CN101448924A - Hydrorefining process - Google Patents
Hydrorefining process Download PDFInfo
- Publication number
- CN101448924A CN101448924A CNA2007800178587A CN200780017858A CN101448924A CN 101448924 A CN101448924 A CN 101448924A CN A2007800178587 A CNA2007800178587 A CN A2007800178587A CN 200780017858 A CN200780017858 A CN 200780017858A CN 101448924 A CN101448924 A CN 101448924A
- Authority
- CN
- China
- Prior art keywords
- oil
- quality
- hydrogen
- catalyzer
- inorganic oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 27
- 239000003921 oil Substances 0.000 claims abstract description 95
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 51
- 239000011148 porous material Substances 0.000 claims description 32
- 239000005864 Sulphur Substances 0.000 claims description 23
- 241001465754 Metazoa Species 0.000 claims description 15
- 235000013311 vegetables Nutrition 0.000 claims description 15
- 239000000314 lubricant Substances 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000005457 triglyceride group Chemical group 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000004438 BET method Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 45
- 150000002739 metals Chemical class 0.000 abstract description 4
- 229910021472 group 8 element Inorganic materials 0.000 abstract 1
- 230000000737 periodic effect Effects 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 83
- 230000000694 effects Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000008676 import Effects 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- -1 fatty acid ester Chemical class 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 3
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010696 ester oil Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 102000004895 Lipoproteins Human genes 0.000 description 2
- 108090001030 Lipoproteins Proteins 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 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 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000007324 demetalation reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
-
- 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
-
- 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
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- 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
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
-
- 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
- B01J35/633—Pore volume less than 0.5 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
- B01J35/63—Pore volume
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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
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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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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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
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The present invention discloses a hydrorefining process which is characterized in that an oil to be processed which contains an oxygen-containing hydrocarbon compound and a sulfur-containing hydrocarbon compound is brought into contact, in the presence of hydrogen, with a catalyst which contains a porous inorganic oxide containing two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and one or more metals selected from group 6A and group 8 elements of the periodic table and loaded on the porous inorganic oxide, at a hydrogen pressure of 2-13 MPa, at a liquid hourly space velocity of 0.1-3.0 h<-1>, at a hydrogen/oil ratio of 150-1500 NL/L, and at a reaction temperature of 180-380 DEG C.
Description
Technical field
[0001] the present invention relates to hydrofinishing process, in more detail, relate to the hydrofinishing process that contains from the processed oil of the lubricant component of vegetable and animals oils.
Background technology
[0002] as the countermeasure that prevents greenhouse effects of the earth, effective utilization of biomass energy gets most of the attention.In the biomass energy, biomass energy from plant can effectively utilize the hydrocarbon that is transformed into by carbonic acid gas by photosynthesis in the process of growth of plant, therefore, consider to have the character of the so-called neutral carbon that can not make the Atmospheric Carbon Dioxide increase from the viewpoint of life cycle.
[0003] about the utilization of this biomass energy, in the transport fuel field, carrying out various researchs.For example, if can use fuel from vegetable and animals oils, just can expect by playing effective function aspect the CO2 emissions reducing with the synergy of the high energy efficiency of diesel motor as diesel oil fuel.As the diesel oil fuel that utilizes vegetable and animals oils, known have fatty acid methyl ester oil (Fatty Acid Methyl Ester).Fatty acid methyl ester oil is by to belonging to the triglyceride structure of the general structure of vegetable and animals oils, carries out transesterification reaction with methyl alcohol and make under the effect of alkali etc.But, in the technology of making fatty acid methyl ester oil, such as following patent documentation 1 record, pointed out and must handle, or will spend cost and energy at aspects such as the olefiant washings of life to the glycerine of by-product.
[patent documentation 1] spy opens the 2005-154647 communique
Summary of the invention
The problem that invention will solve
[0004] in order to use, except the problems referred to above, also has following problem from the lubricant component of vegetable and animals oils or by its fuel of making as raw material.That is, generally have Sauerstoffatom in its molecule from the lubricant component of vegetable and animals oils, therefore, the oxygen composition might bring detrimentally affect to the engine material, and, often be difficult to this oxygen composition is removed to extremely low concentration.In addition, will mix with the petroleum-type hydrocarbons cut from the lubricant component of vegetable and animals oils when using,, just can not fully reduce oxygen composition in this lubricant component and the sulphur composition in the petroleum-type hydrocarbons cut if adopt in the past technology.
[0005] therefore, the objective of the invention is, provide a kind of and contain processed when oil of oxygen-containing hydrocarbon compound and sulfur-bearing hydrocarbon compound, can obtain the hydrofinishing process of the hydrofined oil that oxygen composition and sulphur composition both fully reduce in use.
