CN103666548A - Selective hydrogenation method for gasoline - Google Patents
Selective hydrogenation method for gasoline Download PDFInfo
- Publication number
- CN103666548A CN103666548A CN201210322247.6A CN201210322247A CN103666548A CN 103666548 A CN103666548 A CN 103666548A CN 201210322247 A CN201210322247 A CN 201210322247A CN 103666548 A CN103666548 A CN 103666548A
- Authority
- CN
- China
- Prior art keywords
- oxide
- catalyzer
- hydrogenation
- catalyst
- nickel
- 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
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003921 oil Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 238000000197 pyrolysis Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims abstract description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 4
- 239000011787 zinc oxide Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 15
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- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 14
- 229940079864 sodium stannate Drugs 0.000 claims description 14
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
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- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
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- 229910052728 basic metal Inorganic materials 0.000 claims description 7
- 150000003818 basic metals Chemical class 0.000 claims description 7
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002671 adjuvant Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 15
- 150000001993 dienes Chemical class 0.000 abstract description 10
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 3
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 229910001887 tin oxide Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 38
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 27
- 230000009467 reduction Effects 0.000 description 26
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 24
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 239000005864 Sulphur Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 230000004048 modification Effects 0.000 description 15
- 238000012986 modification Methods 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 230000032683 aging Effects 0.000 description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 13
- 235000018660 ammonium molybdate Nutrition 0.000 description 13
- 229910017604 nitric acid Inorganic materials 0.000 description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 12
- 239000011609 ammonium molybdate Substances 0.000 description 12
- 229940010552 ammonium molybdate Drugs 0.000 description 12
- 230000009849 deactivation Effects 0.000 description 12
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- 239000011148 porous material Substances 0.000 description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
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- 229960001866 silicon dioxide Drugs 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
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- 239000000377 silicon dioxide Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 239000004480 active ingredient Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 229910052785 arsenic Inorganic materials 0.000 description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 229910052622 kaolinite Inorganic materials 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 235000015320 potassium carbonate Nutrition 0.000 description 6
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
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- 150000005673 monoalkenes Chemical class 0.000 description 4
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a selective hydrogenation method for pyrolysis gasoline, which adopts a fixed bed reactor; a nickel-based hydrogenation catalyst characterized in thatThe hydrogenation process conditions are as follows: the liquid volume airspeed is 1.0-4.0 h-1The inlet temperature of the reactor is 30-130 ℃, the reaction pressure is more than or equal to 2.4MPa, and the volume ratio of hydrogen to oil is 100-500: 1. The catalyst takes alumina as a carrier, and comprises 14-19% of nickel oxide, 2-5% of tin oxide, 0.1-8% of alkali metal lithium oxide and/or potassium oxide, 0.5-8% of copper oxide and/or zinc oxide, 0.3-8% of molybdenum oxide and/or tungsten oxide and 0-8% of silicon oxide and/or phosphorus oxide by taking the weight of the catalyst as 100%. The process is suitable for the selective hydrogenation of diolefin in pyrolysis gasoline, and the hydrogenated product can be used as a good gasoline blending component or a raw material for producing aromatic hydrocarbon by further hydrogenation.
Description
Technical field
The present invention relates to a kind of method of hydrotreating of gasoline, the method is applicable to one-stage selective hydrogenation of gasoline splitting technique, is particularly useful for the hydrogenation technique that diolefin selective hydrogenation in full-cut fraction pyrolysis gasoline one-stage hydrogenation reaction is converted into monoolefine.
Background technology
Pyrolysis gasoline cut fraction is the important by-products of ethylene industry, be about 50% ~ 80% of ethylene yield, because it is rich in aromatic hydrocarbons and high-octane alkene, can, as the important sources of Aromatics Extractive Project after two-stage hydrogenation, also can only after one-stage hydrogenation, obtain good gasoline blend component.First paragraph hydrogenation reaction is carried out at low temperatures, generally selects Pd base or Ni catalyst based, and object is to remove the easily component of polymerization such as conjugated dienes, vinylbenzene, but will prevent monoolefin hydrogenation, the device temperature runaway in order to avoid the very exothermic of monoolefin hydrogenation induces reaction.
In recent years, in pyrolysis gasoline hydrogenation charging, the foreign matter content such as arsenic is and continues rising trend, and is often with water, causes hydrogenating materials character variation, causes the running of Pd base pyrolysis gasoline hydrogenation catalyst not good, and regeneration is frequent, has a strong impact on the normal running of device.Compare with Pd is catalyst based, Ni is catalyst based to have a clear superiority in the impurity performances such as anti-arsenic, and price advantage is also obvious simultaneously.Therefore, the pyrolysis gasoline hydrogenation device of domestic many producers adopts Ni catalyst based one after another, especially domestic newly-built large-scale ethylene plant, its supporting pyrolysis gasoline hydrogenation device just adopts Ni catalyst based at the beginning of design, therefore, the Ni-based full-cut fraction pyrolysis gasoline one-stage hydrogenation of development of new catalyzer is the demand of market and technology competition.The subject matter that the development of Ni-based load hydrogenation catalyst faces is how to improve the hydrogenation selectivity of catalyzer, stabilized hydrogenation and thermostability and anti-sulphur, arsenic, colloid performance.
CN200610118522.7 discloses a kind of nickel catalyzator with composite pore structural for selective hydrogenation, mainly solve in prior art, exist the low temperature active of catalyzer low, immunity from interference is weak, hold that glue ability is low, the technical problem of poor stability, resistance to free-water poor performance.Comprise by weight percentage following component: (a) 5.0～40.0% metallic nickel or its oxide compound; (b) 0.01～20.0% be selected from least one element or its oxide compound in molybdenum or tungsten; (c) 0.01～10.0% be selected from least one element or its oxide compound in rare earth; (d) 0.01～2.0% be selected from least one element or its oxide compound in IA in the periodic table of elements or IIA; (e) 0～15.0% be selected from least one element or its oxide compound in silicon, phosphorus, boron or fluorine; (f) 0～10.0% be selected from the element of at least one in IVB or its oxide compound in the periodic table of elements; (g) alumina catalyst support of surplus.Wherein total pore volume of carrier is 0.5 ~ 1.2ml/g, the pore volume of bore dia < 30nm accounts for 5 ~ 65% of total pore volume, the pore volume of bore dia 30～60nm accounts for 20～80% of total pore volume, and the pore volume of bore dia > 60nm accounts for 20～50% of total pore volume.
