CN1024903C - Nickel-sodium-sulfur/alumina catalyst for selective hydrogenation of diolefin to mono-olefin - Google Patents
Nickel-sodium-sulfur/alumina catalyst for selective hydrogenation of diolefin to mono-olefin Download PDFInfo
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- CN1024903C CN1024903C CN 91103617 CN91103617A CN1024903C CN 1024903 C CN1024903 C CN 1024903C CN 91103617 CN91103617 CN 91103617 CN 91103617 A CN91103617 A CN 91103617A CN 1024903 C CN1024903 C CN 1024903C
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- diolefin
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- sodium
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- 150000001993 dienes Chemical class 0.000 title claims abstract description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 23
- 239000003054 catalyst Substances 0.000 title abstract description 17
- CVQKMZJMOWOLPQ-UHFFFAOYSA-N [Na].[Ni]=S Chemical compound [Na].[Ni]=S CVQKMZJMOWOLPQ-UHFFFAOYSA-N 0.000 title 1
- 150000005673 monoalkenes Chemical class 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000005864 Sulphur Substances 0.000 claims description 13
- 241000648001 Anolis alumina Species 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- -1 alkyl benzene compound Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- MERBOASPEBJVLI-UHFFFAOYSA-N trialuminum oxygen(2-) Chemical compound [O--].[O--].[O--].[Al+3].[Al+3].[Al+3] MERBOASPEBJVLI-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A catalyst for selectively hydrogenating diolefin to convert it to monoolefine is composed of Ni, Na, S and alumina carrier. The alumina carrier is a solid substance with amorphous phase as main component and its surface area is less than 100m2(ii)/g, total pore volume less than 1.0cm3(ii) in terms of/g. The nickel content is 5 to 20 wt%, the sodium content is 0.5 to 3 wt%, and the sulfur content is 1 to 5 wt%. The catalyst is in treatment C7～C16Mixtures of hydrocarbons of are particularly effective.
Description
The present invention relates to a kind ofly make diolefin selective ground hydrogenation and be converted into the catalyzer of monoolefine.
Usually in dehydrating alkanes or cracked product, include a spot of lighter hydrocarbons and with the alkane and the diolefin of required monoolefine same carbon atoms number.Lighter hydrocarbons generally can be removed with the method for fractionation or absorption by means of the difference on the boiling point; And diolefin is difficult to direct separation owing to very close on physical properties with purpose product monoolefine and unconverted alkane, simultaneously owing to the existence of diolefin, affects the course of processing in downstream.Owing to generate non-desired by product, increased the raw material consumption of product, thereby influenced the economic benefit of whole process again.Remove unwanted diolefin, use nickel of the present invention, sodium to support sulphurized catalyst in aluminum oxide, can be the diolefin selective ground hydrocracking that mixes in alkane and monoolefine monoolefine, and original monoolefine is not by hydrogenation, so both can remove diolefin effectively, can improve the concentration and the yield of monoolefine again, thereby improve the economic benefit that enterprise produces.
In order to be implemented in the conversion of diolefin in the monoolefine material, done more research at present, to develop suitable catalyzer.Catalyzer such as the platinum that is supported by inert support, palladium, silver, tungsten, nickel, molybdenum, iron all can be used for the purpose of the hydrogenation of diolefin in principle, and palladium that supports and nickel catalyzator then more are subjected to general attention.For example, United States Patent (USP) 3,696,160(KDChomyn) once described be used for that alkylation produces the propylene of aviation kerosene and motor spirit and butene feedstock propadiene and divinyl impurity conversion support nickel and palladium catalyst.But they only limit to use in the unstripped gas of sulfur-bearing not.At United States Patent (USP) 3,234,298(WCVan Zijlllanghout etal) in, sulfurized Ni/Al
2O
3Or Mo/Al
2O
3Catalyzer once was used to the selection hydrogenation of pyrolysis gasoline and kerosene, to improve the stability of vapour, kerosene.United States Patent (USP) 4,440 956(Couvillion) has been mentioned the nickel catalyzator that the aluminum oxide load is worn, and can be effectively used to contain the alkynes hydrogenation in the liquid hydrocarbon material of diolefine, and does not reduce the content of diolefine simultaneously.A disclosed application for a patent for invention [publication number: CN1032157A(mark Ding Jiayinsuo etc. on the Chinese patent communique at present, Uop Inc.)] proposed a kind of catalyzer that is rich in macropore that is used for olefine selective hydrogenation, can make diolefin selective ground hydrogenation.Its distinguishing feature is most pore volume to be provided by the macropore in the above aperture of 500A.