Solve the means of problem
[0006] in order to solve above-mentioned problem, the invention provides hydrofinishing process, it is characterized in that, in the presence of hydrogen, make the processed oil that contains oxygen-containing hydrocarbon compound and sulfur-bearing hydrocarbon compound with contain porous inorganic oxide and on this porous inorganic oxide load be selected from the catalyzer of metal more than a kind in periodictable 6A family and the 8th family's element at hydrogen pressure 2～13MPa, liquid hourly space velocity 0.1～3.0h
-1, 180～380 ℃ of hydrogen-oil ratio 150～1500NL/L, temperature of reaction condition under contact, described porous inorganic oxide contains the element more than 2 kinds that is selected from aluminium, silicon, zirconium, boron, titanium and the magnesium.
[0007] according to hydrofinishing process of the present invention, by the processed oil that contains oxygen-containing hydrocarbon compound and sulfur-bearing hydrocarbon compound is contacted under above-mentioned certain conditions with above-mentioned specific catalyst, can obtain the hydrofined oil that oxygen composition and sulphur composition all fully reduce economically very effectively.
[0008] according to hydrofinishing process of the present invention, be benchmark with the total amount of processed oil, the content of preferred oxygen composition is 0.1～15 quality %, the content of sulphur composition is 1 quality ppm～2 quality %.If the oxygen composition of processed oil and sulphur composition are in respectively in the above-mentioned scope, then can the stable deoxy activity of long term maintenance.
[0009] in addition, according to hydrofinishing process of the present invention, consider that from the viewpoint of effectively utilizing biomass energy the oxygen-containing hydrocarbon compound is preferably the lubricant component from vegetable and animals oils.
[0010] in addition, process necessary viewpoint of energy consideration from reducing starting material, the compound shared ratio in the oxygen-containing hydrocarbon compound with triglyceride structure is preferably 90 moles more than the %.
[0011] in addition, employed catalyzer in the hydrofinishing process of the present invention, preferably it is 0.30～0.85ml/g by the pore volume that nitrogen absorption BET method records, average pore diameter is 5～11nm, is below the 35 capacity % from the pore volume of the pore below the pore diameter 3nm shared ratio in total pore volume.
[0012] and then, the porous inorganic oxide that constitutes catalyzer preferably contains phosphoric.By using the phosphorated porous inorganic oxide, can further improve the deoxy activity of catalyzer.
The invention effect
[0013] according to the present invention, provide when using the processed oil contain oxygen-containing hydrocarbon compound and sulfur-bearing hydrocarbon compound, can obtain the hydrofinishing process of the hydrofined oil that oxygen composition and sulphur composition both fully reduce economically very effectively.
Embodiment
[0014] explains preferred implementation of the present invention below.
[0015] in the present invention, use the processed oil that contains oxygen-containing hydrocarbon compound and sulfur-bearing hydrocarbon compound.As the oxygen-containing hydrocarbon compound, preferably from the lubricant component of vegetable and animals oils.In the lubricant component of the present invention, comprise natural or artificial animal-plant oil of producing, making and vegetable and animals oils composition and/or herein, by the composition of these grease production, manufacturing and the composition that adds for the performance of keeping, improve these oil products.
[0016] as lubricant component, for example can enumerate tallow, rapeseed oil, soybean oil, palm wet goods from vegetable and animals oils.In the present invention, as the lubricant component from vegetable and animals oils, can use any grease, also can be these greases waste oil later.But, consider that from the viewpoint of neutral carbon the preferred plant grease is considered from fatty acid alkyl chain carbon number and reactive viewpoint thereof, more preferably rapeseed oil, soybean oil and plam oil.Illustrated that above-mentioned grease can use a kind separately, perhaps used mixing more than 2 kinds.
[0017] lubricant component from vegetable and animals oils generally has the fatty acid triglycercide structure, also can contain other lipid acid or be processed into the lubricant component of ester bodies such as fatty acid methyl ester.But,, therefore, consider from the viewpoint that reduces CO2 emissions, as Vegetable oil lipoprotein, preferably to have the composition of triglyceride structure owing to when Vegetable oil lipoprotein is made lipid acid or fatty acid ester, can produce carbonic acid gas.In the present invention, the compound shared ratio in the oxygen-containing hydrocarbon compound that processed oil contained with triglyceride structure is preferably 90 moles more than the %, and more preferably 92 moles more than the %, more preferably 95 moles more than the %.
[0018] illustrated, in processed oil, as the oxygen-containing hydrocarbon compound, except above-mentioned lubricant component from vegetable and animals oils, can contain compound, also can contain the synthetic oil that obtains via Fischer-Tropsch reaction as raw material with the synthetic gas that contains carbon monoxide and hydrogen from chemical such as plastics or solvents.
[0019] contained oxygen composition in the processed oil is a benchmark with the total amount of processed oil, is preferably 0.1～15 quality %, 1～15 quality % more preferably, and more preferably 3～14 quality % are preferably 5～13 quality % especially.If the content of oxygen composition less than 0.1 quality %, then exists and is difficult to stably keep deoxy activity and desulphurizing activated tendency.On the other hand,, then need equipment that the water of by-product is handled, or the interaction between water and the support of the catalyst is become excessively, actively reduce or make the catalyst strength reduction thereby make if the content of oxygen composition surpasses 15 quality %.Illustrated that the content of oxygen composition can be measured with common Atomic Absorption SpectrophotometerICP, for example, sample can be transformed into carbon monoxide on platinum carbon, perhaps further be transformed into carbonic acid gas, use the thermal conductivity detector to measure then.