CN97121810.2 discloses a kind of selective hydrogenation catalyst, the aluminum oxide of the NiO of 5 ~ 25 ω %, the lithium of 0.1 ~ 2.0 ω % or alkaline-earth metal and surplus, consists of.This catalyzer is that Ni is made on the alumina supporter containing lithium or alkaline-earth metal, is applicable to the selective hydrogenation process containing the full distillate oil of the distillate, particularly pyrolysis gasoline of diolefin.
CN200610064905.0 discloses a kind of Hydrobon catalyst, preparation method and application, it is active ingredient that catalyzer be take molybdenum, cobalt, nickel, add auxiliary agent, take aluminum oxide as carrier, take total catalyst weight as 100%, catalyzer contains molybdenum oxide 14～20%, cobalt oxide 1～6%, nickel oxide 1～4%, the alkali-metal oxide content of auxiliary agent is 1～3%, auxiliary agent P is or/and the oxide content of Sb is that 1～5%, Si is or/and the oxide content of tin is 2～6%; The pore volume of catalyzer is 0.45～0.65cm
3/ g, specific surface area is 150～280m
2/ g.This catalyzer can be used for the hydrofining of medium-low distillate oil, and hydrogenation saturated mono alkene to greatest extent in hydrogenating desulfurization can adapt to oil product that sulphur content is changeable and the requirement of high-speed, but diolefine is not had to hydrogenation selectivity.
CN200710176670.9 discloses a kind of selective nickel series hydrogenating catalyst and preparation method thereof, take aluminum oxide as carrier, it is characterized in that take that catalyst weight is as 100%, contain active ingredient 14～20% nickel oxide, 2～8% lanthanum trioxides and/or cerium oxide and 1～8% VI B oxides additive, 2～8% silicon-dioxide, 1～8% alkaline earth metal oxide, specific surface area of catalyst 60～150m
2/ g, pore volume 0.4～0.6ml/g.This catalyzer has good Hydrogenation, especially has the ability of anti-impurity and anticol matter, and has good stabilized hydrogenation performance, is specially adapted to medium-low distillate oil diene selective hydrogenation, is particularly useful for full-cut fraction pyrolysis gasoline diolefin selective hydrogenation.
CN200510060612.0 discloses a kind of preparation method of loading type nickel-based catalyst of high dispersive, and employing complex ni-ion is that presoma, direct impregnation load on the microsphere silica gel, alumina microsphere with very high mechanical strength and wear resisting property.Complex ni-ion comprises: nickel-ammonia complex ion [Ni (NH
3)
x(H
2o)
6-x]
2+(x=1～6); Ethylenediamine nickel [Ni (en)
x(H
2o)
6-2x]
2+(x=1～3) (en: quadrol); Ethylenediamine tetraacetic acid (EDTA) closes nickel [Ni (EDTA)]
2-(EDTA ethylenediamine tetraacetic acid (EDTA)); Nickel acetylacetonate (CH
3cOCHC (CH
3) O)
2ni etc.; In catalyzer 1～30% of the charge capacity vehicle weight of nickel.
CN200610064904.6 discloses a kind of monoolefin hydrogenation that is suitable for, and is particularly suited for nickel catalyst of cracking carbon nine cut fraction hydrogenation and preparation method thereof.Catalyzer be take aluminum oxide and silicon oxide and is prepared from as carrier adopts coprecipitation method, weight percent hundred content meters that form with catalyzer: containing NiO40 ~ 70%, and La
2o
32 ~ 5%, X
1oxide compound 2 ~ 5%, X
2oxide compound 20 ~ 50%, X
1be selected from one or more in Cu, Mg, Zr, X
2be selected from Al and/or Si.
For the hydrotreatment of pyrolysis gasoline, first to select good selective hydrogenation catalyst, secondly also under gentle operational condition, carry out hydrogenation, to adapt to one-stage selective hydrogenation of gasoline splitting technique, reach good hydrogenation effect.Therefore, need to develop the process for selective hydrogenation that a kind of reaction conditions relaxes, adaptability to raw material is strong.
Summary of the invention
The object of the present invention is to provide a kind of process for selective hydrogenation of pyrolysis gasoline, the method is used the nickel-base catalyst that comprises the metal oxide components such as Ni, Sn, be applicable to the selective hydrogenation of diolefin in pyrolysis gasoline, hydrogenated products can be used as the raw material of good gasoline blend component or further hydrogenation production aromatic hydrocarbons.
The invention provides a kind of pyrolysis gasoline process for selective hydrogenation, adopt fixed-bed reactor; Used catalyst is nickel-base hydrogenation catalyst, take aluminum oxide as carrier, take catalyst weight as 100%, containing nickel oxide 14 ~ 19%, preferably 15 ~ 18%, stannic oxide 2 ~ 5%, preferably 2.6 ~ 4.5%, basic metal Lithium Oxide 98min and/or potassium oxide 0.1 ~ 8%, preferably 0.6 ~ 5.5%, cupric oxide and/or zinc oxide 0.5 ~ 8%, preferably 1.5 ~ 5.5%, molybdenum oxide and/or Tungsten oxide 99.999 0.3 ~ 8%, preferably 0.5 ~ 5.5%, silicon oxide and/or phosphorus oxide 0 ~ 8%, preferably 0 ~ 6.9%.Hydrogenation technique condition is: liquid volume air speed 1.0 ~ 4.0h
-1, 30 ~ 130 ℃ of reactor inlet temperatures, reaction pressure>=2.4MPa, hydrogen to oil volume ratio 100 ~ 500:1.
Process for selective hydrogenation provided by the invention, its fixed-bed reactor can be that fixed bed adiabatic reactor can be also fixed bed isothermal reactor, preferably fixed bed adiabatic reactor; Liquid volume air speed is preferably 1.5 ~ 3.5h
-1, preferably 45 ~ 110 ℃ of reactor inlet temperatures, reaction pressure is preferably 2.6 ~ 3.0MPa, and hydrogen to oil volume ratio is preferably than 100 ~ 300.
Method of hydrotreating used catalyst of the present invention is to adopt pickling process to make.The carrier of catalyzer is δ crystal formation aluminum oxide or take δ type as main δ, α mixing crystal formation aluminum oxide; When carrier is δ, α mixing crystal formation aluminum oxide, best alpha-crystal form quality of alumina content <20% wherein.
