CN100506379C - Large Pore Volume Sulfur-Containing Nickel Catalysts for Selective Hydrogenation - Google Patents
Large Pore Volume Sulfur-Containing Nickel Catalysts for Selective Hydrogenation Download PDFInfo
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- CN100506379C CN100506379C CNB2006101178543A CN200610117854A CN100506379C CN 100506379 C CN100506379 C CN 100506379C CN B2006101178543 A CNB2006101178543 A CN B2006101178543A CN 200610117854 A CN200610117854 A CN 200610117854A CN 100506379 C CN100506379 C CN 100506379C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 43
- 239000011148 porous material Substances 0.000 title claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 title description 7
- 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 16
- 230000000737 periodic effect Effects 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 238000000197 pyrolysis Methods 0.000 abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000004215 Carbon black (E152) Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- 150000001993 dienes Chemical class 0.000 description 17
- 239000003921 oil Substances 0.000 description 16
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000005303 weighing Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000000470 constituent Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002803 maceration Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 241000219793 Trifolium Species 0.000 description 5
- 229910001593 boehmite Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 238000011017 operating method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229940068984 polyvinyl alcohol Drugs 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer 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
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to large pore volume sulfur-including nickel catalyst used for selective hydrogenation, which mainly solves the problems existing in the prior art that the low-temperature activity of the catalyst is low and the stability is poor. The invention comprises the following component according to weight percentage: 5.0 to 40.0 percent of metallic nickel or the oxide thereof, 0.01 to 20.0 percent of at least one element or the oxide thereof selected from molybdenum or tungsten, 0.01 to 10.0 percent of at least one element or the oxide thereof selected from rare earth, 0.01 to 2.0 percent of at least one element or the oxide thereof selected from IA or IIA in the periodic table, 0 to 15.0 percent of silicon, phosphorus, boron or fluoride, 0 to 10.0 percent of at least one element or the oxide thereof selected from periodic table IVB, 0.01 to 10.0 percent of sulfur or the compound thereof, surplus quantity of alumina catalyst carrier, wherein, the specific surface area of the carrier is 100 to 180 meters <2>/g, and the total pore volume is 0.5 to 1.2 ml/g. The invention can be used for the industrial production of pyrolysis gasoline selective hydrogenation.
Description
Technical field
The present invention relates to a kind of macropore capacity sulfureous-containing nickel catalyst that is used for selective hydrogenation, particularly is the Raney nickel of the pyrolysis gasoline hydrogenation of 204 ℃ hydrocarbon compound full-cut fraction pyrolysis gasoline or C6～C8 hydrocarbon compound midbarrel about a kind of C5 of being used for hydrocarbon～do.
Background technology
The utilization of drippolene is to improve one of main path of device overall economic efficiency in the ethylene unit.Because drippolene is formed complicated, poor heat stability, usually, remove alkadienes and styrene through one-stage selective hydrogenation earlier, after the secondary hydrogenation desulfurization, be mainly used in the aromatic hydrocarbons extracting.It mainly is Pd system or Ni series catalysts with catalyst that present industrial drippolene is selected hydrogenation, midbarrel (C
6～C
8The hydrocarbon compound cut) hydrogenation or full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) hydrogenation technique.Because the difference of each ethylene unit cracking stock and cracking condition, each installs drippolene raw material composition and differs bigger, and particularly the diene of drippolene, colloid and As, content of beary metal exist than big-difference; The device raw pyrolysis gasoline diene, the colloid height that have, and toxic content such as colloid and As, heavy metal is higher in the device raw pyrolysis gasoline raw material that has, toxic contents such as individual device raw pyrolysis gasoline diene, colloid and As, heavy metal are all high, these all can cause operating operating mode and worsen the easy inactivation of Pd series catalysts.Therefore, although traditional Pd series catalysts has been obtained effect preferably in commercial Application, but still have certain limitation, especially to containing the higher raw material of As, the Pd series catalysts often is difficult to satisfy the needs of operation steady in a long-term under harsh working condition.Anti-As performance that Ni is catalyst based and low-temperature stability make it have important purposes in drippolene especially full-cut fraction pyrolysis gasoline process for selective hydrogenation, raw material need not to take off As and handles, thereby save a large amount of operating costs, and reduce catalyst causes active decline because of the As accumulation parking regeneration expense; Ni is catalyst based, and to compare price lower with the Pd series catalysts; Low form Ni is catalyst based at cracking by-product such as C
4, C
5, C
9Hydrogenation utilize the aspect will bring into play and important effect.Therefore, Ni is catalyst based is applied to full cut or selects the cut fraction pyrolysis gasoline selective hydrogenation to have good prospect at replacement Pd series catalysts.