[0020] in addition, do not have particular restriction, can enumerate particularly, sulfide, disulphide, polysulfide, mercaptan, thiophene, thionaphthene, dibenzothiophene and their derivative etc. for sulfur-bearing hydrocarbon compound contained in the processed oil.Contained sulfur-bearing hydrocarbon compound can be single compound in the processed oil, perhaps also can be the mixture more than 2 kinds.And then, also the petroleum-type hydrocarbons cut that contains the sulphur composition can be mixed in the processed oil.
[0021], can use the cut that in the petroleum refinement operation, obtains usually as the petroleum-type hydrocarbons cut.For example, also can use that from atmospheric distillation plant or vacuum distillation apparatus, obtain and the suitable cut of boiling spread regulation or from hydrodesulfurization unit, hydroeracking unit, residual oil direct desulfurization unit, fluidized catalytic cracker etc., obtain, with the suitable cut of boiling spread of regulation.Illustrated that the cut that obtains can use a kind separately from above-mentioned each device, perhaps used mixing more than 2 kinds.
[0022] contained sulphur composition in the processed oil is a benchmark with the total amount of processed oil, is preferably 1 quality ppm～1 quality %, more preferably 15 quality ppm～0.5 quality %, more preferably 30 quality ppm～0.1 quality %.If less than 1 quality ppm, then there is the tendency that is difficult to stably keep deoxy activity in the content of sulphur composition.On the other hand, if the content of sulphur composition surpasses 1 quality %, then contained sulphur component content has the tendency of increase in the hydrofined oil, when the fuel as diesel motor etc. uses, might disadvantageous effect be arranged to engine exhaust emission control device.Illustrated that the sulphur composition among the present invention is meant the mass content of the sulphur composition that records according to the method for putting down in writing among JIS K 2541 " sulphur component testing method " or the ASTM-5453.
[0023] the sulfur-bearing hydrocarbon compound can mix with processed oil in advance, then this mixture is imported in the reactor of hydro-refining unit, perhaps also can supply with the sulfur-bearing hydrocarbon compound at the leading portion of reactor when importing to processed oil in the reactor.
[0024] the processed oil that uses among the present invention preferably contains boiling point at the cut more than 300 ℃, in addition, does not preferably contain the heavy ends that boiling point surpasses 700 ℃.Do not contain the processed oil of boiling point if use, then have the tendency that causes being difficult to obtain satisfied yield owing to overcracking at the cut more than 300 ℃.On the other hand, when processed oil contained boiling point and surpasses 700 ℃ heavy ends, heavy ingredient can promote carbon separating out on catalyzer, has to cause the active tendency that reduces.Illustrated that the boiling point among the present invention is the value that records according to the method for putting down in writing among JIS K 2254 " distillation test method " or the ASTM-D86.
[0025] in hydrofinishing process of the present invention, use contain porous inorganic oxide and on this porous inorganic oxide load be selected from the catalyzer of metal more than a kind in periodictable 6A family and the 8th family's element, described porous inorganic oxide contains the element more than 2 kinds that is selected from aluminium, silicon, zirconium, boron, titanium and the magnesium.
[0026], use aforesaid by containing the porous inorganic oxide of from aluminium, silicon, zirconium, boron, titanium and magnesium, selecting that constitutes more than 2 kinds as the carrier of the catalyzer that uses among the present invention.As described porous inorganic oxide, consider from can further improving deoxy activity and desulphurizing activated viewpoint, preferably contain from aluminium, silicon, zirconium, boron, titanium and magnesium, select more than 2 kinds, more preferably contain the inorganic oxide composite oxides of the formation of other oxide compound (aluminum oxide with) of aluminium and other element.
[0027] when porous inorganic oxide contained the aluminium of conduct formation element, the content of aluminium was benchmark with the porous inorganic oxide total amount, pressing aluminum oxide converts, be preferably 1～97 quality %, more preferably 10～97 quality %, more preferably 20～95 quality %.If the content of aluminium is pressed aluminum oxide and converted less than 1 quality %, then rerum natura such as support acidity matter is not good, has and can not give full play to deoxy activity and desulphurizing activated tendency.On the other hand, convert above 97 quality % if the content of aluminium is pressed aluminum oxide, then catalyst surface area becomes big inadequately, and activity has the tendency of reduction.
[0028] do not have particular restriction for constituting the method that silicon, zirconium, boron, titanium and the magnesium of element be incorporated in the carrier, use as raw material as long as will contain the solution etc. of these elements as the carrier beyond the aluminium.For example, for silicon, can use silicic acid, water glass, silicon dioxide gel etc.; For boron, can use boric acid etc.; For phosphorus, can use an alkali metal salt of phosphoric acid or phosphoric acid etc.; For titanium, can use titanium sulfide, titanium tetrachloride or various alkoxide etc.; For zirconium, can use zirconium sulfate or various alkoxide etc.