The present invention also provides a kind of selectivity Ni-based hydrogenation catalyst preparation method, comprise the following steps: 1) at 20 ~ 40 ℃ by the compound of alkali metal containing Li and/or K and promotor and water wiring solution-forming, spray aluminium hydroxide powder, mediates to powder the compound making it with alkali metal containing Li and/or K simultaneously and fully contacts; In the aluminium hydroxide powder of above-mentioned alkali metal containing Li and/or K, add the compound containing Si and/or P, mediate extruded moulding, 100 ~ 140 ℃ of dry 2 ~ 4h, 900 ~ 1100 ℃ of roasting 4 ~ 6h, make the alumina supporter containing auxiliary agent; 2) at 20 ~ 40 ℃, the salt that contains active component nickel, the salt that contains adjuvant component Sn, Cu and/or Zn, Mo and/or W are dissolved in the water, add again complexing agent, make steeping fluid, dipping is containing after the alumina supporter of auxiliary agent, 100 ~ 140 ℃ of dry 2 ~ 4h, 350 ~ 550 ℃ of roasting 4 ~ 6h, make catalyzer.
In the present invention, promotor can be citric acid and/or oxalic acid.The add-on of promotor changes according to the height of the add-on of basic metal Li and/or K, and the present invention is not limited especially, and the mol ratio of citric acid and/or oxalic acid and basic metal Li and/or K atom is preferably 0.35:1 ~ 0.8:1.
In nickel catalyzator use procedure, nickle atom there is migration and coalescent be the one of the main reasons that causes catalyst deactivation.Improving dispersiveness and the tack of nickel component on carrier, is the key that guarantees the steady running of catalyzer long period.Adopt basic metal to carry out to carrier the acidity that modification can regulate carrier, make support acidity moderate, but carrier still exists the problem that defect concentrations in crystals is low, electron affinity is poor, while making active ingredient Ni, tack, bad dispersibility; The present invention adopts compound and promotor and the water wiring solution-forming spray aluminium hydroxide powder of basic metal Li and/or K, when the compound that guarantees alkali metal containing Li and/or K fully contacts with powder, can avoid excessive water to be incorporated in aluminium hydroxide powder; Because completing aluminum hydroxide slurry aluminium hydroxide skeleton after super-dry of plastic process basically forms, and forming section micropore, on this basis, with the solution of alkali metal containing Li and/or K complex compound, it is carried out to modification, can peptization micropore, effectively eliminate micro-holes ratio, hydroxide ion on simultaneously can dissolved hydrogen aluminum oxide skeleton, prevents in the time of Effective Regulation acidity that too much B acid from producing; Can make carrier surface trend micritization, equally distributed state, when reducing support acidity, can increase the defect concentrations in crystals of carrier, produce new active constituent loading center, and improve the electron affinity of carrier, be conducive to improve dispersiveness and the tack of active ingredient on carrier, and then improve the stabilized hydrogenation of catalyzer, make the steady running of catalyzer long period.
The solution that the aqueous solution of complexing agent and active ingredient and auxiliary agent forms is due to the feature of component molecular structure, and generation self-association and cross association, can form that surface tension is little, viscosity is low, clarification is stable, the Associated Solutions that has weak chemical action, this special steeping fluid can avoid nickel salt to occur coacervation in dipping and drying process.In the present invention, complexing agent is one or more in glycol or glycol ether, triglycol, Tetraglycol 99 etc., preferably triglycol and/or Tetraglycol 99.The add-on of complexing agent changes according to the height of the add-on of nickel, and the present invention is not limited especially, and the mass ratio of complexing agent and nickel oxide is preferably 0.3:1 ~ 0.8:1, and the too high large amount of organic that easily causes in roasting process decomposes, and causes catalyst breakage.The too low effect that cannot reach raising active ingredient dispersity.
The adjuvant component Mo and/or the W that in the present invention, add can compete NiO with carrier, suppress Ni
2alO
4or the generation of nickel aluminate, because the reduction temperature of nickel molybdate, wolframic acid nickel or many nickel molybdates compares Ni
2alO
4or nickel aluminate is slightly low, can improves to a certain extent the growing amount of the NiO of performance active function, and then improve the hydrogenation activity of active ingredient utilization ratio and catalyzer; The consumption of adjuvant component Mo and/or W requires suitably, and consumption too much can cause catalyst selectivity to decline.
Adjuvant component Sn plays isolation and the fixedly effect of active component nickel, be conducive to improve metallic nickel in the distribution of carrier surface, prevent growing up of nickel crystallite, improve the thermostability of catalyzer, make catalyzer there is good thermal activation performance, can bear high temperature reduction and manipulation of regeneration.Sn acts synergistically with Cu and/or Zn simultaneously, improves the electronegativity of Ni, makes monoolefine, benzene, and the impurity such as sulphur, arsenic are difficult to absorption, the impurity performances such as the diolefin hydrogenation selectivity of raising catalyzer and anti-sulphur, arsenic.
In the present invention, active component nickel, auxiliary agent Cu and/or Zn can be vitriol, carbonate, nitrate, halogenide, acetate etc., require soluble in water, to fully dissolve, solution-stabilized; Additive alkali metal can be nitrate, carbonate, oxyhydroxide etc., Sn adds with the form of sodium stannate, the present invention can not directly use stannic oxide and nitric acid tin, causes solution not clarify, thus the catalyst hydrogenation weak effect of preparation because stannic oxide and nitric acid tin are easy to hydrolysis; The soluble salt of Mo and/or W can be ammonium molybdate, ammonium tungstate, Sodium orthomolybdate or sodium wolframate, preferably ammonium molybdate or ammonium tungstate.
The present invention also provides a kind of method of reducing that is applicable to nickel catalyzator used in this method of hydrotreating process, the present invention in hydrogenation unit outside (in device) or hydrogenation unit (outside device) adopt the method for segmentation reduction to carry out reducing catalyst.In device, reducing process condition is: pressure 0.5MPa, the volume ratio 700 ~ 1300Nm of hydrogen and catalyzer
3/ m
3/ h, with 30～60 ℃/h temperature rise rate, be warmed up to 230～260 ℃ and maintain 9～12h, then the speed with 7～12 ℃/h is warmed up to 300～330 ℃, maintain 6～10h, then the speed with 10～15 ℃/h is warmed up to 350～380 ℃, maintains 10～15h, is warmed up to 390～450 ℃ more afterwards with 10～20 ℃/h, maintain 2～6h, reduction finishes.When catalyzer is when hydrogenator reduces outward, the catalyst activity component nickel after reduction also needs to carry out surface oxidation, and this surface oxidation adopts the general technology in this area to process.The reduction process of catalyzer is with reducing in device, after reduction finishes, cool to 30 ~ 40 ℃, pass into the gas mixture of nitrogen and air, and progressively strengthen air capacity until complete blowing air completes passivation, control whole process beds temperature rise≤40 ℃, the catalyzer of this surface passivation before for hydrogenation reaction, need be in hydrogenator under 150 ~ 200 ℃ of conditions with hydrogen reducing 10 ~ 16h.