Full-cut fraction pyrolysis gasoline is rich in C
5, C
9 +(carbon nine and more than) unsaturated component, the diene height, easily polymerization, colloid (high molecular polymer that unsaturated component polymerization reaction take place such as alkadienes and styrene generates) height, heavy ends are many, coke powder content height, poor stability, lack effective water-oil separating means owing to form azeotropic mixture or commercial plant, cause raw material free water content height, poisonous substances such as heavy metal easily are enriched in C
9 +In (carbon nine and more than) cut and characteristics such as the hydrogenation thermal discharge is big, make the very fast inactivation of catalyst, thereby catalyst have to frequent activation and regeneration.The Ni/Al of present commercial Application
2O
3Catalyst is difficult to adapt in the ethylene industry requirement of the frequent fluctuation of raw material quality in the drippolene one-stage hydrogenation and high selectivity, high-speed and long-term operation, be still waiting to improve in diene low temperature hydrogenation activity, selectivity, air speed and aspects such as interference free performance such as water-fast, wish that hydrogenation catalyst has better anti-interference, suitable appearance glue ability, higher low temperature active and selectivity, increasing the catalyst regeneration cycle, thereby prolong catalyst service life.
A kind of hydrogenation catalyst and technology and application are disclosed among the Chinese patent CN1644656A.This catalyst weight percentage consists of NiO 10～30%, Al
2O
370～90%.This catalyst is applicable to the distillate that contains alkadienes and styrene and derivative thereof, and reaction process condition is 50～200 ℃ of temperature, pressure 2.0～4.0MPa, liquid air speed 1～10 hour
-1, hydrogen to oil volume ratio is H
2This catalyst and technology directly high aromatic solvent naphtha of hydrogenation preparing and high-knock rating gasoline are adopted in/oil=100～300.The shortcoming of this catalyst is the preparation process complexity of catalyst carrier, and carrier needs to feed steam reaming 1～4 hour at 600～700 ℃, and roasting then just can obtain the carrier of high-ratio surface, macropore.
A kind of selective hydrocatalyst is disclosed among the Chinese patent CN1218822A.This catalyst is by the NiO of 5～25 heavy %, and 0.1～2.0 weighs lithium or the alkaline-earth metal (preferably magnesium) of %, and the aluminium oxide of surplus composition, is applicable to the selective hydrogenation process of the full distillate oil of the distillate that contains diolefin, particularly drippolene.The shortcoming of this catalyst is that the specific area of catalyst is lower (60～85 meters
2/ gram), pore volume less (0.28～0.36 milliliter/gram), reactivity is relatively low, reaction temperature higher (80～160 ℃).
