WO2007006473A1 - Process for improving the quality as a fuel of hydrotreated hydrocarbon blends - Google Patents
Process for improving the quality as a fuel of hydrotreated hydrocarbon blends Download PDFInfo
- Publication number
- WO2007006473A1 WO2007006473A1 PCT/EP2006/006577 EP2006006577W WO2007006473A1 WO 2007006473 A1 WO2007006473 A1 WO 2007006473A1 EP 2006006577 W EP2006006577 W EP 2006006577W WO 2007006473 A1 WO2007006473 A1 WO 2007006473A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- hydrotreated
- ranging
- alumina
- silico
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 230000008569 process Effects 0.000 title claims abstract description 51
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 27
- 239000000446 fuel Substances 0.000 title claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 239000010457 zeolite Substances 0.000 claims abstract description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 22
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 21
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 19
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 150000002739 metals Chemical class 0.000 claims abstract description 15
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- 150000001491 aromatic compounds Chemical class 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000001588 bifunctional effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 35
- 150000001875 compounds Chemical class 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 230000009467 reduction Effects 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 238000009835 boiling Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- -1 alkyl-benzene compounds Chemical class 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 235000010210 aluminium Nutrition 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000004996 alkyl benzenes Chemical group 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000012438 extruded product Nutrition 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 101100352919 Caenorhabditis elegans ppm-2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001137251 Corvidae Species 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- YZWGEMSQAMDWEM-UHFFFAOYSA-N benzo[c]chrysene Chemical group C1=CC2=CC=C3C=CC=CC3=C2C2=C1C1=CC=CC=C1C=C2 YZWGEMSQAMDWEM-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 235000015108 pies Nutrition 0.000 description 1
- 125000003367 polycyclic group Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- 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
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- 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
- B01J21/12—Silica and alumina
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7469—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7669—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/307—Cetane number, cetane index
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Definitions
- the present invention relates to a process for improv- ing the quality as a fuel of hydrotreated hydrocarbon blends.
- it relates to a partial dearomatiza- tion process of hydrotreated hydrocarbon blends with the limited formation of products have a lower molecular weight with respect to the charge.
- the hydrotreated hydrocarbon blends can be hydrotreated oil cuts or hydrotreated cuts of a petrochemical origin. This process comprises the enrichment of blends resulting in alkyl-benzene compounds, at least partially deriving from the conversion of the naph- tho-aromatic structures contained in said hydrotreated blends.
- the process of the present invention produces an increase in the cetane index and a reduction in the density of the blends obtained, wherein said reduction in the density is equivalent to that obtained by means of total dearomatization, but it is effected with a much lower hy- drogen consumption.
- the process is carried out in the pres- ence of a bifunctional catalytic system comprising one or more metals selected from Pt, Pd, Ir, Rh, Ru and Re, and a silico-aluminate of an acidic nature selected from a micro- mesoporous silico-alumina having a suitable composition and a zeolite belonging to the MTW family.
- the catalysts generally used in this process consist of a metallic phase deposited on a carrier having a medium- low acidity. It should be pointed out, however, that the hydrogenation of the aromatic structures causes high hydrogen consumptions .
- the catalysts used in this case are of the bifunctional type, i.e. consisting of metals which have a dehydrogenating function supported on a generally more acid phase than that of the carriers used in the previous case .
- MI2004A000798 describes the upgrading of distillates containing naphthene compounds by the transformation of these compounds into the corresponding paraffinic derivatives, which uses catalysts containing Pt, Pd, Ir, Rh, Ru and Re and an acid silico-aluminate selected from a suitable micro-mesoporous silico-alumina and an MTW zeolite.
- the Applicants have novr unexpectedly found a process which produces a substantial improvement in the properties of hydrotreated hydrocarbon cuts, in particular in terms of cetane index (number) , density and distillation curve, which has proved to be equivalent to that obtained by the simple hydrogenation of aromatic structures.
- the process, object of the invention causes a negligible formation of low molecular weight products and requires lower hydrogen consumptions with respect to the known processes .
- a first object of the present invention therefore relates to a process for improving the properties as a fuel of hydrotreated hydrocarbon blends which comprises the treatment of said blends, in the presence of hydrogen, with a catalytic system comprising: a) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re b) a silico-aluminate of an acidic nature selected from a zeolite belonging to the MTW group and a completely amorphous micro-mesoporous silico-alumina having a molar ratio SiO 2 /Al 2 O 3 ranging from 30 to 500, a surface area greater than 500 m 2 /g, a pore volume ranging from 0.3 to 1.3 ⁇ nl/g, an average pore diameter lower than 40 A.
