JP2011522688A - 含酸劣質原油改質触媒、その製造方法、およびその応用 - Google Patents
含酸劣質原油改質触媒、その製造方法、およびその応用 Download PDFInfo
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- JP2011522688A JP2011522688A JP2011509840A JP2011509840A JP2011522688A JP 2011522688 A JP2011522688 A JP 2011522688A JP 2011509840 A JP2011509840 A JP 2011509840A JP 2011509840 A JP2011509840 A JP 2011509840A JP 2011522688 A JP2011522688 A JP 2011522688A
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- catalyst
- acid
- crude oil
- medium pore
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- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- 239000010779 crude oil Substances 0.000 title claims abstract description 90
- 239000002253 acid Substances 0.000 title claims abstract description 76
- 238000002407 reforming Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 92
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 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 18
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 10
- 239000013335 mesoporous material Substances 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 41
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000001833 catalytic reforming Methods 0.000 claims description 28
- 239000004927 clay Substances 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
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- 239000000047 product Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052621 halloysite Inorganic materials 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 239000011959 amorphous silica alumina Substances 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011799 hole material Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 23
- 150000007524 organic acids Chemical class 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 6
- 235000005985 organic acids Nutrition 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 28
- 239000002585 base Substances 0.000 description 15
- 239000011575 calcium Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 8
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 238000001694 spray drying Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
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- 150000007522 mineralic acids Chemical class 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical group [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
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- 238000010408 sweeping Methods 0.000 description 1
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
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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
- B01J21/14—Silica and magnesia
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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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
- B01J35/615—100-500 m2/g
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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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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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
- B01J35/638—Pore volume more than 1.0 ml/g
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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
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Abstract
Description
ナトリウム水ガラス:市販品、SiO2 濃度26.0重量%、モジュール(module)3.2
ハロイサイト:Suzhou Kaolin Company製、固形成分含有量74.0重量%
擬似ベーム石:Shandong Aluminum Plant製工業製品、固形成分含有量62.0重量%
アルミナゾル:Sinopec Catalyst Company Qilu Division製、Al2 O3 含有量21.5重量%
実施例1〜6によれば、本発明が、耐熱性無機酸化物も粘土も含まない劣質原油接触改質触媒、並びにその調製方法を提供することが判る。