Before charging, also need the catalyzer after activation to carry out Passivation Treatment, so that catalyzer has stable hydrogenation activity, be convenient to reaction to control.
The present invention also provides the deactivating process for the treatment of of nickel catalyzator used.Its suitable processing condition are: working pressure 0.5MPa, and passivation temperature is 30 ~ 70 ℃, preferably 40 ~ 50 ℃, passivated oil sulphur content 100 ~ 650ug/g, preferred 250 ~ 500ug/g, passivated oil air speed is < 10h
-1, preferred 2 ~ 7h
-1, passivation time is 10 ~ 20h, preferably 12 ~ 16h.Passivated oil can be Performance Test of First Stage Hydrogenation Catalyst of Pyrolysis Gasoline product oil, petroleum naphtha and hexanaphthene, wherein said passivated oil diene value < 1.0gI/100g, bromine valency < 10.0gBr/100g.
Adopt pyrolysis gasoline process for selective hydrogenation provided by the invention to select to comprise the nickel-base catalyst of the metal oxide components such as Ni, Sn, this catalyzer has that hydrogenation activity is good, hydrogenation selectivity is high, stabilized hydrogenation and the feature such as thermostability is strong and the poisonous substance ability such as anti-sulphur, arsenic is strong, applicable to one-stage selective hydrogenation of gasoline splitting technique, be particularly useful for full-cut fraction pyrolysis gasoline one-stage selective hydrogenation technique.
One-stage selective hydrogenation of gasoline splitting method operation condition provided by the invention is gentle, the strong adaptability to different material; Can make nickel-base catalyst have suitable initial activity, excellent hydrogenation selectivity and stabilized hydrogenation performance, be conducive to the long-term operation of device.
Embodiment
Kaolinite Preparation of Catalyst main raw material used source:
Al
2o
3: Zibo Wanlin Chemical Technology Co., Ltd. provides, pore volume 0.90 ~ 0.95ml/g, specific surface area 300 ~ 320m
2/ g;
Nickelous nitrate: analytical pure, Yixing Shen Sheng catalyzer company limited produces;
Zinc nitrate: analytical pure, Nantong Long Sheng Chemical Co., Ltd.;
Cupric nitrate: Yixing Xu Chi Chemical Co., Ltd. produces;
Ammonium tungstate: Jiangyan City Run Dong metal products company limited;
Ammonium molybdate: analytical pure, Anda, Jiangyan City non-ferrous metal company limited;
Sodium stannate: analytical pure, Cologne, Guangzhou Hua Bo Instrument Ltd..
Analytical procedure and standard:
The metal content measuring method of catalyzer: adopt metal content in atomic absorption detecting catalyzer;
Bromine valency: SH/T 0630-1996 petroleum products bromine valency, bromine index assay method (coulometry);
Diene: UOP326-07 Maleic Anhydride Method;
Hydrogenating materials: Dushanzi petrochemical industry provides pyrolysis gasoline, and oil property is as described in Table 1.
Table 1 C
5~ C
9stock oil character
Embodiment 1
20.7g citric acid is dissolved in 30 ℃ of water, add 10.4g Quilonum Retard to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water, 5ml nitric acid (content 60%) and 9.7g silicon sol (containing 40% silicon-dioxide), extruded moulding after continuing to mediate, 120 ℃ of dry 4h in air, 980 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 30 ℃ of conditions, 86.4g nickelous nitrate, 7.2g sodium stannate, 17.1g zinc nitrate, 14.3g cupric nitrate, 3.3g ammonium molybdate are mixed with to the 90ml aqueous solution, add again 6.5g Tetraglycol 99, then impregnated on 100g modified support, ageing 6h, 120 ℃ of dry 2h in air, 350 ℃ of roasting 4h, make catalyzer C-1.
Comparative example 1
20.7g citric acid is dissolved in 30 ℃ of water, add 10.4g Quilonum Retard to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water, 5ml nitric acid (content 60%) and 9.7g silicon sol (containing 40% silicon-dioxide), extruded moulding after continuing to mediate, 120 ℃ of dry 4h in air, 980 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 30 ℃ of conditions, 81.3g nickelous nitrate, 13.5g cupric nitrate, 3.1g ammonium molybdate are mixed with to the 90ml aqueous solution, then add 6.0g Tetraglycol 99, then impregnated on 100g modified support ageing 6h, 120 ℃ of dry 2h in air, 350 ℃ of roasting 4h, make catalyzer D-1.
In 500ml adiabatic reactor hydrogenation unit, carry out the reduction of catalyzer C-1 and D-1: at the volume ratio 1200Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, with 45 ℃/h temperature rise rate, be warmed up to 250 ℃, maintain 10h, with the speed of 10 ℃/h, be warmed up to 300 ℃, maintain 9h, with the speed of 10 ℃/h, be warmed up to 350 ℃, maintain 12h, with 10 ℃/h, be warmed up to 430 ℃, maintain 5h more afterwards; Cool to 50 ℃, employing air speed is 4h
-1, the sulphur content hexanaphthene that is 400ug/g is two catalyst deactivation 12h; Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.8MPa, and 35 ~ 50 ℃ of reactor inlet temperatures, liquid volume air speed 3h
-1, hydrogen with oil volume than the 200h that turns round under 400:1 condition.Hydrogenation reaction the results are shown in Table 2.
Table 2 Embodiment C-1 and comparative example D-1 catalyzer 200h hydrogenation reaction result
| Project | Embodiment C-1 | Comparative example D-1 |
| Products benzene ethylene content/% | 1.14 | 1.32 |
| Products benzene rate of loss/% | 0.80 | 1.63 |
Adopt method of hydrotreating of the present invention, with respect to catalyzer D-1, styrene content and the benzene rate of loss of catalyzer C-1 hydrogenated products are all lower, illustrate that catalyzer C-1 has good anti-arsenic performance and hydrogenation selectivity.
Embodiment 2
42.6g citric acid is dissolved in 35 ℃ of water, add 18.7g Quilonum Retard to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water, 5ml nitric acid (content 60%) and 9.7g phosphoric acid (content 85%), extruded moulding after continuing to mediate, 130 ℃ of dry 2h in air, 1050 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 30 ℃ of conditions, 80.7g nickelous nitrate, 6.6g sodium stannate, 9.8g zinc nitrate, 4.9g ammonium molybdate, 4.5g ammonium tungstate are mixed with to the 90ml aqueous solution, add again 10.0g triglycol, then impregnated on 100g modified support, ageing 6h, 120 ℃ of dry 3h in air, 500 ℃ of roasting 6h, make catalyzer C-2.