- a catalytic system comprising: a) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re b) a silico-aluminate of an acidic nature selected
- the hydrotreated hydrocarbon blends used in the process of the present invention can derive from oil cuts or cuts of a petrochemical origin which have been subjected to hydrotreatment .
- the process of the present invention allows a substantial increase in the cetane index (number) to be obtained together with a decrease in the density and T95 of the hydrotreated hydrocarbon blends .
- the blends thus obtained are, among other things, enriched in alkylbenzene compounds which at least partially derive from the par- tially hydrogenated polycyclic aromatic compounds of the benzonaphthene type present in the hydrocarbon cuts which have undergone a hydrotreatment.
- the catalysts used in the present invention are therefore unexpectedly capable of directing the process towards the formation of alkylbenzene structures by the hydrodecy- clization of the naphthene ring of naphtho-benzene or di- naphtho-benzene structures, thus obtaining the best possible compromise between hydrogen consumption and improvement in the properties of the product, at the same time limiting both the complete hydrogenation reaction of the aromatic rings and the cracking reaction to form light products .
- the formation of light products by means of the hydrocracking reaction should this take place, would, in this case, have a double disadvantage: a decrease in the yields in the product of interest and a greater hydrogen consumption.
- the component of an acidic nature (b) of the catalytic composition used in the present invention can be selected from zeolites of the MTW type: the MTW group is described in Atlas of zeolite structure types, W.M.Meier and D.H.Olson, 1987, Butterworths .
- the zeolite of the MTW structural type which can be appropriately used in the present invention, is a silico-aluminate with a molar ratio SiO 2 /Al 2 O 3 greater than or equal to 20. This zeolite and its preparation are described in A. Katovic and G. Giordano, Chem. Ind. (Dekker) (Synthesis of Porous Materials) 1997, 69, 127-137.
- the zeolite ZSM-12 described in US 3,832,449 and in Ernst et al . , Zeolites, 1987, Vol. 7, September, is used.
- the zeolite In the preparation of the catalytic composition, the zeolite is used in its acidic form. If the component of an acidic nature (b) is a silico- alu ⁇ iina, a preferred aspect is for the molar ratio
- the SiO 2 /Al 2 O 3 to range from 50 to 300.
- the silico-alumina has a porosity ranging from 0.4 to 0.5 ml/g.
- MSA Completely amorphous micro-mesoporous silico-aluminas which can be used for the present invention, called MSA, and their preparation are described in US 5,049,536, EP 659,478, EP 812,804. Their XRD spectrum from powders does not have a crystalline structure and does not show any peak.
- Catalytic compositions which can be used in the present invention, wherein the acid component is a silico- alumina of the MSA type are described in EP 582,347.
- the silico-aluminas which can be adopted for the process of the present invention can be prepared, according to EP 659,478, starting from tetra-alkylammonium hydroxide, an aluminum compound hydrolyzable to Al 2 O 3 , and a silicon compound hydrolyzable to SiO 2 , wherein said tetra- alkylammonium hydroxide is a tetra (C 2 -C 5 ) alkylammonium hydroxide, said hydrolyzable aluminum compound is an aluminum tri (C 2 -C 4 ) -alkoxide and said hydrolyzable silicon compound is a tetra (Ci-C 5 ) alkylorthosilicate: these reagents are subjected to hydrolysis and gelification operating at a temperature equal to or higher than the boiling point, at atmospheric
- the procedure comprises preparing an aqueous solution of tetra-alkylammonium hydroxide and aluminum trialkoxide and the tetra-alkylorthosilicate is added to this aqueous solution, operating at a temperature lower than the hydrolysis temperature, with a quantity of reagents which is such as to respect the molar ratios SiO 2 /Al 2 O 3 from 30/1 to 500/1, tetra-alkylammonium hydroxide/Si0 2 from 0.05/1 to 0.2/1 and H 2 O/SiO 2 from 5/1 to 40/1, and the hydrolysis and gelification are triggered by heating ⁇ * to a temperature higher than about 65°C to about 110 0 C, operating in an autoclave at the autogenous pressure of the system or at atmospheric pressure in a reactor equipped with a con- denser.
- the metallic component of the catalytic compositions used in the process of the present invention is selected from Pt, Pd, Ir, Ru, Rh, Re and their mixtures.