実施例10〜12では、本発明の接触改質触媒の接触改質効果を示す。
実施例13〜15では、本発明の接触改質触媒の接触改質効果を示す。
実施例16〜18では、本発明の接触改質触媒の接触改質効果を示す。
Claims (19)
- アルカリ土類金属酸化物と、シリカと、アルミナとを含有する無形性物質であり、
酸化物の重量パーセントに基づいて、無水化学式(0〜0.3)Na2 O・(1〜50)MO・(6〜58)Al2 O3 ・(40〜92)SiO2 (式中、Mは、Mg、Ca、およびBaから選択される一つまたは複数の元素を示す)を有し、
比表面積が200〜400m2 /gであり、
孔容積が0.5〜2.0ml/gであり、
平均孔径が8〜20nmであり、
最確孔径が5〜15nmであることを特徴とする中孔材料。 - 酸化物の重量パーセントに基づいて、無水化学式(0〜0.2)Na2 O・(2〜30)MO・(6〜35)Al2 O3 ・(60〜92)SiO2 を有することを特徴とする請求項1に記載の中孔材料。
- 酸化物の重量パーセントに基づいて、Na2 Oを0.1〜0.2重量%、SiO2 を60〜85重量%、Al2 O3 を6〜20重量%含むことを特徴とする請求項2に記載の中孔材料。
- 酸化物の重量パーセントに基づいて、MOを5〜30重量%含むことを特徴とする請求項2に記載の中孔材料。
- 上記アルカリ土類金属Mは、MgおよびCaからなる群から選択されることを特徴とする請求項1に記載の中孔材料。
- 上記孔容積が1.0〜2.0ml/gであり、
上記平均孔径が10〜20nmであり、
上記最確孔径が10〜15nmであることを特徴とする請求項1に記載の中孔材料。 - 室温から85℃の範囲の温度でアルミ源、シリカ源、およびアルカリ土類金属溶液を中和してゲルを形成する工程と、
酸またはアルカリを用いてゲルの終末pHを7〜9に調整する工程と、
室温から90℃の範囲の温度で1〜10時間熟成させる工程と、
得られた固体沈殿物のアンモニア交換によって不純物イオンを取り除いてアンモニア交換ゲルを得る工程と、
またはさらに乾燥して焼成する工程とを備えることを特徴とする請求項1に記載の中孔材料の調製方法。 - 上記アルミ源は、硝酸アルミニウム、硫酸アルミニウム、塩化アルミニウム、およびアルミン酸ナトリウムからなる群から選択される一つまたは複数の種類であり、
上記シリカ源は、水ガラス、ケイ酸ナトリウム、テトラエチルシラン(silicon tetraethyl)、およびシリカからなる群から選択される一つまたは複数の種類であり、
上記酸は、硫酸、塩酸、および硝酸からなる群から選択される一つまたは複数の種類であり、
上記アルカリは、アンモニア水、水酸化カリウム、および水酸化ナトリウムからなる群から選択される一つまたは複数の種類であることを特徴とする請求項7に記載の方法。 - 全量に対して、請求項1〜6の何れか一項に記載の中孔材料を1〜95重量%、耐熱性無機酸化物を0〜99重量%、粘土を0〜70重量%含むことを特徴とする接触改質触媒。
- 全量に対して、上記中孔材料を10〜50重量%、耐熱性無機酸化物を10〜70重量%、粘土を0〜60重量%含むことを特徴とする請求項9に記載の接触改質触媒。
- 全量に対して、上記中孔材料を30〜50重量%、耐熱性無機酸化物を20〜40重量%、粘土を30〜50重量%含むことを特徴とする請求項10に記載の接触改質触媒。
- 上記耐熱性無機酸化物は、アルミナ、シリカ、および無定形シリカ−アルミナからなる群から選択される一つまたは複数の種類であり、
上記粘土は、カオリン、ハロイサイト、モンモリロナイト、珪藻岩、エンデライト、サポナイト、レクトライト、海泡石、アタパルガイト、水滑石、およびベントナイトからなる群から選択される一つまたは複数の種類の混合物であることを特徴とする請求項9に記載の接触改質触媒。 - 耐熱性無機酸化物の全部または一部および/またはその前駆体と水とを混合してスラリーにする工程と、
粘土を添加するまたは添加しない工程と、
中孔材料を添加する工程と、
得られたスラリーを乾燥させる工程と、
焼成する工程とを備え、
中孔材料の添加前、粘土の添加前または添加後に酸を添加してスラリーのpHを1〜5に調整し、
スラリーを30〜90℃で0.1〜10時間熟成させ、
熟成工程後、残存耐熱性無機酸化物および/またはその前駆体を添加し、
各成分の量によって、最終触媒が、全量に対して、上記中孔材料を1〜95重量%、耐熱性無機酸化物を0〜99重量%、粘土を0〜70重量%含むようになることを特徴とする請求項9に記載の触媒の調製方法。 - 熟成工程前、耐熱性無機酸化物の一部および/またはその前駆体を添加し、
熟成工程後、残存耐熱性無機酸化物および/またはその前駆体を添加し、
先に添加した一部と後で添加した一部によって、先に添加した耐熱性無機酸化物と後で添加した耐熱性無機酸化物との重量比が、触媒中で1:0.1〜10となることを特徴とする請求項13に記載の方法。 - 請求項1に記載の中孔材料または請求項9〜12の何れか一項に記載の接触改質触媒を用いて含酸劣質原油を改質する方法であって、
原油を100〜250℃に予熱する工程と、
反応炉に導入して請求項1に記載の中孔材料または請求項9〜12の何れか一項に記載の接触改質触媒と接触させて、接触改質を行う工程と、
反応後、反応石油およびガスとコークス化触媒とに分離する工程とを備え、
分離反応石油およびガスに対して後続の分離を行い、軽産物分と脱酸化・脱金属化された原油を得ると共に、
分離触媒を回収・炭化によって再生した後に再循環させることを特徴とする方法。 - 上記接触改質は、反応温度が300〜600℃、反応圧力が0.15〜0.4MPa、重量空間速度が1〜150h-1、炭化水素油に対する触媒の質量比が1〜30で行われることを特徴とする請求項15に記載の方法。
- 上記接触改質は、反応温度が350〜520℃、反応圧力が0.15〜0.35MPa、重量空間速度が1〜100h-1、炭化水素油に対する触媒の質量比が2〜15で行われることを特徴とする請求項16に記載の方法。
- 上記原油は、全酸価が0.5mgKOH/gを超え、コンラドソン炭素数(conradson carbon number) が3重量%を超えることを特徴とする請求項15に記載の方法。
- 上記原油は、全酸価が1mgKOH/gを超え、コンラドソン炭素数が5重量%を超え、Ni含有量が10μg/gを超え、Fe含有量が10μg/gを超え、Ca含有量が10μg/gを超えることを特徴とする請求項18に記載の方法。
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JP2011212648A (ja) * | 2010-04-02 | 2011-10-27 | Sankyo Hagata Kogyo:Kk | プラスチック油化用シリカアルミナ触媒及びそれを用いたプラスチック油化装置、プラスチック油化方法 |
JP2019055401A (ja) * | 2017-09-21 | 2019-04-11 | 水澤化学工業株式会社 | 二金属分散Al酸化物からなる排ガス浄化用触媒担体 |
JP7061299B2 (ja) | 2017-09-21 | 2022-04-28 | 水澤化学工業株式会社 | 二金属分散Al酸化物からなる排ガス浄化用触媒担体 |
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CA2724999C (en) | 2016-11-08 |
US20110139682A1 (en) | 2011-06-16 |
KR20110018905A (ko) | 2011-02-24 |
US9259711B2 (en) | 2016-02-16 |
CA2724999A1 (en) | 2009-11-26 |
WO2009140847A1 (zh) | 2009-11-26 |
KR101536187B1 (ko) | 2015-07-13 |
BRPI0912829A2 (pt) | 2015-10-13 |
BRPI0912829B1 (pt) | 2023-09-26 |
JP5587297B2 (ja) | 2014-09-10 |
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