[0029] and then, porous inorganic oxide preferably contains as the phosphorus that constitutes element.The content of phosphorus is benchmark with the porous inorganic oxide total amount, is preferably 0.1～10 quality %, more preferably 0.5～7 quality %, more preferably 2～6 quality %.When the content of phosphorus during less than 0.1 quality %, existence can not be given full play to deoxy activity and desulphurizing activated tendency, in addition, if surpass 10 quality %, then might carry out overcracking, thereby the yield of hydrofined oil is reduced.
[0030] raw material of above-mentioned aluminum oxide carrier constituent in addition preferably adds in the operation before the carrier sintering.For example, can after in containing aluminum water solution, adding above-mentioned raw materials in advance, be mixed with the aluminum hydroxide gel that contains these constituents, also can in the good aluminum hydroxide gel of mediation, add above-mentioned raw materials.Perhaps, also can in commercially available aluminum oxide intermediate or boehmite powder, add water or acidic aqueous solution and carry out adding above-mentioned raw materials in the mixing operation, but more preferably make its coexistence in the stage of mediation aluminum hydroxide gel.Though the mechanism that the carrier constituent beyond the aluminum oxide plays a role may not be clear, but can infer, be because these compositions and aluminium have formed compound oxide compound state, can think, so just can make the carrier surface area increase or produce interaction, thereby activity is exerted an influence with reactive metal.
[0031] make above-mentioned porous inorganic oxide load as carrier be selected from metal more than a kind in periodictable 6A family and the 8th family's element.In the middle of these metals, preferably combination is used the metal of selecting more than 2 kinds from cobalt, molybdenum, nickel and tungsten.As preferred combination, for example can enumerate cobalt-molybdenum, nickel-molybdenum, nickel-cobalt-molybdenum, nickel-tungsten.Wherein, the more preferably combination of nickel-molybdenum, nickel-cobalt-molybdenum and nickel-tungsten.When carrying out hydrofining, the state that these metals is changed into sulfide uses.
[0032] as being the content of the reactive metal of benchmark with the catalyst quality, the scope of the total charge capacity of tungsten and molybdenum is pressed oxide compound and is converted, and is preferably 12～35 quality %, more preferably 15～30 quality %.If the total charge capacity of tungsten and molybdenum is less than 12 quality %, then reduce in the active centre, exists to can not get sufficient active tendency.On the other hand, if surpass 35 quality %, then metal can not disperse effectively, exists to can not get sufficient active tendency.The scope of the total charge capacity of cobalt and nickel is pressed oxide compound and is converted, and is preferably 1.0～15 quality %, more preferably 1.5～12 quality %.If the total charge capacity of cobalt and nickel less than 1.0 quality %, then can not get sufficient promotor effect, activity has the tendency of reduction.On the other hand, if surpass 15 quality %, then metal can not disperse effectively, exists to can not get sufficient active tendency.
[0033] make the method that catalyzer contains these reactive metals not have particular determination, the known method that uses in the time of can adopting common manufacturing desulfurization catalyst.Usually, the preferred method that adopts the solution of the salt that makes the support of the catalyst dipping contain reactive metal.In addition, also preferred equilibrium adsorption method, consent method, the beginning profit pickling process etc. of adopting.For example, the consent method is to measure the pore volume of carrier in advance, makes the method for the metal salt solution of its dipping and its same volume.Illustrated that dipping method does not have particular determination, can adopt appropriate means to flood according to the rerum natura of content of metal and support of the catalyst.
[0034] in the present invention, the species number of employed Hydrobon catalyst does not have particular determination.For example, catalyzer be can be used alone, various active metal or the different catalyzer of carrier constituent also can be used.As the preferably combination under the situation of using multiple different catalysts, for example can enumerate, contain the catalyzer of cobalt-molybdenum in the back segment use of the catalyzer that contains nickel-molybdenum; Back segment at the catalyzer that contains nickel-molybdenum uses the catalyzer that contains nickel-cobalt-molybdenum; Back segment at the catalyzer that contains nickel-tungsten uses the catalyzer that contains nickel-cobalt-molybdenum; Back segment at the catalyzer that contains nickel-cobalt-molybdenum uses the catalyzer that contains cobalt-molybdenum.Also can further make up nickel-molybdenum catalyst at the leading portion and/or the back segment of these combinations.
[0035] when multiple catalyst combination that carrier components is different, for example, total mass with carrier is a benchmark, can be more than the 30 quality % and less than the back segment of the catalyzer of 80 quality %, using the content of aluminum oxide is the catalyzer of 80～99 quality % scopes at the content that uses aluminum oxide.
[0036] and then; except Hydrobon catalyst; as required; to follow dirty composition (sacale) that processed oil flows into or support also can use guard catalyst, catalyst for demetalation, inertia weighting material by Hydrobon catalyst for zone (り is cut in the district) part that makes catalyst bed in order to capture.Illustrated that they may be used singly or in combin.