- the metal is platinum, irid- ium or their mixtures.
- the metal or mixture of metals is preferably in a quantity ranging from 0.1 to 5% by weight with respect to the total weight of the catalytic composition, and prefera- bly ranges from 0.3 to 1.5%.
- the weight percentage of the metal, or metals refers to the metal content expressed as metallic element; in the final catalyst, after calcination, said metal is in the form of an oxide .
- the catalyst is activated by the known techniques, for example by means of a reduction treatment, and preferably by drying and subsequent reduction. The drying is carried out in an inert atmosphere at temperatures ranging from 25 to 100 0 C, whereas the reduc- tion is obtained by thermal treatment of the catalyst in a reducing atmosphere (H 2 ) at a temperature ranging from 300 to 45O 0 C, and a pressure preferably ranging from 1 to 50 atm.
- a reducing atmosphere H 2
- the component of an acidic nature (b) of the catalyst used in the process of the present invention can be in the form of an extruded product with traditional ligands, such as for example aluminum oxide, bohemite or pseudobohemite .
- the extruded product can be prepared according to the methods well known to experts in the field.
- the component of an acidic nature (b) and the ligand can be premixed in weight ratios ranging from 30:70 to 90:10, preferably from 50:50 to 70:30. At the end of the mixing, the product obtained is consolidated into the desired final form, for example in the form of extruded pellets or tablets.
- the component of an acid nature (b) is wet with an aqueous solution of a compound of the metal, operating, for example, at room temperature, and at a pH ranging from 1 to 4.
- the aqueous solution preferably has a metal concentration expressed as g/1 ranging from 0.2 to 2.0.
- the resulting product is dried, preferably in air, at room temperature, and is calcined in an oxidizing atmos- phere at a temperature ranging from 200 to 600 0 C.
- the acid component (b) is suspended in an alcohol solution containing the metal. After impregnation, the solid is dried and calcined. According to the ionic exchange technique, the acid component (b) is suspended in an aqueous solution of a complex or salt of the metal, operating at room temperature and at a pH ranging from 6 to 10. After the ionic exchange, the solid is separated, washed with water, dried and finally thermally treated in an inert or oxidizing atmos- phere. Temperatures useful for the purpose are those rang- ing from 200 to 600 0 C.
- Metal compounds which can be used in the preparations described above are: H 2 PtCl 6 , Pt (NH 3 ) 4 (OH) 2 , Pt(NH 3 J 4 Cl 2 ,
- the impregnation is carried out as follows: the acid component
- (b) also in extruded form, is wet with a solution of a compound of a first metal, the resulting product is dried, it is optionally calcined, and is impregnated with a solu- tion of a compound of a second metal. It is dried and a calcination is then effected in an oxidizing atmosphere at a temperature ranging from 200 to 600 0 C.
- a single aqueous solution containing two or more compounds of different metals can be used for contemporaneously intro- ducing said metals .
- the hydrotreated hydrocarbon blends which can be subjected to the process of the present invention are blends having boiling points ranging from about 50 0 C to about 450 0 C, preferably from 150 0 C to 400 0 C, more preferably from 180 0 C to 38O 0 C at atmospheric pressure.
- the hydrocarbon cuts can be obtained by the hydrotreatment of oil cuts such as naphthas, diesel, kerosene, jet fuel, light cycle oil (LCO) , HVGO or FCC heavy fraction, or by the hydrotreatment of cuts of a pet- rochemical origin, such as, for example, FOK (fuel oil cracking) .
- oil cuts such as naphthas, diesel, kerosene, jet fuel, light cycle oil (LCO) , HVGO or FCC heavy fraction
- LCO light cycle oil
- HVGO light cycle oil
- FCC heavy fraction a pet- rochemical origin
- the hydrocarbon cuts subjected to hydrotreatment for providing the hydrotreated hydrocarbon blends used in the process of the present invention have a content of aromatic compounds preferably greater than 20%, and even more preferably greater than 40%, mainly consisting of mono-aromatic compounds, diaromatic compounds and, to a lesser degree, triaromatic compounds.
- the hydrotreatment varies the nature and composition of the hydrocarbon cut subjected thereto and, among other things, enriches the cut in benzonaphthene compounds .
- Hydrotreatment is a process which is well-known to experts in the field and is described, for example, in Ca- talysis-Science and Technology, Edited by R. Anderson and M. Boudart, Volume 11, Springer-Verlag, of 1996. It can be effected in one or more fixed bed reactors, and the catalytic beds can contain the same or different catalysts.