Summary of the invention
Technical problem to be solved by this invention be exist the low temperature active of catalyst low in the prior art, the technical problem of poor stability, a kind of new macropore capacity sulfureous-containing nickel catalyst that is used for selective hydrogenation is provided.This catalyst is applicable to C
6～C
8Hydrocarbon compound midbarrel and full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) pyrolysis gasoline hydrogenation, and have the advantage of good low temperature active, selectivity and stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of macropore capacity sulfureous-containing nickel catalyst that is used for selective hydrogenation comprises following component by weight percentage: (a) 5.0～40.0% metallic nickel or its oxide; (b) 0.01～20.0% be selected from least a element or its oxide in molybdenum or the tungsten; (c) 0.01～10.0% be selected from least a element or its oxide in the rare earth; (d) 0.01～2.0% be selected from least a element or its oxide among IA in the periodic table of elements or the IIA; (e) 0～15.0% be selected from least a element or its oxide in silicon, phosphorus, boron or the fluorine; (f) 0～10.0% be selected from least a element among the IVB or its oxide in the periodic table of elements; (g) 0.01～10.0% sulphur or its compound; (h) alumina catalyst support of surplus; Wherein total pore volume of carrier is 0.5～1.2 a milliliter/gram.
In the technique scheme, by weight percentage, the content preferable range of metallic nickel or its oxide is 10.0～30.0%; Being selected from least a element in molybdenum or the tungsten or the content preferable range of its oxide is 0.1～15.0%; Being selected from least a element in the rare earth or the content preferable range of its oxide is 0.1～5.0%; Being selected from least a element among IA in the periodic table of elements or the IIA or the content preferable range of its oxide is 0.2～0.8%; Being selected from least a element in silicon, phosphorus, boron or the fluorine or the content preferable range of its oxide is 0.5～10.0%; The content preferable range that is selected from least a element among the IVB in the periodic table of elements or its oxide is 0.1～5.0%; The content preferable range of sulphur or its compound is 0.1～8.0%.The element preferred version that is selected from the rare earth is at least a for being selected from lanthanum or the cerium; The element preferred version that is selected from IA in the periodic table of elements is a potassium; The element preferred version that is selected from IIA in the periodic table of elements is at least a for being selected from calcium, magnesium or the barium; The element preferred version that is selected from IVB in the periodic table of elements is at least a for being selected from titanium or the zirconium.Carrier specific area preferable range is 100～180 meters
2/ gram, more preferably scope is 120～160 meters
2/ gram, total pore volume preferable range are 0.8～1.1 milliliter/gram.
The preparation method of carrier of the present invention comprise with aluminium oxide and modifier, peptizing agent, water mix in the desired amount, behind the extruded moulding, earlier 50～120 ℃ dry 1～24 hour down, then 700～1150 ℃ of following roastings 1～10 hour, obtain carrier.
Preparation of catalysts method of the present invention is: with the solution impregnation that carrier is made into the cocatalyst component of using in the nickel compound of aequum and the catalyst, the soaked carrier drying, 350～500 ℃ of roastings promptly get the oxidative catalyst finished product in air.Can repeat above-mentioned steps and make required nickel content.Presulfiding of catalyst is divided in the device and the outer 2 kinds of methods of presulfurization of device.In the device presulfurization be catalyst reduction good after, directly feeding contains the feedstock oil of vulcanizing agent; The outer presulfurization of device is with in the catalyst of reduction/passivation and the reactor that recharges after vulcanizing agent combines.
Catalyst of the present invention is applicable to the alkynes of petroleum hydrocarbon or the selection hydrogenation of diolefin, is preferably the full cut (C of drippolene
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) or C
6～C
8The hydrogenation of hydrocarbon compound midbarrel.
Catalyst of the present invention is being used for full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) have good low temperature active, selectivity and stability during the drippolene selective hydrogenation.At 50 ℃ of inlet temperatures, reaction pressure 2.7Mpa, hydrogen/oil volume ratio is 100: 1, and the green oil air speed is 3.8 hours
-1, total air speed 7.6 hours
-1Under the condition, to full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) drippolene carries out selective hydrogenation reaction, and its outlet diene mean value is 0.37 gram iodine/100 gram oil, and the diolefin hydrogenation rate is 98.15%, has obtained better technical effect.
The present invention is further elaborated below by embodiment.But these embodiment in no case are construed as limiting scope of the present invention.