[0037] pore volume that the above-mentioned catalyzer that uses among the present invention adopts nitrogen absorption BET method to record is preferably 0.30～0.85ml/g, more preferably 0.45～0.80ml/g.When this pore volume during less than 0.30ml/g, the dispersiveness of the metal of institute's load becomes insufficient, might cause the active centre to be reduced.In addition, if this pore volume surpasses 0.85ml/g, then catalyst strength becomes insufficient, and efflorescence, fragmentation might take place catalyzer during use.
[0038] in addition, the average pore diameter of the catalyzer that employing said determination method is obtained is preferably 5～11nm, more preferably 6～9nm.If average pore diameter is less than 5nm, then response matrix can not fully spread in pore, and reactivity might reduce.In addition, if average pore diameter surpasses 11nm, then the pore surface-area reduces, and it is insufficient that activity might become.
[0039] and then, in above-mentioned catalyzer,, give full play to activity in order to keep effective catalyzer pore, be preferably below the 35 capacity % from the pore volume of the pore below the pore diameter 3nm shared ratio in total pore volume.
[0040] in the present invention, can use a kind in the above-mentioned catalyzer separately, also various active metal or the different catalyst combination of carrier constituent can be used.As the preferably combination under the situation of using multiple catalyzer, for example can enumerate, the back segment that contains the catalyzer of nickel-molybdenum in use uses the catalyzer that contains cobalt-molybdenum; The back segment that contains the catalyzer of nickel-molybdenum in use uses the catalyzer that contains nickel-cobalt-molybdenum; The back segment that contains the catalyzer of nickel-tungsten in use uses the catalyzer that contains nickel-cobalt-molybdenum; The back segment that contains the catalyzer of nickel-cobalt-molybdenum in use uses the catalyzer that contains cobalt-molybdenum.Also can further make up nickel-molybdenum catalyst at the leading portion and/or the back segment of these combinations.
[0041] and then; except above-mentioned catalyzer (Hydrobon catalyst); as required; to follow dirty composition (sacle) that processed oil flows into or support also can use guard catalyst, catalyst for demetalation, inertia weighting material by Hydrobon catalyst for zone (り is cut in the district) part that makes catalyst bed in order to capture.Illustrated that they may be used singly or in combin.
Condition when [0042] conduct makes above-mentioned processed oil contact with catalyzer in the presence of hydrogen, hydrogen pressure is 2～13MPa, liquid hourly space velocity (LHSV) is 0.1～3.0h
-1, hydrogen-oil ratio (hydrogen/oil ratio) is 150～1500NL/L; Preferably, hydrogen pressure is 4.5～12MPa, and liquid hourly space velocity is 0.3～1.5h
-1, hydrogen-oil ratio is 380～1200NL/L; More preferably, hydrogen pressure is 6～15MPa, and liquid hourly space velocity is 0.3～1.5h
-1, hydrogen-oil ratio is 350～1000NL/L.These conditions are the factor of control reactive behavior, for example, when hydrogen pressure and hydrogen-oil ratio during less than above-mentioned lower value, have reactive the reduction or the active tendency that sharply reduces.On the other hand, when hydrogen pressure and hydrogen-oil ratio surpass above-mentioned higher limit, there is the tendency that needs excessive facility investments such as compressor.In addition, liquid hourly space velocity is low more, and is favourable more to reaction, but when its during less than above-mentioned lower value, just need the reactor of very big internal volume, thus the excessive facility investment of needs; On the other hand, when liquid hourly space velocity surpassed above-mentioned higher limit, reaction had the tendency that can not fully carry out.
[0043] as the form of reactor, can adopt the fixed bed mode.That is, can adopt hydrogen is any form in adverse current or the following current with respect to processed oil.In addition, also can use a plurality of reactors, also can adopt form adverse current, following current combination.As general form, can adopt flow downward, the two following current forms of gas-liquid.In addition, reactor can be independent or a plurality of combination, also can adopt the structure that is divided into a plurality of catalyst beds at an inside reactor.
[0044] having carried out hydrorefined hydrofined oil through gas-liquid separation operation or rectification working process etc. in reactor, is the hydrofined oil that contains the regulation cut by fractionation.For example, fractionation is a diesel oil (original text: light oil) cut and residue oil fraction.And then as required, also fractionation is gas, naphtha fraction, kerosene(oil)fraction sometimes.Part by this light fractions that will generate is reformed in the steam reforming device, can make hydrogen.The hydrogen of Zhi Zaoing owing to be used for the hydrocarbon that the raw material of steam reforming comes authigenic material, therefore has the feature of so-called neutral carbon like this, can reduce carrying capacity of environment.Illustrated, follow the oxygen composition that processed oil contains or the reaction of sulphur composition, might produce water, carbon monoxide, carbonic acid gas, hydrogen sulfide etc., but also can between a plurality of reactors or in the product recovery process gas-liquid separation equipment be set or other by-product gas is removed device.