- Catalysts based on metallic compounds of Group VI, and/or Group VIII, are usually used, on a carrier, preferably an amorphous carrier, such as, for example, alumina or silica- alumina.
- Metals which can be well used are, for example, nickel, cobalt, molybdenum and tungsten. Examples of suitable catalysts and their preparation are described in Hy- drocracking Science and Technology, J. Scherzer and A.J. Gruia, Marcel Dekker, 1996.
- the hydrotreatraent catalysts are used in sulfidated form.
- the sulfidation can be obtained, for example, by- sending a suitable charge onto the catalyst, containing a sulfurated compound such as Dimethyldisulfide (DMDS) , Di- methy ⁇ sulfoxide (DMSO) or other compounds which, upon decomposing, lead to the formation of H 2 S.
- DMDS Dimethyldisulfide
- DMSO Di- methy ⁇ sulfoxide
- the hydrotreatment is preferably carried out at a temperature ranging from 200 0 C to 400 0 C.
- the pressure normally range from 20 to 100 bars, in relation to the catalyst used, an expert in the field can easily identify the best conditions for the catalyst selected.
- the charge undergoes saturation reactions of the aromatic rings with a reduction in the content of aromatic carbon and an enrichment in naphtho-aromatic compounds .
- the process of the present invention which allows an increase in the cetane number, a decrease in the density and T95 of hydrotreated hydrocarbon blends, is preferably carried out at a temperature ranging form 240 to 380 0 C, at a pressure ranging from 10 to 100 atm, at a WHSV ranging from 0.5 to 5 hours "1 and with a ratio between hydrogen and charge (H 2 /HC) ranging from 400 to 2000 Nlt/kg.
- the temperature preferably ranges from 250 to 330 0 C when the acid component (b) is a zeolite of the MTW type, whereas it preferably ranges from 300 to 380 0 C when the acid component (b) is a silico-alumina .
- Example 1 The following experimental examples are provided for a better illustration of the present invention.
- Example 1 The following experimental examples are provided for a better illustration of the present invention.
- the slurry ob- tained is homogeneous, with a milky appearance.
- the slurry is centrifuged.
- the discharged solid is washed by redisper- sion in water, centrifuged again, dried at 120 0 C and calcined at 55O 0 C for 5 hours.
- the solid obtained Upon X-ray diffraction analysis, the solid obtained proves to consist of pure ZSM-12.
- the solid obtained is subsequently exchanged into ammonia form by treatment with a solution of ammonium acetate 3 M.
- a volume of 200 ml of this solution was added to 30 g of the zeolite prepared as described above, so that all the solid was covered by the solution, to avoid heterogeneity in the platinum distribution.
- the suspension thus obtained was maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
- the solvent was subsequently removed by heating to about 70 0 C under vacuum.
- the dry product was finally calcined under a stream of air with the following temperature profile 25-350 0 C in two hours, 360 0 C for 3 hours.
- a ZSM-12 zeolite is obtained, containing 1.0% by weight of platinum.
- a volume of 400 ml of this solution was added to 30 g of the solid prepared as described in the previous step (a) , so that all the solid is covered by the solution, in order to avoid heterogeneity in the iridium distribution.
- the sus- pension thus obtained is maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature .
- the solvent is subsequently removed by heating to about 70 0 C under vacuum.
- the dry product is finally cal- cined under a stream of air with the following temperature profile 25-350 0 C in two hours, 350 0 C for 2 hours, 350-400 0 C in 50 min., at 400 0 C for 3 hours.
- a ZSM-12 zeolite is obtained, containing 1% of Iridium.
- the product is left to rest for about 6-8 hours and is then dried by maintaining it in a stream of air at 100 0 C until the weight becomes constant. It is finally calcined in a muffle at 55O 0 C for 8 hours in air.
- the solid Upon X-ray analysis, the solid proves to be sub- stantially amorphous, the XRD spectrum from powders does not have a crystalline structure and does not show any peak.
- the suspension thus obtained was maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
- the solvent was subsequently removed by heating to about 7O 0 C under vacuum.
- the dry product was finally calcined under a stream of air with the following temperature profile 25- 350 0 C in two hours, 350 0 C for 2 hours, 350-400 0 C in 50 min. , 400 0 C for 3 hours.
- a volume of 400 ml of this solution was added to 30 g of the solid prepared as described in the previous step (a) , so that all the solid is covered by the solution, in order to avoid heterogeneity in the iridium distribution.