Comparative example 2
42.6g citric acid is dissolved in 35 ℃ of water, add 18.7g Quilonum Retard to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water, 5ml nitric acid (content 60%) and 9.7g phosphoric acid (content 85%), extruded moulding after continuing to mediate, 130 ℃ of dry 2h in air, 1050 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 30 ℃ of conditions, 84.0g nickelous nitrate, 6.9g sodium stannate, 10.2g zinc nitrate, 7.7g ammonium molybdate, 7.1g ammonium tungstate are mixed with to the 90ml aqueous solution, add again 10.5g triglycol, then impregnated on 100g modified support, ageing 6h, 120 ℃ of dry 3h in air, 500 ℃ of roasting 6h, make catalyzer D-2.
In 500ml adiabatic reactor hydrogenation unit, carry out the reduction of catalyzer C-2 and D-2: at the volume ratio 900Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, with 50 ℃/h temperature rise rate, be warmed up to 260 ℃, maintain 9h, with the speed of 8 ℃/h, be warmed up to 320 ℃, maintain 7h, with the speed of 15 ℃/h, be warmed up to 350 ℃, maintain 12h, with 10 ℃/h, be warmed up to 420 ℃, maintain 6h more afterwards; Cool to 45 ℃, employing air speed is 5h
-1, the sulphur content hexanaphthene that is 500ug/g is two catalyst deactivation 14h; Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.8MPa, and 35 ~ 55 ℃ of reactor inlet temperatures, liquid volume air speed 2.5h
-1, hydrogen with oil volume than the 200h that turns round under 300:1 condition.Hydrogenation reaction the results are shown in Table 3.
Table 3 Embodiment C-2 and comparative example D-2 catalyzer 200h hydrogenation reaction result
| Project | Embodiment C-2 | Comparative example D-2 |
| Products benzene ethylene content/% | 1.08 | 0.7 |
| Products benzene rate of loss/% | 0.52 | 6.51 |
Adopt method of hydrotreating of the present invention, with respect to catalyzer C-2, the styrene content of catalyzer D-2 hydrogenated products is low, benzene rate of loss is high, illustrates that catalyzer D-2 activity is higher, and selectivity is poor.
Embodiment 3
3.0g citric acid and 1.3g oxalic acid are dissolved in 40 ℃ of water, add 5.3g salt of wormwood to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water and 5ml nitric acid (content 60%) and 24.9g silicon sol (containing 40% silicon-dioxide), extruded moulding after continuing to mediate, 120 ℃ of dry 3h in air, 1100 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 40 ℃ of conditions, 79.4g nickelous nitrate, 5.7g sodium stannate, 5.6g zinc nitrate, 3.9g cupric nitrate, 1.5 ammonium molybdates, 1.4g ammonium tungstate are mixed with to the 90ml aqueous solution, add again 6.9g triglycol, then impregnated on 100g modified support, ageing 6h, 120 ℃ of dry 3h in air, 550 ℃ of roasting 3h, make catalyzer C-3.
Comparative example 3
3.0g citric acid and 1.3g oxalic acid are dissolved in 40 ℃ of water, add 5.3g salt of wormwood to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water and 5ml nitric acid (content 60%) and 24.9g silicon sol (containing 40% silicon-dioxide), extruded moulding after continuing to mediate, 120 ℃ of dry 3h in air, 1100 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 40 ℃ of conditions, 77.5g nickelous nitrate, 5.5g sodium stannate, 5.4g zinc nitrate, 3.8g cupric nitrate are mixed with to the 90ml aqueous solution, then add 6.8g triglycol, then impregnated on 100g modified support ageing 6h, 120 ℃ of dry 3h in air, 550 ℃ of roasting 3h, make catalyzer D-3.
In 500ml adiabatic reactor hydrogenation unit, carry out the reduction of catalyzer C-3 and D-3: at the volume ratio 1000Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, with 55 ℃/h temperature rise rate, be warmed up to 255 ℃, maintain 11h, with the speed of 9 ℃/h, be warmed up to 310 ℃, maintain 8h, with the speed of 12 ℃/h, be warmed up to 370 ℃, maintain 10h, with 15 ℃/h, be warmed up to 400 ℃, maintain 6h more afterwards; Cool to 40 ℃, employing air speed is 3.5h
-1, the sulphur content hexanaphthene that is 350ug/g is catalyst deactivation 13h; Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.6MPa, and 40 ~ 60 ℃ of reactor inlet temperatures, liquid volume air speed 2.0h
-1, hydrogen with oil volume than the 200h that turns round under 250:1 condition.Hydrogenation reaction the results are shown in Table 4.
Table 4 Embodiment C-3 and comparative example D-3 catalyzer 200h hydrogenation reaction result
| Project | Embodiment C-3 | Comparative example D-3 |
| Products benzene ethylene content/% | 0.95 | 1.23 |
| Products benzene rate of loss/% | 0.65 | 0.61 |
Adopt method of hydrotreating of the present invention, with respect to catalyzer C-3, in the situation that hydrogenated products benzene rate of loss is suitable, catalyzer D-3 vinylbenzene is higher, active not good enough.
Embodiment 4
10.6g citric acid is dissolved in 40 ℃ of water, add 5.1g Quilonum Retard to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water, 5ml nitric acid (content 60%) and 3.0g phosphoric acid (content 85%), extruded moulding after continuing to mediate, 120 ℃ of dry 4h in air, 1000 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 30 ℃ of conditions, 77.2g nickelous nitrate, 5.9g sodium stannate, 8.5g zinc nitrate, 4.4g ammonium tungstate are mixed with to the 95ml aqueous solution, add again 3.1g triglycol and 3.1g Tetraglycol 99, then impregnated on 100g modified support, ageing 6h, 120 ℃ of dry 2h in air, 380 ℃ of roasting 4h, make catalyzer C-4.
Comparative example 4
10.6g citric acid is dissolved in 40 ℃ of water, add 5.1g Quilonum Retard to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water, 5ml nitric acid (content 60%) and 3.0g phosphoric acid (content 85%), extruded moulding after continuing to mediate, 120 ℃ of dry 4h in air, 1000 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 30 ℃ of conditions, 74.7g nickelous nitrate, 8.2g zinc nitrate, 4.2g ammonium tungstate are mixed with to the 95ml aqueous solution, then add 3.0g triglycol and 3.0g Tetraglycol 99, then impregnated on 100g modified support ageing 6h, 120 ℃ of dry 2h in air, 380 ℃ of roasting 4h, make catalyzer D-4.