The specific embodiment
[embodiment 1]
Take by weighing boehmite 300 grams, 150 gram alpha-aluminium oxides, 9 gram sesbania powder mix, add afterwards and contain poly-vinyl alcohol solution (mass concentration is 5%) 25 grams, nitric acid 4.0 grams, concentration are 85% phosphatase 11 .8 gram, potassium nitrate 1.5 grams, 360 milliliters of the aqueous solution of magnesium nitrate 2 grams, be extruded into the clover of 2.5 millimeters of φ, wet bar through 120 ℃ of dryings after 4 hours in 1150 ℃ of roastings 2 hours, obtain carrier Z1.Take by weighing ammonium molybdate 2.5 gram, lanthanum nitrate 1.0 grams, zirconium nitrate 4.0 grams add entry 130 grams, are that 14% nickel liquid 50 grams mix and are made into maceration extract with concentration.Carrier is carried out equivalent impregnation in maceration extract, 60 ℃ of dryings 8 hours, 450 ℃ of roastings 4 hours, it is catalyst based to make oxidation state Ni.With oxidation state Ni catalyst based be 2.7MPa at Hydrogen Vapor Pressure, temperature is that 450 ℃ and hydrogen flowing quantity are reduction 12 hours under the condition of 1500 ml/min, logical nitrogen and the passivation of Air mixing gas after temperature drops to below 35 ℃, it is catalyst based to make reduction/passivation Ni.Take by weighing two uncle's nonyl polysulfides, 0.8 gram, add cyclohexane 80 grams and be made into sulfur agent solution, will reduce/the catalyst based equivalent impregnation that in sulfur agent solution, carries out of passivation Ni, make the catalyst based C1 of sulfur-bearing Ni.Catalyst composition and specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
[embodiment 2]
Adopt carrier Z2, the preparing carriers method is with embodiment 1, and vehicle group becomes to see Table 1.Take by weighing ammonium molybdate 10.0 gram, ammonium tungstate 5.0 grams, lanthanum nitrate 3.5 grams, cerous nitrate 3.0 grams, titanium chloride 4.5 grams, potassium borohydride 2.0 grams, potassium fluoride 3.0 grams add entry 30 grams, are that 14% nickel liquid 150 grams mix and are made into maceration extract with concentration.Make the catalyst based C2 of sulfur-bearing Ni with embodiment 1 same operating procedure and condition.Catalyst composition and specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
[embodiment 3]
Take by weighing boehmite 300 grams, 45 gram diatomite, 9 gram sesbania powder, mix, add afterwards and contain poly-vinyl alcohol solution (mass concentration is 5%) 25 grams, nitric acid 3.5 grams, 360 milliliters of the aqueous solution of calcium nitrate 1.0 grams, be extruded into the clover of 2.5 millimeters of φ, wet bar through 50 ℃ of dryings after 24 hours in 750 ℃ of roastings 4 hours, obtain carrier Z3.Take by weighing ammonium molybdate 25 gram, cerous nitrate 3.0 grams, zirconium nitrate 0.5 gram adds entry 80 grams, is that 14% nickel liquid 100 grams mix and are made into maceration extract with concentration.Make the catalyst based C3 of sulfur-bearing Ni with embodiment 1 same operating procedure and condition.Catalyst composition and specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
[embodiment 4]
Take by weighing boehmite 345 grams, 9 gram sesbania powder, mix, add afterwards and contain poly-vinyl alcohol solution (mass concentration is 5%) 25 grams, nitric acid 3.5 gram, 345 milliliters of the aqueous solution of calcium nitrate 1.0 grams are extruded into the clover of 2.5 millimeters of φ, wet bar through 50 ℃ of dryings after 24 hours in 750 ℃ of roastings 4 hours, obtain carrier Z4.Take by weighing ammonium tungstate 8 gram, lanthanum nitrate 3 grams, zirconium nitrate 0.5 gram adds entry 70 grams, is that 14% nickel liquid 100 grams mix and are made into maceration extract with concentration.Make the catalyst based C4 of sulfur-bearing Ni with embodiment 1 same operating procedure and condition.Catalyst composition and specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