Catalyzer of the present invention is converted into monoolefine for 7 diolefins more than the carbon atom and has excellent excellent selecting property.This catalyzer is to make carrier with aluminum oxide, and contain 5～20%(weight) nickel, 1～3%(weight) sodium and 1～5%(weight) sulphur, do not contain precious metal in this catalyzer, have lower surface-area and pore volume, its carrier can be with manufacturings such as common forming method extrusion, compressing tablets.
Produce or consume monoolefine in many petrochemical process, wherein by-product and diolefin that sneak into is regarded as impurity.As: in pyrolysis gasoline and coker gasoline, all contain a certain amount of monoolefine and diolefin, diolefin wherein is easy to take place polymerization, cause in the gasoline storage process, generating colloid, therefore must remove by refinement treatment, monoolefine in these gasoline products is more stable comparatively speaking, and it has the raising that is beneficial to gasoline octane rating, therefore then should be kept in treating process, and diolefin selective hydrogenation is the ideal process that reaches this requirement.For another example, in the production of the linear alkylbenzene of composite technology flow process, alkane is also produced a part of diolefin simultaneously inevitably through dehydrogenation workshop section manufacture order alkene.Monoolefine generates the linear alkylbenzene product in alkylation workshop section and benzene reaction, and diolefin then causes the generation of undesirable byproduct such as heavy alkyl benzene compound, and these impurity will directly influence the quality and the output of product.The existence of diolefin not only consumes benzene feedstock, has also increased the consumption of hydrofluoric acid in the subsequent process simultaneously.In this class flow process, diolefin is regarded as unwanted composition, if the selection hydrogenation that carries out diolefin with catalyzer of the present invention after dehydrogenation workshop section then can solve the problem that exists in the said process satisfactorily.
Catalyzer of the present invention is used to diolefin selective hydrogenation is changed into monoolefine.Fig. 1 and Fig. 2 are respectively this catalyzer and the three kinds percentage (weight) of diolefin and monoolefine in the effluent liquid when carrying out the hydrogenation experiment with reference to catalyzer.
Catalyzer of the present invention is to be carrier with a kind of aluminum oxide that is mixed with sodium, and supports 5～20%(weight) nickel and 1～5%(weight) sulphur.This carrier is characterised in that its surface-area is less than 100m
2/ g, total pore volume is less than 1.0cm
3/ g.
The reaction mass that is applicable to catalyzer of the present invention can have the hydrocarbon mixture of suitable scope carbonatoms.Can include alkane, monoolefine, diolefin therein.This catalyzer is being handled C
7～C
16The mixture of hydrocarbon the time effective especially.
Usually selective hydrogenation process all is to carry out under gentle relatively condition.Be enough to keep under the condition that reactant is a liquid hydrocarbon, hydrogenation reaction just can be carried out.The suitable operational condition scope of broad is pressure 0.2～2.0MPa, 25～300 ℃ of temperature, liquid hourly space velocity 0.5～25h
-1, and the good conditions scope should be pressure 0.5～1.4MPa, 160～230 ℃ of temperature, liquid hourly space velocity 5～15h
-1The ratio of hydrogen and diolefin normally very important condition when operation in selective hydrogenation process.Avoid monoolefine to be converted into unwanted stable hydrocarbon, the consumption of necessary strict control hydrogen, this is to be difficult to realize in practice.Catalyzer of the present invention then has its outstanding characteristics, for the ratio of hydrogen and diolefin the scope of broad can be arranged, and promptly 0.5: 1～18: the 1(mol ratio), optimal conditions will depend on the composition and the desired factors such as diolefin degree of saturation that reach of raw material.But the molar ratio that general situation preferably is hydrogen and diolefin is 1: 1～2: 1.