The device that carries out catalyzer C-4 and D-4 on 150L fixed bed device reduces outward: at the volume ratio 1200Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, with 50 ℃/h temperature rise rate, be warmed up to 250 ℃ and maintain 10h, with the speed of 10 ℃/h, be warmed up to 300 ℃, maintain 9h, with the speed of 14 ℃/h, be warmed up to 360 ℃, maintain 13h, with 15 ℃/h, be warmed up to 430 ℃ more afterwards, maintain 6h, reduction finishes, and cools to 40 ℃, pass into the gas mixture of nitrogen and air, and progressively strengthen air capacity until complete blowing air completes passivation, and control whole process beds temperature rise≤40 ℃, obtain prereduction surface passivation state catalyzer C-4 and D-4.
Catalyzer C-4 and D-4 are packed in 500ml adiabatic reactor hydrogenation reaction device, under 180 ℃ of conditions, use hydrogen reducing 16h; Cool to 55 ℃, employing air speed is 4.5h
-1, the sulphur content petroleum naphtha that is 300ug/g is catalyst deactivation 10h; Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.6MPa, and 55 ~ 75 ℃ of reactor inlet temperatures, liquid volume air speed 2.5h
-1, hydrogen with oil volume than the 300h that turns round under 300:1 condition.Hydrogenation reaction the results are shown in Table 5.
Table 5 Embodiment C-4 and comparative example D-4 catalyzer 300h hydrogenation reaction result
Adopt method of hydrotreating of the present invention, with respect to catalyzer D-4, catalyzer C-4 better heat stability, during high temperature reduction, metallic nickel is difficult for assembling, and catalyst selectivity is better.
Embodiment 5
8.9g oxalic acid is dissolved in 40 ℃ of water, add 10.6g salt of wormwood to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water, 5ml nitric acid (content 60%), 8.1g phosphoric acid (content 85%) and 7.5g silicon sol (containing 40% silicon-dioxide), extruded moulding after continuing to mediate, 120 ℃ of dry 4h in air, 1050 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 40 ℃ of conditions, 99.3g nickelous nitrate, 10.7g sodium stannate, 22.7g zinc nitrate, 6.2g ammonium molybdate are mixed with to the 95ml aqueous solution, add again 6.0g triglycol and 7.6g Tetraglycol 99, then impregnated on 100g modified support, ageing 6h, 120 ℃ of dry 3h in air, 530 ℃ of roasting 6h, make catalyzer C-5.
Comparative example 5
140ml water and 5ml nitric acid (content 60%), 8.1g phosphoric acid (content 85%) and 7.5g silicon sol (containing 40% silicon-dioxide) are added in 300g pseudo-boehmite aluminum oxide powder, extruded moulding after mediating, 130 ℃ of dry 2h in air, 550 ℃ of roasting 5h, make Al
2o
3carrier.9.8g salt of wormwood is mixed with to the 180ml aqueous solution, on dipping and 200g carrier, 130 ℃ of dry 2h in air, 1030 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 40 ℃ of conditions, 99.3g nickelous nitrate, 10.7g sodium stannate, 22.7g zinc nitrate, 6.2g ammonium molybdate are mixed with to the 95ml aqueous solution, add again 6.0g triglycol and 7.6g Tetraglycol 99, then impregnated on 100g modified support, ageing 6h, 120 ℃ of dry 3h in air, 550 ℃ of roasting 5h, make catalyzer D-5.
In 500ml adiabatic reactor hydrogenation unit, carry out the reduction of catalyzer C-5 and D-5: at the volume ratio 1100Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, with 60 ℃/h temperature rise rate, be warmed up to 240 ℃, maintain 12h, with the speed of 7 ℃/h, be warmed up to 315 ℃, maintain 10h, with the speed of 13 ℃/h, be warmed up to 380 ℃, maintain 10h, with 15 ℃/h, be warmed up to 410 ℃, maintain 6h more afterwards; Cool to 50 ℃, employing air speed is 3.0h
-1, the sulphur content petroleum naphtha that is 250ug/g is catalyst deactivation 7h; Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.7MPa, and 50 ~ 85 ℃ of reactor inlet temperatures, liquid volume air speed 2.0h
-1, hydrogen with oil volume than the 588h that turns round under 200:1 condition.Hydrogenation reaction the results are shown in Table 6.
Table 6 Embodiment C-5 and comparative example D-5 catalyzer 500h hydrogenation reaction result
Adopt method of hydrotreating of the present invention, with respect to catalyzer D-4, in the situation that identical reaction temperature in and temperature raising speed are slower, catalyzer C-4 products benzene ethylene content is lower, illustrates that C-4 catalyzer has better stabilized hydrogenation performance.
Embodiment 6
23.9g oxalic acid is dissolved in 40 ℃ of water, add 16.3g Quilonum Retard to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water, 5ml nitric acid (content 60%) and 18.9g silicon sol (containing 40% silicon-dioxide), extruded moulding after continuing to mediate, 120 ℃ of dry 4h in air, 990 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 40 ℃ of conditions, 84.0g nickelous nitrate, 7.4g sodium stannate, 7.9g cupric nitrate, 1.8g ammonium tungstate, 2.4g ammonium molybdate are mixed with to the 95ml aqueous solution, add again 8.8g triglycol, then impregnated on 100g modified support, ageing 6h, 120 ℃ of dry 3h in air, 450 ℃ of roasting 5h, make catalyzer C-6.
In 500ml adiabatic reactor hydrogenation unit, carry out the reduction of catalyzer C-6: at the volume ratio 800Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, with 50 ℃/h temperature rise rate, be warmed up to 230 ℃, maintain 9h, with the speed of 10 ℃/h, be warmed up to 310 ℃, maintain 10h, with the speed of 10 ℃/h, be warmed up to 360 ℃, maintain 10h, with 15 ℃/h, be warmed up to 390 ℃, maintain 6h more afterwards; Cool to 50 ℃, employing air speed is 2h
-1, the sulphur content Performance Test of First Stage Hydrogenation Catalyst of Pyrolysis Gasoline product oil that is 400ug/g is catalyst deactivation 7h; Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.8MPa, and 50 ~ 60 ℃ of temperature ins, fresh feed oil air speed 2h
-1, hydrogen with oil volume than the 200h that turns round under 200:1 condition.Hydrogenation reaction the results are shown in Table 7.
Comparative example 6
In 500ml adiabatic reactor hydrogenation unit, carry out the reduction of catalyzer C-6: at the volume ratio 800Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, with 50 ℃/h temperature rise rate, be warmed up to 230 ℃, maintain 9h, with the speed of 10 ℃/h, be warmed up to 310 ℃, maintain 10h, with the speed of 10 ℃/h, be warmed up to 360 ℃, maintain 10h, with 15 ℃/h, be warmed up to 390 ℃, maintain 6h more afterwards, cool to 50 ℃.Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.8MPa, and 50 ~ 60 ℃ of reactor inlet temperatures, liquid volume air speed 2h
-1, hydrogen with oil volume than the 200h that turns round under 200:1 condition.Hydrogenation reaction the results are shown in Table 7.