[embodiment 5]
Take by weighing boehmite 300 grams, 45 gram diatomite, 9 gram sesbania powder, mix, add afterwards and contain poly-vinyl alcohol solution (mass concentration is 5%) 25 grams, nitric acid 3.5 grams, 360 milliliters of the aqueous solution of calcium nitrate 1.0 grams, be extruded into the clover of 2.5 millimeters of φ, wet bar through 50 ℃ of dryings after 24 hours in 750 ℃ of roastings 4 hours, obtain carrier Z5.Take by weighing ammonium molybdate 17 gram, cerous nitrate 3.0 grams add entry 85 grams, are that 14% nickel liquid 100 grams mix and are made into maceration extract with concentration.Make the catalyst based C5 of sulfur-bearing Ni with embodiment 1 same operating procedure and condition.Catalyst composition and specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
[comparative example 1]
Take by weighing boehmite 300 gram, 9 gram sesbania powder, 45 gram graphite mix, and are extruded into the clover of 2.5 millimeters of φ, wet bar through 120 ℃ of dryings after 4 hours in 1050 ℃ of roastings 4 hours, obtain carrier D1.Make the catalyst based CD1 of Ni with embodiment 1 same operating procedure and condition.Catalyst composition and specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
Table 1
| The embodiment numbering | 1 | 2 | 3 | 4 | 5 | Comparative example 1 |
| The catalyst numbering | C1 | C2 | C3 | C4 | C5 | CD1 |
| Bearer number | Z1 | Z2 | Z3 | Z4 | Z5 | D1 |
| Ni content, % (weight) | 10 | 30 | 20 | 20 | 20 | 20 |
| Molybdenum, W elements content, % (weight) | Mo-0.1 | Mo-5.0 W-5.0 | Mo-15.0 | W-10.0 | Mo-10.0 | 0 |
| Ree content, % (weight) | La-0.1 | La-2.5 Ce-2.5 | Ce-2.5 | La-2.5 | Ce-2.5 | 0 |
| The IA constituent content, % (weight) | K-0.3 | K-0.5 | 0 | 0 | 0 | 0 |
| The IIA constituent content, % (weight) | Mg-0.5 | Ba-0.1 | Ca-0.2 | Ca-0.2 | Ca-0.2 | 0 |
| Silicon, phosphorus, boron, fluorine element content, % (weight) | P-0.5 | B-5.0 F-5.0 | Si-10.0 | 0 | Si-10.0 | 0 |
| The IVB constituent content, % (weight) | Zr-2.5 | Ti-5.0 | Zr-0.1 | Zr-0.1 | 0 | 0 |
| Sulfur content, % (weight) | 0.2 | 8.0 | 4.3 | 2.1 | 5.8 | 0 |
| Specific area, rice 2/ gram | 122.4 | 138.7 | 157.2 | 129.3 | 148.6 | 102.3 |
| Pore volume, milliliter/gram | 1.05 | 0.91 | 0.84 | 0.99 | 0.88 | 0.56 |
[embodiment 6]
Present embodiment explanation embodiment 1～5 gained catalyst is at full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) drippolene selects the application in the hydrogenation.
Getting each 80 milliliters of the embodiment of the invention 1～5 catalyst, is 2.7MPa at Hydrogen Vapor Pressure, and temperature is that 450 ℃ and hydrogen flowing quantity are reduction 12 hours under the condition of 1500 ml/min.At Hydrogen Vapor Pressure 2.7MPa, 50 ℃ of inlet temperatures, green oil air speed 3.8 hours
-1(total air speed 7.6 hours
-1), feed the full-cut fraction pyrolysis gasoline raw material under the condition of hydrogen/oil volume than 100: 1 and test.Full-cut fraction pyrolysis gasoline raw material weight percentage consists of C
5Hydrocarbon 15.5%, C
6Hydrocarbon 21.8%, C
7Hydrocarbon 23.3%, C
8Hydrocarbon 21.3%, C
9 +Hydrocarbon 18.1%, diene value 27.12.Hydrogenation the results are shown in Table 2.
