with a tank of 80 cm 3 and a mixing speed of 30 rpm.
• the alumina powder is placed in the bowl of the kneader.
• the MoNi solution (P) is added to the syringe for about 2 minutes at 15 rpm.
• the kneading is maintained 15 minutes after obtaining a paste at 50 rpm.
• the paste thus obtained is introduced into the MTS capillary rheometer through a 2.1 mm die at 10 mm / min. the extrudates thus obtained are then dried overnight in an oven at 80 ° C. and then calcined for 2 hours in air (1 L / h / g) in a tubular oven at 400 ° C.
• Example 3 (Comparative) Preparation of a catalyst E by dry impregnation of an aluminum support
• Catalyst E is a catalyst prepared by boehmite extrusion-mixing, followed in the order of calcination and hydrothermal treatment before dry impregnation of the S (E) support with an aqueous solution so that the metals is the same as that introduced by comalaxing on the catalyst A1.
• Catalyst E is prepared by dry impregnation of an aluminum support S (E) prepared as hereinafter.
• the synthesis of an alumina is carried out in a reactor in 5 I in 3 steps.
• the concentration of the precursor is: aluminum sulphate Al 2 (S0 4) 3 to 102g / L of Al 2 O 3 and NaAIOO sodium aluminate in 155g / L of Al 2 0 3 ..
• Alumina is manufactured according to the following steps:
• a first co-precipitation of aluminum sulphate Al 2 (SO 4 ) 3 and sodium aluminate NaAlOO at 30 ° C. and pH 9.1 in 8 min: the degree of progress is 20% .
• the rate of progress corresponds to the proportion of alumina formed during the first stage, ie a final alumina concentration of 45 g / l. If one works in a reactor of 5 I and that one aims 4 I alumina suspension of Al 2 0 3 final concentration of 45 g / l, with a targeted progress rate of 20% for the first step of precipitation, 20% of the total alumina must be provided during step a) of precipitation
• the precipitation pH of the first step is set at 9.1.
• the amount of water initially present in the reactor is 1330 ml.
• the flow rate of aluminum sulfate should be 15.2 ml / min, the flow of sodium aluminate is 19 ml / min and the water flow rate is 49.2 mL / min.
• the weight ratio of sodium aluminate to aluminum sulfate is therefore 1.91.
• the flow rate of aluminum sulphate must be 16.5 ml / min, the sodium aluminate flow rate is 20 ml / min and the flow rate of water is 30.1 mL / min.
• the weight ratio of sodium aluminate to aluminum sulfate is therefore 1.84.
• the cake is dried (step e) in an oven for at least one night at 120 ° C.
• the powder is obtained which must be shaped.
• the shaping is carried out on a Brabender kneader with an acid level (total, expressed relative to dry alumina) of 1%, a neutralization rate of 20% and acid and basic fire losses respectively of 62 and 64%.
• the catalyst After impregnation, the catalyst undergoes a maturing stage of 24 hours in a saturated water atmosphere, before being dried for 12 hours at 120 ° C. in air and then calcined under air at 400 ° C. for 2 hours. Catalyst E is obtained. The metal contents have been checked and are reported in Table 2 above.
• Catalyst A2 is prepared by comalaxing the active phase with a calcined Al (A2) alumina from a non-compliant alumina gel (non-compliant first stage advance rate).
• alumina Al (A2) is carried out by following the steps of Example 2 (Alumina Al (A1)).
• the operating conditions are strictly identical, with the exception of the following two points:
• step a) of first precipitation the advancement rate is 20%.
• step c) of second precipitation the rate of progress is 80%.
• the synthesis of an alumina used according to the invention is carried out in a reactor in 5 I in 3 steps.
• the concentration of the precursor is: aluminum sulphate Al 2 (S0 4) 3 to 102g / L of Al 2 0 3 and NaAIOO sodium aluminate in 155g / L of Al 2 0 3.
• the precipitation pH of the first step is set at 9.1.
• the amount of water initially present in the reactor is 1330 ml.
• the flow rate of aluminum sulfate should be 15.2 ml / min, the flow of sodium aluminate is 19 ml / min and the water flow rate is 49.2 mL / min.
• the weight ratio of sodium aluminate to aluminum sulfate is therefore 1.91.
• the flow rate of aluminum sulphate must be 16.5 ml / min, the sodium aluminate flow rate is 20 ml / min and the flow rate of water is 30.1 mL / min.
• the weight ratio of sodium aluminate to aluminum sulfate is therefore 1.84.
• the comalaxing takes place in a "Brabender" mixer with a tank of 80 cm3 and a kneading speed of 30 rpm.
• the alumina powder is placed in the bowl of the kneader.
• MoNi solution A (P) is added to the syringe for about 2 minutes at 15 rpm.
• the kneading is maintained 15 minutes after obtaining a paste at 50 rpm.