[0045] hydrogen generally is the processed oil that is accompanied by by before or after the process furnace, import from initial reactor inlet, but the present invention is different therewith, for the temperature in can controlling reactor, keep simultaneously hydrogen pressure whole in the reactor again, can be from importing hydrogen between the catalyst bed or between several reactor.Generally the hydrogen that will import like this is called quenching hydrogen.Quenching hydrogen is preferably 10～60 capacity % with respect to the ratio of the hydrogen of following processed oil to import, more preferably 15～50 capacity %.If the ratio of quenching hydrogen is less than 10 capacity %, then the reaction at the reactive site of back segment has the tendency that can not fully carry out, and if the ratio of quenching hydrogen surpasses 60 capacity %, then near the reaction reactor inlet has the tendency that can not fully carry out.
[0046] when the hydrofined oil that the present invention is made uses as the diesel oil distillate base material, the preferred boiling point that contains at least is 260～300 ℃ a cut, the content of sulphur composition is that 15 quality ppm content following and the oxygen composition is below the 0.5 quality %, and more preferably the content of sulphur composition is that 12 quality ppm content following and the oxygen composition is below the 0.3 quality %.When sulphur composition and oxygen composition surpassed above-mentioned higher limit, the strainer that uses in might the exhaust gas disposal apparatus to diesel motor and other material of catalyzer and engine exerted an influence.
[0047] hydrofined oil of manufacturing of the present invention is particularly suitable as solar oil and the use of heavy oil base material.Hydrofined oil can use as solar oil or heavy oil base material separately, also can be used as the solar oil or the heavy base material that are mixed with compositions such as other base material and uses.As other base material, can be diesel oil distillate and/or the kerosene(oil)fraction that generally in the petroleum refinement operation, obtains, also can mix with residual oil (residual さ) cut that obtains in the hydrofinishing process of the present invention.And then, also can with the so-called synthetic gas of forming by hydrogen and carbon monoxide as raw material, the combined diesel oil or the synthetic kerosene that obtain via Fischer-Tropsch reaction etc. mix.The feature of these combined diesel oils or synthetic kerosene is, contains aromatic component hardly, but is principal constituent with the stable hydrocarbon, and its cetane value height.Illustrated,, can be used known method, this is not had particular determination as the manufacture method of synthetic gas.
[0048] residue oil fraction that adopts hydrofinishing process of the present invention to obtain, the content of its sulphur composition is below the 0.1 quality %, the content of oxygen composition is below the 1 quality %, can be used as low-sulfur heavy base material and uses.In addition, this residue oil fraction is suitable as catalytic cracking and uses with stock oil.By so low-sulfur content residue oil fraction being fed in the catalytic cracking unit, can make the few gasoline base of sulphur content or other oil fuel base material.And then this residue oil fraction also can be used as hydrocracking and uses with stock oil.By this residue oil fraction is fed in the hydroeracking unit, can realize the raising of cracking activity and high-qualityization of each cut proterties of generation oil.
Embodiment
[0049] be described more specifically the present invention based on embodiment and comparative example below, but the present invention is not subjected to any qualification of following examples.
[0050] (Preparation of catalysts)
＜catalyst A 〉
To concentration is to add No. 3 18.0g of water glass among the sodium aluminate aqueous solution 3000g of 5 quality %, and it is joined in the container of 65 ℃ of insulations.In addition, in another container of 65 ℃ of insulations, in concentration is the aluminum sulfate aqueous solution 3000g of 2.5 quality %, add phosphoric acid (concentration 85%) 6.0g, be mixed with solution, to wherein splashing into the above-mentioned aqueous solution that contains sodium aluminate.PH value with mixing solutions reaches at 7.0 o'clock as terminal point, filters the product of collecting the pulp-like that obtains with strainer, obtains the slurry of filter cake shape.
[0051] slurry with filter cake shape is transferred in the container that reflux exchanger is installed, to wherein adding distilled water 150ml and 27% ammonia soln 10g, 75 ℃ of following heated and stirred 20 hours.This slurry is joined in the kneading device,,, obtain claylike mixing thing Yi Bian carry out mixingly Yi Bian be heated to more than 80 ℃ removing moisture.It is the cylindrical of 1.5mm that the mixing thing that obtains is extruded into diameter with extrusion shaping machine, after under 110 ℃ dry 1 hour, carries out sintering under 550 ℃, obtains shaping carrier.
[0052] the shaping carrier 50g that obtains is joined in the eggplant-shape bottle, outgas on one side with rotatory evaporator, on one side will contain molybdic oxide 17.3g, nickelous nitrate (II) hexahydrate 13.2g, phosphoric acid (concentration 85%) 3.9g and oxysuccinic acid 4.0g dipping solution be injected in the flask.Impregnated sample after under 120 ℃ dry 1 hour, is carried out roasting under 550 ℃, obtain catalyst A.The rerum natura of the catalyst A of preparation is shown in table 1.
[0053]＜catalyst B 〉
With concentration is that the sodium aluminate aqueous solution 3000g of 5 quality % joins in the container of 65 ℃ of insulations.In addition, in another container of 65 ℃ of insulations, compound concentration is the aluminum sulfate aqueous solution 3000g of 2.5 quality %, to wherein splashing into above-mentioned sodium aluminate aqueous solution.PH value with mixing solutions reaches at 7.0 o'clock as terminal point, filters with strainer and collects the pulp-like product that obtains, and obtains the slurry of filter cake shape.