[comparative example 2]
Get comparative example 1 catalyst CD180 milliliter, reduce with embodiment 6 same conditions.Test with embodiment 6 same raw material, reaction conditions, hydrogenation the results are shown in Table 2.
Table 2
[embodiment 7]
2 catalyst C2 are at full cut (C for the present embodiment explanation embodiment of the invention
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) drippolene selects in the hydrogenation 1000 hours result of the test.
Get 80 milliliters of embodiment 2 catalyst C2, repeat the reduction process of embodiment 6,50 ℃ of temperature, reaction pressure 2.65MPa, green oil air speed 3.8 hours
-1(total air speed 7.6 hours
-1), feed the full-cut fraction pyrolysis gasoline raw material under the condition of hydrogen/oil volume than 100: 1 and test.Full-cut fraction pyrolysis gasoline raw material weight percentage consists of C
5Hydrocarbon 15.5%, C
6Hydrocarbon 21.8%, C
7Hydrocarbon 23.3%, C
8Hydrocarbon 21.3%, C
9 +Hydrocarbon 18.1%, diene value 27.12.Hydrogenation the results are shown in Table 3.
[comparative example 3]
Get 80 milliliters of comparative example 1 catalyst CD1, reduce with embodiment 6 same conditions.Test with embodiment 7 same raw material, reaction conditions, hydrogenation the results are shown in Table 3.
Table 3
[embodiment 8]
2 catalyst C2 are at C for the present embodiment explanation embodiment of the invention
6～C
81000 hours result of the test in the drippolene selection hydrogenation of hydrocarbon compound midbarrel.
Get embodiment 2 catalyst C280 milliliters, repeat the reduction process of embodiment 6,50 ℃ of temperature, reaction pressure 2.65MPa, green oil air speed 3.0 hours
-1(total air speed 7.5 hours
-1), feed C6～C8 midbarrel drippolene raw material under the condition of hydrogen/oil volume than 110: 1 and test.C6～C8 midbarrel drippolene raw material weight percentage consists of C
6Hydrocarbon 32.8%, C
7Hydrocarbon 35.1%, C
8Hydrocarbon 32.1%, diene value 23.99 gram iodine/100 gram oil.Hydrogenation the results are shown in Table 4.
Table 4
| Reaction time (hour) | The average diene of product (gram iodine/100 gram oil) | Average diolefin hydrogenation rate (%) |
| 50 | 0.63 | 96.85 |
| 100 | 0.45 | 97.75 |
| 150 | 0.77 | 96.15 |
| 200 | 0.51 | 97.45 |
| 250 | 0.66 | 96.70 |
| 300 | 0.48 | 97.60 |
| 350 | 0.69 | 96.55 |
| 400 | 0.54 | 97.30 |
| 450 | 0.62 | 96.90 |
| 500 | 0.46 | 97.70 |
Claims (5)
1, a kind of macropore capacity sulfureous-containing nickel catalyst that is used for selective hydrogenation comprises following component by weight percentage:
(a) 5.0～40.0% metallic nickel or its oxide;
(b) 0.01～20.0% be selected from least a element or its oxide in molybdenum or the tungsten;
(c) 0.01～10.0% be selected from least a element or its oxide in the rare earth;
(d) 0.01～2.0% be selected from least a element or its oxide among IA in the periodic table of elements or the IIA;
(e) 0～15.0% be selected from least a element or its oxide in silicon, phosphorus, boron or the fluorine;
(f) 0～10.0% be selected from least a element among the IVB or its oxide in the periodic table of elements;
(g) 0.01～10.0% sulphur or its compound;
(h) alumina catalyst support of surplus;
Wherein total pore volume of carrier is 0.5～1.2 a milliliter/gram.