• the paste thus obtained is introduced into the MTS capillary rheometer through a 2.1 mm die at 10 mm / min. the extrudates thus obtained are then dried overnight in an oven at 80 ° C. and then calcined for 2 hours in air (1 L / h / g) in a tubular oven at 400 ° C.
• the catalyst A2 is obtained.
• the catalyst A2 has the characteristics reported in Table 2. It has in particular an excessively high macroporous volume, to the detriment of the mesoporous volume which remains low and the median mesoporous diameter (Dpmeso) which remains low (less than 8 nm).
• Example 5 (Comparative): Preparation of non-compliant comalaxed catalyst A3
• the non-compliant catalyst A3 is prepared by comalaxing the active phase with a non-calcined boehmite powder B (A3).
• the concentration of the precursor is: aluminum sulphate Al 2 (S0 4) 3 to 102g / l of Al 2 0 3 and NaAIOO sodium aluminate in 155g / l of Al 2 0 3.
• Boehmite B (A3) is manufactured according to the following steps a) to e), under the same conditions as in example 1, but without step f) of calcination:
• a first co-precipitation of aluminum sulphate Al 2 (SO 4 ) 3 and sodium aluminate NaAlOO at 30 ° C. and pH 9.1 in 8 min: the degree of progress is 10% .
• the rate of progress corresponds to the proportion of alumina formed during the first stage, ie a final concentration of alumina at 45 g / l.
• Solution A is kneaded in the presence of the alumina precursor powder B (A3) (in AIOOH form) obtained in step e), without subjecting it to any additional heat treatment. It is therefore a boehmite powder.
• the mixing conditions implemented are strictly the same as those described above.
• the comalaxing takes place in a "Brabender" mixer with a tank of 80 cm3 and a kneading speed of 30 rpm.
• the powder is placed in the bowl of the mixer.
• the MoNi solution (P) is added to the syringe for about 2 minutes at 15 rpm.
• the kneading is maintained 15 minutes after obtaining a paste at 30 rpm.
• the paste thus obtained is introduced into the MTS capillary rheometer through a 2.1 mm die at 10 mm / min.
• the extrudates thus obtained are then dried overnight in an oven at 80 ° C. and then calcined for 2 hours in air (1 L / h / g) in a tubular oven at 400 ° C.
• the catalyst A3 obtained has the characteristics reported in Table 2. Compared to the catalyst A2, the macroporous volume is lower, but it remains too high. Moreover, the mesoporous volume is very small and the median mesoporous diameter (D pmos ) unchanged with respect to the catalyst A2, therefore less than 8 nm.
• the catalysts previously described in Examples 2 to 5 are in-situ sulfide-dynamic in the fixed-bed tubular reactor passed through a Microcat-type pilot unit (manufacturer: Vinci Company), the fluids flowing from top to bottom.
• the measurements of hydrogenating activity are carried out immediately after sulphurization under pressure and without re-airing with the hydrocarbon feedstock which was used to sulphurize the catalysts.
• the sulfurization and test load is composed of 5.8% dimethyl disulphide (DMDS), 20% toluene and 74.2% cyclohexane (by weight).
• DMDS dimethyl disulphide
• the sulfurization and test load is composed of 5.8% dimethyl disulphide (DMDS), 20% toluene and 74.2% cyclohexane (by weight).
• the stabilized catalytic activities of equal volumes of catalysts are thus measured in the hydrogenation reaction of toluene.
• the detailed conditions for activity measurement are as follows:
• Catalyst volume 4 cm 3 (extruded length between 2 and 4 mm)
• T unconverted toluene
• MCC6 methylcyclohexane
• EtCC5 ethylcyclopentane
• DMCC5 dimethylcyclopentanes
• Table 3 Comparison of the hydrogenation performance of toluene catalysts according to the invention (A1, B1) and comparison with non-compliant catalysts
• the reactor is cooled and after triple stripping the atmosphere under nitrogen (10 minutes at 1 MPa), the effluent is collected and analyzed by X-ray fluorescence (sulfur and metals)
• the HDS ratio is defined as follows:
• HDS (%) ((% wt S) load - (% wt S) re ce) / (% wt S) load x 100 Similarly, the HDM ratio is defined as follows:
• HDM (%) ((ppm wt Ni + V) cha rge- (ppm wt Ni + V) reCet ) / (ppm wt Ni + V) cha rge x 100
• the catalysts A1 and B1 prepared according to the invention were compared in a petroleum residue hydrotreatment test with, in comparison, the performances of the catalyst E.
• the charge consists of a mixture of an atmospheric residue (RA) of Middle East origin (Arabian medium) and a vacuum residue (RSV) of Middle Eastern origin (Arabian Light).
• the feedstock is characterized by high contents of Conradson carbon (14.4% by weight) and asphaltenes (6.1% by weight) and a high amount of nickel (25 ppm by weight), vanadium (79 ppm by weight) and sulfur (3.90% by weight).
• the full characteristics of this load are reported in Table 7.
• Table 7 Characteristics of RA AM / RSV AL Loads Used for Testing

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