[0054] the filter cake shape slurry is transferred in the container that reflux exchanger is installed, adds distilled water 150ml and 27% ammonia soln 10g, 75 ℃ of following heated and stirred 10 hours.This slurry is joined in the kneading device,,, obtain claylike mixing thing Yi Bian carry out mixingly Yi Bian be heated to more than 80 ℃ removing moisture.It is the cylindrical of 1.5mm that the mixing thing that obtains is extruded into diameter with extrusion shaping machine, after under 110 ℃ dry 1 hour, carries out sintering under 550 ℃, obtains shaping carrier.
[0055] the shaping carrier 50g that obtains is joined in the eggplant-shape bottle, outgas on one side with rotatory evaporator, on one side will contain molybdic oxide 17.3g, nickelous nitrate (II) hexahydrate 13.2g, phosphoric acid (concentration 85%) 3.9g and oxysuccinic acid 4.0g dipping solution be injected in the flask.Impregnated sample after under 120 ℃ dry 1 hour, is carried out roasting under 550 ℃, obtain catalyst B.The rerum natura of the catalyst B of preparation is shown in table 1.
[0056] [table 1]
| Catalyst A | Catalyst B | |
| Al 2O 3Content (quality % is a benchmark with the carrier quality) | 91.2 | 100 |
| SiO 2Content (quality % is a benchmark with the carrier quality) | 4.8 | - |
| P 2O 5Content (quality % is a benchmark with the carrier quality) | 4.0 | - |
| MoO 3Content (quality % is a benchmark with the catalyst quality) | 24.0 | 24.0 |
| NiO content (quality % is a benchmark with the catalyst quality) | 2.6 | 2.5 |
| P 2O 5Content (quality % is a benchmark with the catalyst quality) | 4.0 | 4.0 |
| Pore volume (ml/g) | 0.75 | 0.47 |
| Average pore diameter (nm) | 7.0 | 5.2 |
| Pore volume shared ratio (capacity %) in total pore volume from the pore below the pore diameter 3nm | 22 | 39 |
[0057] (embodiment 1)
To be filled with first reaction tubes (internal diameter 20mm) of catalyst A (50ml) in series is installed in the fixed bed flow type reaction unit with second reaction tubes (internal diameter 20mm) that is filled with catalyst A (50ml) equally.Then, use the straight-run diesel oil (sulphur content 3 quality %) that has added dimethyl disulfide, at 300 ℃ of catalyst layer medial temperatures, hydrogen dividing potential drop 6MPa, liquid hourly space velocity 1h
-1, hydrogen/oil ratio 200NL/L condition under, catalyzer carried out 4 hours prevulcanized.
[0058] after the prevulcanized, uses by in plam oil, adding dimethyl disulfide the sulphur component content in the processed oil is adjusted to the processed oil of 51 quality ppm, carry out hydrofining.The density of processed oil in the time of 15 ℃ is 0.916g/ml, and the content of oxygen composition is 11.4 quality %.In addition, about hydrorefined condition, the temperature of reaction of first and second reaction tubess is 280 ℃, and pressure is 10MPa, and liquid hourly space velocity is 0.6h
-1Illustrated that the volume ratio of the hydrogen that imports between first reaction tubes and second reaction tubes (quenching hydrogen ratio) is total 20 capacity % that import hydrogen, hydrogen/oil ratio of obtaining according to the total hydrogen amount that imports is 500NL/L.What obtain the results are shown in table 2.
[0059] (comparative example 1)
Except using catalyst B replacement catalyst A, all the other carry out hydrofining similarly to Example 1.What obtain the results are shown in table 2.
[0060] (comparative example 2)
The temperature of reaction of first and second reaction tubess when making hydrofining was 160 ℃, all the other carried out hydrofining similarly to Example 1.What obtain the results are shown in table 2.
[0061] (comparative example 3)
The temperature of reaction of first and second reaction tubess when making hydrofining was 410 ℃, all the other carried out hydrofining similarly to Example 1.What obtain the results are shown in table 2.
[0062] [table 2]
Claims (6)
1, hydrofinishing process, it is characterized in that, in the presence of hydrogen, make the processed oil that contains oxygen-containing hydrocarbon compound and sulfur-bearing hydrocarbon compound with contain porous inorganic oxide and on this porous inorganic oxide load be selected from the catalyzer of metal more than a kind in periodictable 6A family and the 8th family's element at hydrogen pressure 2～13MPa, liquid hourly space velocity 0.1～3.0h
-1, 180～380 ℃ of hydrogen-oil ratio 150～1500NL/L, temperature of reaction condition under contact,
Described porous inorganic oxide contains the element more than 2 kinds that is selected from aluminium, silicon, zirconium, boron, titanium and the magnesium.