According to the described macropore capacity sulfureous-containing nickel catalyst that is used for selective hydrogenation of claim 1, it is characterized in that by weight percentage that 2, the content of metallic nickel or its oxide is 10.0～30.0%; Being selected from least a element in molybdenum or the tungsten or the content of its oxide is 0.1～15.0%; Being selected from least a element in the rare earth or the content of its oxide is 0.1～5.0%; Being selected from least a element among IA in the periodic table of elements or the IIA or the content of its oxide is 0.2～0.8%; Being selected from least a element in silicon, phosphorus, boron or the fluorine or the content of its oxide is 0.5～10.0%; The content that is selected from least a element among the IVB in the periodic table of elements or its oxide is 0.1～5.0%; The content of sulphur or its compound is 0.1～8.0%.
3, according to the described macropore capacity sulfureous-containing nickel catalyst that is used for selective hydrogenation of claim 1, the element that it is characterized in that being selected from the rare earth is selected from lanthanum or the cerium at least a; The element that is selected from IA in the periodic table of elements is a potassium; Be selected from that the element of IIA is selected from calcium, magnesium or the barium at least a in the periodic table of elements; Be selected from that the element of IVB is selected from titanium or the zirconium at least a in the periodic table of elements.
4, according to the described macropore capacity sulfureous-containing nickel catalyst that is used for selective hydrogenation of claim 1, the specific area that it is characterized in that carrier is 100～180 meters
2/ gram, total pore volume are 0.8～1.1 milliliter/gram.
5, according to the described macropore capacity sulfureous-containing nickel catalyst that is used for selective hydrogenation of claim 4, the specific area that it is characterized in that carrier is 120～160 meters
2/ gram.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101178543A CN100506379C (en) | 2006-11-02 | 2006-11-02 | Large Pore Volume Sulfur-Containing Nickel Catalysts for Selective Hydrogenation |
| PCT/CN2007/002776 WO2008040175A1 (en) | 2006-09-20 | 2007-09-20 | A nickel catalyst for selective hydrogenation |
| US12/442,150 US8236726B2 (en) | 2006-09-20 | 2007-09-20 | Nickel catalyst for selective hydrogenation |
| JP2009528579A JP5261801B2 (en) | 2006-09-20 | 2007-09-20 | Nickel catalysts for selective hydrogenation |
| KR1020097007686A KR101404770B1 (en) | 2006-09-20 | 2007-09-20 | A nickel catalyst for selective hydrogenation |
| TW096135282A TWI445575B (en) | 2006-09-20 | 2007-09-20 | A nickel catalyst for selective hydrogenation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101178543A CN100506379C (en) | 2006-11-02 | 2006-11-02 | Large Pore Volume Sulfur-Containing Nickel Catalysts for Selective Hydrogenation |
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| CN100506379C true CN100506379C (en) | 2009-07-01 |
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| KR102300823B1 (en) * | 2017-12-29 | 2021-09-09 | 한화솔루션 주식회사 | Hydrogenation catalyst and process for preparing thereof |
| KR102735172B1 (en) | 2019-06-28 | 2024-11-28 | 한화솔루션 주식회사 | Catalyst for nickel-based hydrogenation reaction, and preparation method thereof |
| KR102735177B1 (en) * | 2019-06-28 | 2024-11-28 | 한화솔루션 주식회사 | Nickel catalyst for hydrogenation reaction and preparation method thereof |
| KR102528310B1 (en) | 2019-06-28 | 2023-05-02 | 한화솔루션 주식회사 | Catalyst for hydrogenation reaction and preparation method thereof |
| KR20210001781A (en) * | 2019-06-28 | 2021-01-06 | 한화솔루션 주식회사 | Catalyst for hydrogenation and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB860839A (en) * | 1958-12-03 | 1961-02-08 | British Petroleum Co | Improvements relating to the production of alkyl aryl compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB860839A (en) * | 1958-12-03 | 1961-02-08 | British Petroleum Co | Improvements relating to the production of alkyl aryl compounds |
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