- the suspension thus obtained is maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
- the solvent is subsequently removed by heating to about 70 0 C in a stream of air.
- the dry product is finally calcined under a stream of air with the following temperature profile 25-350 0 C in two hours, 350 0 C for 2 hours, 350-400 0 C in 50 min. , at 400 0 C for 3 hours.
- a silico-alumina of the MSA type is obtained, containing 1% of Ir.
- An aluminum borate is prepared in accordance with EP 667,184 using the following procedure: 40 g of alumina in extruded form with a surface area of 200 m 2 /g are immersed in 80 ml of an aqueous solution containing 2.06 g of H 3 BO 3 and left at 70 0 C for 23 hours. The solid is separated from the water by filtration and is then washed on a filter, dried at 120 0 C for 16 hours and calcined at 55O 0 C for 3 hours.
- the catalytic tests were carried out on a continuous laboratory plant shown in Figure 1.
- the system consisted of a tubular fixed bed reactor (4) with a useful volume of the charge of 20 cm 3 corresponding to a height of the catalytic bed in the isotherm section of 10 cm.
- the feeding of the charge, contained in the tank (1) and hydrogen to the reactor are effected by means of a dosage pump (2) and a mass flow meter, respectively.
- the system is also equipped with two gas lines (air and nitrogen) which are used in the re- generation phase of the catalyst.
- the reactor operates in an equicurrent down flow system.
- the temperature of the reactor is regulated by means of an oven with two heating elements (3) whereas the temperature control of the catalytic bed is effected by means of a thermocouple (10) posi- tioned inside the reactor.
- the pressure of the reactor is regulated by means of a valve (8) situated downstream of the reactor.
- the reaction products are collected in a separator (5) which operates at room temperature and atmospheric pressure.
- the products leaving the separator (5) pass into a condenser (6) cooled to 5 0 C and are subsequently sent to a gas meter (CL.) (7) and then to the blow-down (B.D.).
- (9) is the breakage disk.
- the distribution of the products and conversion level are determined by means of mass balance and gas chromatographic analysis of the reaction products.
- Catalysts A, B, C, D and E of examples 1, 2, 3, 4 and 5 were tested in the process of the present invention, in the equipment described above, using hydrotreated LCO as substrate, whose characteristics are indicated in the fol- lowing Table A.
- Table A
- Diaromatic compounds w% 9.1 Triaromatic compounds, w% 0.6
- the percentage of alkylbenzenes in the hydrotreated charge is equal to 7.6% of the aromatic compounds present.
- the hydrotreated charge was obtained by hydrogenation of a commercial LCO, whose characteristics are indicated in Table B, effected in a fixed bed pilot plant with two reactors (RXl, RX2 ) using a commercial desulfuration catalyst based on nickel and molybdenum (Criterion CR424) under the following operative conditions:
- Triaromatic compounds w% 4.8
- the catalysts were activated as follows : 1) 1 hour at room temperature in a nitrogen stream;
- the temperature is kept constant at 380 0 C for 3 hours in a hydrogen stream, and is then cooled to 200 0 C.
- the pressure in the reactor is maintained at between 2.0 and 6.0 MPa (20 and 60 atm) .
- the Yield 180+ 0 C SIMDIST 2887 is the percentage of the products with a boiling point higher than 180 0 C, deter- mined by simulated distillation SIMDIST 2887;
- the Cetane Index (4v) 180+ 0 C is the cetane number of the products, with a boiling point higher than 180 0 C, determined by means of the distillate D86 and density at 15°C;
- SIMDIST 2887 is the temperature at which 95% of the products are distilled, determined by simulated dis- tillation SIMDIST 2887.
- the data in the first line of Table B refer to the characteristics of the hydrotreated blend before being fed to the process of the present invention.
- the data indicated in the last column of Table C represent the relative hydrogen consumption taking 100% as the hydrogen consumption obtained using the comparative cata- lyst E at 280 0 C.
- the catalytic tests were carried out on a pilot plant in continuous.
- the system consisted of a 1825 mm fixed bed tubular reactor having an internal diameter of 40 mm with a useful charge volume of 800 cm 3 .
- the feeding of the charge, contained in the tank and of the hydrogen to the reactor are effected by means of a dosage pump and mass flow meter, respectively.
- the reactor runs in an eguicurrent down flow system.