Comparative example 7
In 500ml adiabatic reactor hydrogenation unit, carry out the reduction of catalyzer C-6: at the volume ratio 1000Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, with 30 ℃/h temperature rise rate, be warmed up to 300 ℃ and maintain 20h, with the speed of 20 ℃/h, be warmed up to 400 ℃, maintain 20h; Cool to 50 ℃, employing air speed is 2h
-1, the sulphur content Performance Test of First Stage Hydrogenation Catalyst of Pyrolysis Gasoline product oil that is 400ug/g is catalyst deactivation 7h; Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.8MPa, and 50 ~ 60 ℃ of reactor inlet temperatures, liquid volume air speed 2h
-1, hydrogen with oil volume than the 200h that turns round under 200:1 condition.Hydrogenation reaction the results are shown in Table 7.
Comparative example 8
In 500ml adiabatic reactor hydrogenation unit, carry out the reduction of catalyzer C-6: at the volume ratio 800Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, with 50 ℃/h temperature rise rate, be warmed up to 230 ℃, maintain 9h, with the speed of 10 ℃/h, be warmed up to 310 ℃, maintain 10h, with the speed of 10 ℃/h, be warmed up to 360 ℃, maintain 10h, with 15 ℃/h, be warmed up to 390 ℃, maintain 6h more afterwards; Cool to 50 ℃, employing air speed is 3h
-1, the sulphur content Performance Test of First Stage Hydrogenation Catalyst of Pyrolysis Gasoline product oil that is 800ug/g is catalyst deactivation 20h; Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.8MPa, and 55 ℃ of reactor inlet temperatures, liquid volume air speed 2h
-1, hydrogen with oil volume than the 100h that turns round under 200:1 condition.Hydrogenation reaction the results are shown in Table 7.
Table 7 embodiment 6 and comparative example 6,7,8 catalyzer 100h hydrogenation reaction results
Adopt method of hydrotreating of the present invention, with respect to embodiment 6, comparative example 6 catalyzer unpassivated are processed, and throw stock oil post-reactor temperature runaway; During comparative example 7 catalyst reduction, metallic nickel is easily assembled, and causes catalyst selectivity on the low side; Comparative example 8 catalyst deactivations are excessive, and after throwing stock oil, bed, substantially without temperature rise, does not react.
Embodiment 7
3.5g citric acid is dissolved in 35 ℃ of water, add 1.7g salt of wormwood to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water, 5ml nitric acid (content 60%), 11.2g phosphoric acid (content 85%) and 20g silicon sol (containing 40% silicon-dioxide), extruded moulding after continuing to mediate, 130 ℃ of dry 2h in air, 1000 ℃ of roasting 4h, make Modification on Al
2o
3carrier.
Under 35 ℃ of conditions, 93.6g nickelous nitrate, 9.4g sodium stannate, 12.1g cupric nitrate, 1.3g ammonium molybdate are mixed with to the 90ml aqueous solution, then add 9.3g triglycol, then impregnated on 100g modified support ageing 6h, 120 ℃ of dry 3h in air, 400 ℃ of roasting 5h, make catalyzer C-7.
In 500ml adiabatic reactor hydrogenation unit, carry out the reduction of catalyzer C-7: at the volume ratio 1000Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, be warmed up to 220 ℃ maintain 9h with 50 ℃/h temperature rise rate, with the speed of 10 ℃/h, be warmed up to 300 ℃, maintain 10h, with the speed of 10 ℃/h, be warmed up to 370 ℃, maintain 10h, be warmed up to 400 ℃ more afterwards with 15 ℃/h, maintain 6h, reduction finishes; Cool to 45 ℃, employing air speed is 2h
-1, the sulphur content petroleum naphtha that is 350ug/g is catalyst deactivation 9h; Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.8MPa, and 45 ~ 60 ℃ of reactor inlet temperatures, liquid volume air speed 2h
-1, hydrogen with oil volume than the 200h that turns round under 250:1 condition.Hydrogenation reaction the results are shown in Table 8.
Comparative example 9
This comparative example catalyzer is according to the method Kaolinite Preparation of Catalyst D-6 described in CN200610118522.7 embodiment 5, and the reduction of catalyzer, passivation and hydrogenation technique condition are with embodiment 7, and hydrogenation reaction the results are shown in Table 8.
Comparative example 10
This comparative example catalyzer is according to the method Kaolinite Preparation of Catalyst D-7 described in CN97121810.2 embodiment 1, and the reduction of catalyzer, passivation and hydrogenation technique condition are with embodiment 7, and hydrogenation reaction the results are shown in Table 8.
Table 8 embodiment 7 and comparative example 9,10 catalyzer 200h hydrogenation reaction results
| Project | Embodiment C-7 | Comparative example D-6 | Comparative example D-7 |
| Styrene content/% | 1.14 | 1.32 | 2.01 |
| Benzene rate of loss/% | 0.8 | 1.63 | 1.33 |
Adopt identical method of hydrotreating, with respect to catalyzer C-7, catalyzer D-6 and D-7 hydrogenation activity and selectivity are slightly poor.
Embodiment 8
9.2g citric acid is dissolved in 40 ℃ of water, add 6.7g salt of wormwood to be mixed with the 60ml aqueous solution, with this solution spraying 300g pseudo-boehmite aluminum oxide powder, mediate on spray limit, limit, add again 80ml water and 5ml nitric acid (content 60%), extruded moulding after continuing to mediate, 120 ℃ of dry 3h in air, 1030 ℃ of roasting 4h, make Modification on Al
2o
3carrier.Under 40 ℃ of conditions, 101.3g nickelous nitrate, 4.6g sodium stannate, 13.9g cupric nitrate, 0.5g ammonium tungstate, 2.9g ammonium molybdate are mixed with to the 90ml aqueous solution, add again 17.7g triglycol, then impregnated on 100g modified support, ageing 6h, 120 ℃ of dry 3h in air, 400 ℃ of roasting 3h, make catalyzer C-8.