2, the described hydrofinishing process of claim 1 is characterized in that, is benchmark with the total amount of above-mentioned processed oil, and the content of oxygen composition is 0.1～15 quality %, and the content of sulphur composition is 1 quality ppm～1 quality %.
3, claim 1 or 2 described hydrofinishing process is characterized in that, above-mentioned oxygen-containing hydrocarbon compound is the lubricant component from vegetable and animals oils.
4, each described hydrofinishing process of claim 1～3 is characterized in that, the compound shared ratio in above-mentioned oxygen-containing hydrocarbon compound with triglyceride structure is 90 moles more than the %.
5, each described hydrofinishing process of claim 1～4, it is characterized in that, in above-mentioned catalyzer, the pore volume that records by nitrogen absorption BET method is 0.30～0.85ml/g, average pore diameter is 5～11nm, is below the 35 capacity % from the pore volume of the pore below the pore diameter 3nm shared ratio in total pore volume.
6, each described hydrofinishing process of claim 1～5 is characterized in that above-mentioned porous inorganic oxide contains phosphoric.
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| JP138292/2006 | 2006-05-17 | ||
| JP2006138292A JP5196734B2 (en) | 2006-05-17 | 2006-05-17 | Hydrorefining method |
| PCT/JP2007/059948 WO2007132843A1 (en) | 2006-05-17 | 2007-05-15 | Hydrorefining process |
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| KR (1) | KR101452793B1 (en) |
| CN (1) | CN101448924B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102989462A (en) * | 2012-10-24 | 2013-03-27 | 中国海洋石油总公司 | Method for preparing oils and fats hydrogenation catalyst with high activity |
| CN111036250A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Phosphorus-containing catalyst, preparation method and application thereof, and glycerol hydrogenolysis method |
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| WO2009139313A1 (en) * | 2008-05-14 | 2009-11-19 | 新日本石油株式会社 | Method for producing hydrocarbon oil |
| JP5070169B2 (en) | 2008-09-18 | 2012-11-07 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing hydrocarbon oil |
| JP5070170B2 (en) * | 2008-09-18 | 2012-11-07 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing hydrocarbon oil |
| FR2940144B1 (en) * | 2008-12-23 | 2016-01-22 | Inst Francais Du Petrole | PROCESS FOR TRANSFORMING EXCELLENT QUALITY RENEWABLE FUEL ORIGLENT EFFLUENTS USING A MOLYBDENATED CATALYST |
| JP2011148909A (en) * | 2010-01-21 | 2011-08-04 | Tokyo Univ Of Agriculture & Technology | Biohydrocarbon, method for manufacturing biohydrocarbon and apparatus for manufacturing biohydrocarbon |
| JP7366043B2 (en) * | 2018-09-28 | 2023-10-20 | 日揮触媒化成株式会社 | Catalyst for hydrotreating hydrocarbon oil, method for producing the same, and method for hydrotreating hydrocarbon oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4532351A (en) * | 1982-06-16 | 1985-07-30 | Exxon Research And Engineering Co. | Process for hydrogenating organic compounds by use of Group VIII aluminum-silicate catalysts |
| JPS59108088A (en) * | 1982-11-10 | 1984-06-22 | Honda Motor Co Ltd | Production of paraffin hydrocarbon |
| CA2016817C (en) * | 1989-05-16 | 1998-06-23 | Cornelis Martinus Lok | Nickel/silica catalyst and the preparation and use thereof |
| JP2989704B2 (en) * | 1991-03-11 | 1999-12-13 | 花王株式会社 | Production of desulfurized fat and oil of fatty acid ester, production of alcohol using the same fat and oil or fatty acid ester |
| JP2934073B2 (en) * | 1991-05-31 | 1999-08-16 | 花王株式会社 | Process for producing desulfurized fat or oil or fatty acid ester |
| CN1040452C (en) * | 1993-08-05 | 1998-10-28 | 中国石油化工总公司 | Refining process for hydrodesulfurization, hydrodenitrification and hydrodearsenication of naphtha and saturation of aromatic hydrocarbon |
| JP2003171670A (en) * | 2001-12-07 | 2003-06-20 | Kawaken Fine Chem Co Ltd | Method for producing hydrocarbons and catalyst for producing hydrocarbons |
| US7232935B2 (en) * | 2002-09-06 | 2007-06-19 | Fortum Oyj | Process for producing a hydrocarbon component of biological origin |
| JP2007308564A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrogenation purification method |
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| CN102989462A (en) * | 2012-10-24 | 2013-03-27 | 中国海洋石油总公司 | Method for preparing oils and fats hydrogenation catalyst with high activity |
| CN111036250A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Phosphorus-containing catalyst, preparation method and application thereof, and glycerol hydrogenolysis method |
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| KR101452793B1 (en) | 2014-10-21 |
| JP5196734B2 (en) | 2013-05-15 |
| JP2007308563A (en) | 2007-11-29 |
| KR20090026768A (en) | 2009-03-13 |
| MY151081A (en) | 2014-04-15 |
| WO2007132843A1 (en) | 2007-11-22 |
| CN101448924B (en) | 2012-12-12 |
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