- the temperature of the reactor is regulated by means of six electrically heated outer blocks whereas the temperature control of the catalytic bed is effected by means of 18 thermocouples positioned inside the reactor in a sheath having an outer diameter of 10 mm.
- the pressure of the reactor is regulated by means of a valve situated downstream of the reactor.
- the gases are separated in a separator which operates under pressure and the reaction products are collected in a separator which operates at room temperature and atmospheric pressure.
- the products leaving the high and low pressure separator pass into a cooled condenser and are subsequently sent to a gas meter and then to the blow-down.
- the distribution of the products and the conversion level are determined by means of mass balance and gas chromatographic analysis of the reaction products .
- the hydrotreated charge, described in Example 6, in Table A, and the hydrogen were passed onto catalyst D based on Ir supported on mesoporous amorphous MSA silico-alumina, prepared according to Example 4. 255 g of catalyst pelleted and granulated to 0.5-1 mm (corresponding to a volume of 420 ml) diluted 1/1 v/v with SiC (carborundum) , were charged.
- the catalyst was activated as follows :
- Diaromatic compounds w% 0.2 Triaromatic compounds, w% 0.0
- Triaromatic compounds w% 0.0
- the products obtained according to Example 7 have a higher content of aromatic compounds and a much lower hydrogen content .
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Abstract
Description
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Priority Applications (10)
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DE602006014151T DE602006014151D1 (en) | 2005-07-08 | 2006-07-03 | METHOD FOR IMPROVING THE QUALITY OF HYDROCARBONIZED HYDROCARBON BLENDS AS FUEL |
CN200680029057.8A CN101238201B (en) | 2005-07-08 | 2006-07-03 | Process for improving the quality as a fuel of hydrotreated hydrocarbon blends |
EA200702690A EA013273B1 (en) | 2005-07-08 | 2006-07-03 | Process for improving the quality as a fuel of hydrotreated hydrocarbon blends |
BRPI0612664-2A BRPI0612664A2 (en) | 2005-07-08 | 2006-07-03 | process for improving the properties of hydrotreated hydrocarbon mixtures as fuel |
DK06762434.6T DK1902116T3 (en) | 2005-07-08 | 2006-07-03 | Process for improving the quality of hydrogen-treated hydrocarbon mixtures as a fuel |
CA002614367A CA2614367A1 (en) | 2005-07-08 | 2006-07-03 | Process for improving the quality as a fuel of hydrotreated hydrocarbon blends |
AT06762434T ATE466920T1 (en) | 2005-07-08 | 2006-07-03 | METHOD FOR IMPROVING THE QUALITY OF HYDROGENATION-TREATED HYDROCARBON BLENDS AS FUEL |
JP2008519859A JP2009500478A (en) | 2005-07-08 | 2006-07-03 | Method for improving the quality of a hydrotreated hydrocarbon mixture as a fuel |
EP06762434A EP1902116B1 (en) | 2005-07-08 | 2006-07-03 | Process for improving the quality as a fuel of hydrotreated hydrocarbon blends |
MX2008000348A MX2008000348A (en) | 2005-07-08 | 2006-07-03 | Process for improving the quality as a fuel of hydrotreated hydrocarbon blends. |
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IT001295A ITMI20051295A1 (en) | 2005-07-08 | 2005-07-08 | PROCESS TO IMPROVE QUALITIES AS HYDROCARBED HYDROCARBONIC MIXTURE FUEL |
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EP (1) | EP1902116B1 (en) |
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Also Published As
Publication number | Publication date |
---|---|
ES2345943T3 (en) | 2010-10-06 |
CN101238201A (en) | 2008-08-06 |
DK1902116T3 (en) | 2010-08-30 |
CA2614367A1 (en) | 2007-01-18 |
US20070187295A1 (en) | 2007-08-16 |
EP1902116B1 (en) | 2010-05-05 |
ATE466920T1 (en) | 2010-05-15 |
DE602006014151D1 (en) | 2010-06-17 |
JP2009500478A (en) | 2009-01-08 |
BRPI0612664A2 (en) | 2012-10-02 |
MX2008000348A (en) | 2008-03-07 |
ITMI20051295A1 (en) | 2007-01-09 |
US8236171B2 (en) | 2012-08-07 |
CN101238201B (en) | 2013-01-09 |
PT1902116E (en) | 2010-08-11 |
EA013273B1 (en) | 2010-04-30 |
EP1902116A1 (en) | 2008-03-26 |
EA200702690A1 (en) | 2008-06-30 |
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