In 500ml adiabatic reactor hydrogenation unit, carry out the reduction of catalyzer C-8: at the volume ratio 900Nm of pressure 0.5MPa, hydrogen and catalyzer
3/ m
3under/h condition, be warmed up to 250 ℃ maintain 9h with 30 ℃/h temperature rise rate, with the speed of 10 ℃/h, be warmed up to 300 ℃, maintain 10h, with the speed of 10 ℃/h, be warmed up to 370 ℃, maintain 10h, be warmed up to 400 ℃ more afterwards with 15 ℃/h, maintain 5h, reduction finishes; Cool to 40 ℃, employing air speed is 2h
-1, the sulphur content hexanaphthene that is 450ug/g is catalyst deactivation 8h; Afterwards with C
5~ C
9full distillate oil is raw material, at reaction pressure 2.8MPa, and 50 ~ 60 ℃ of reactor inlet temperatures, liquid volume air speed 2.5h
-1, hydrogen with oil volume than the 200h that turns round under 350:1 condition.Hydrogenation reaction the results are shown in Table 9.
Comparative example 11
This comparative example catalyzer is according to the method Kaolinite Preparation of Catalyst D-8 described in CN200710176670.9 embodiment 2, and the reduction of catalyzer, passivation and hydrogenation technique condition are with embodiment 8, and hydrogenation reaction the results are shown in Table 9.
Comparative example 12
This comparative example catalyzer is according to the method Kaolinite Preparation of Catalyst D-9 described in CN200610064904.6 embodiment 1, and the reduction of catalyzer, passivation and hydrogenation technique condition are with embodiment 8, and hydrogenation reaction the results are shown in Table 9.
Comparative example 13
This comparative example catalyzer is according to the method Kaolinite Preparation of Catalyst D-10 described in CN200610064905.0 embodiment 2, and the reduction of catalyzer, passivation and hydrogenation technique condition are with embodiment 8, and hydrogenation reaction the results are shown in Table 9.
Table 9 embodiment 8 and comparative example 11,12,13 catalyzer 200h hydrogenation reaction results
| Project | Embodiment C-8 | Comparative example D-8 | Comparative example D-9 | Comparative example D-10 |
| Styrene content/% | 1.08 | 1.10 | 0 | Do not react |
| Benzene rate of loss/% | 0.50 | 1.20 | 11.5 | / |
Under identical hydrogenation conditions, with respect to catalyzer C-8, catalyzer D-8 hydrogenation selectivity is on the low side, catalyzer D-9 is olefine saturation hydrogenation catalyzer, do not there is hydrogenation selectivity, catalyzer D-10 is cobalt-molybdenum-nickel Hydrobon catalyst, and temperature of reaction need, more than 200 ℃, not reacted under low temperature.
Table 10 embodiment catalyst components content
Table 11 comparative example catalyst components content
Claims (14)
1. a pyrolysis gasoline process for selective hydrogenation, adopts fixed-bed reactor; Nickel-base hydrogenation catalyst, is characterized in that, hydrogenation technique condition is: liquid volume air speed 1.0 ~ 4.0h
-1, 30 ~ 130 ℃ of reactor inlet temperatures, reaction pressure>=2.4MPa, hydrogen to oil volume ratio 100 ~ 500:1; Used catalyst be take aluminum oxide as carrier, take catalyst weight as 100%, containing nickel oxide 14 ~ 19%, stannic oxide 2 ~ 5%, basic metal Lithium Oxide 98min and/or potassium oxide 0.1 ~ 8%, cupric oxide and/or zinc oxide 0.5 ~ 8%, molybdenum oxide and/or Tungsten oxide 99.999 0.3 ~ 8%, silicon oxide and/or phosphorus oxide 0 ~ 8%.
2. method according to claim 1, is characterized in that fixed-bed reactor are fixed bed adiabatic reactor or fixed bed isothermal reactor.
3. method according to claim 1, is characterized in that liquid volume air speed is 1.5 ~ 3.5h
-1.
4. method according to claim 1, is characterized in that reactor inlet temperature is 45 ~ 110 ℃, and reaction pressure is 2.6 ~ 3.0MPa.
5. method according to claim 1, is characterized in that hydrogen to oil volume ratio is 100 ~ 300.
6. method according to claim 1, is characterized in that catalyzer contains nickel oxide 15 ~ 18%.
7. method according to claim 1, is characterized in that catalyzer contains stannic oxide 2.6 ~ 4.5%.
8. method according to claim 1, is characterized in that catalyzer alkali metal containing Lithium Oxide 98min and/or potassium oxide 0.6 ~ 5.5%, cupric oxide and/or zinc oxide 1.5 ~ 5.5%, molybdenum oxide and/or Tungsten oxide 99.999 0.5 ~ 5.5%, silicon oxide and/or phosphorus oxide 0 ~ 6.9%.
9. method according to claim 1, it is characterized in that support of the catalyst is δ crystal formation aluminum oxide or take δ type as main δ, α mixing crystal formation aluminum oxide, when described carrier is δ, α mixing crystal formation aluminum oxide, alpha-crystal form quality of alumina content <20% wherein.
10. according to the method described in claim 1 ~ 9 any one, it is characterized in that the preparation of catalyzer comprises the following steps:
1) at 20 ~ 40 ℃ by the compound of alkali metal containing Li and/or K and promotor and water wiring solution-forming, spray aluminium hydroxide powder, powder is mediated to the compound making it with alkali metal containing Li and/or K simultaneously and fully contacts; In the aluminium hydroxide powder of above-mentioned alkali metal containing Li and/or K, add the compound containing Si and/or P, mediate extruded moulding, 100 ~ 140 ℃ of dry 2 ~ 4h, 900 ~ 1100 ℃ of roasting 4 ~ 6h, make the alumina supporter containing auxiliary agent;
2) at 20 ~ 40 ℃, the salt that contains active component nickel, the salt that contains adjuvant component Sn, Cu and/or Zn, Mo and/or W are dissolved in the water, add again complexing agent, make steeping fluid, dipping is containing after the alumina supporter of auxiliary agent, 100 ~ 140 ℃ of dry 2 ~ 4h, 350 ~ 550 ℃ of roasting 4 ~ 6h, make catalyzer.
11. methods according to claim 10, is characterized in that promotor is citric acid and/or oxalic acid, and the mol ratio of citric acid and/or oxalic acid and basic metal Li and/or K atom is 0.35:1 ~ 0.8:1.
12. methods according to claim 10, is characterized in that complexing agent is one or more in glycol, glycol ether, triglycol or Tetraglycol 99.
13. methods according to claim 10, the mass ratio that it is characterized in that complexing agent and nickel oxide is 0.3:1 ~ 0.8:1.
14. methods according to claim 10, the salt that it is characterized in that catalyst component Sn is sodium stannate.
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| CN114433094A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | High-activity nickel catalyst and preparation method and application thereof |
| CN114433094B (en) * | 2020-10-20 | 2024-01-09 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
| CN114433095B (en) * | 2020-10-20 | 2024-05-03 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
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