Catalyzer of the present invention preferably uses in the fixed-bed reactor of sphere or cylindrical catalytic bed, and reaction mass moves with vertical direction in bed, and reaction mass upwards stream passes through reactor by reactor or downward stream.Adopt this dual mode can obtain result preferably, hydrogen can earlier and react this mixing of materials during reaction, through after giving heat, enters reactor again; Also can be mixed into reactor with the reaction mass that gives heat at the reactor inlet place.The residual hydrogen in reaction back can directly enter downstream process.
Catalyzer of the present invention shape preferably is that diameter is the spherical of 3～5mm or is the cylindric of φ 3 * 5mm.This can obtain by mold pressing, extrusion or spin.The alumina catalyst support particulate preparation of this catalyzer is by being made by the aluminium hydrate powder dehydration.Raw aluminum hydroxide mainly is the gibbsite crystalline phase.With the raw material mineral acid, example hydrochloric acid carries out acidifying earlier, after 24 hours, washes with water, when pH is raised to 6,100 ℃ of oven dry down, adds NaOH solution then, carries out extrusion.After the moulding, 120 ℃ of bakings 8 hours, 500 ℃ of roastings are 10 hours then, and the aluminum oxide that obtains is the solid based on amorphous phase.
Compare with the alumina supporter of other modes of employing or method preparation, what carrier used in the present invention will be good on performance is many.Although this carrier has lower surface-area, less pore volume has more excellent selective hydrogenation performance.General alumina supporter after heat treatment, surface-area has bigger reduction, but simultaneously total pore volume has certain increase, the crystal of simultaneous oxidation aluminium also can be gradually to γ-Al
2O
3Change, if heat up again also can become δ-, θ-, α-.
Outside alumina supporter, active ingredient is the most important part of catalyzer of the present invention.At first for the nickel component, it is to be evenly distributed in the whole carrier, and nickel carrying capacity suitable in the finished catalyst is 5～20%(weight).Best carrying capacity is 10～15%(weight).The nickel component can directly add in the aluminum oxide moulding process.Be preferably by impregnation method the nickel component is joined on the catalyzer.Normally alumina supporter molded, that roasting is good is immersed in the aqueous solution of single nickel salt, nickelous nitrate, nickelous chloride or nickelous acetate, then through evaporation, drying.Also nickelous carbonate can be mixed by a certain percentage with aluminum oxide, moulding, drying will be dried under 120 ℃ after the drying, more then in certain temperature, as 550 ℃ of roastings.Secondly, mainly in alumina supporter, this component concentrations is preferably the weight at 0.5～3%(in the interpolation of sodium component) scope in, the scope of the sodium component the best among the present invention is 0.5～1.0%(weight).The adding of sodium can be with NaOH or Na
2CO
3It is good that the aqueous solution is immersed in molded drying, but as yet not on the alumina supporter of roasting, but preferably with NaOH or Na
2CO
3The aqueous solution directly and the aluminium hydrate powder mixing, and make the alumina supporter that contains sodium.
The introducing of sulphur component also is the key step that catalyzer of the present invention forms.The sulphur component concentrations is preferably the weight at 1～5%() between, best sulphur carrying capacity is 2～3%(weight on this catalyzer).The introducing of sulphur component can be to add sulfide and carry out when the aluminum oxide moulding.But be preferably the body formed and sodium at carrying alumina, the nickel component is added to the sulphur component on this catalyzer after all having added.In vulcanisation step, sulfuration can be carried out under liquid-phase condition, also can carry out under gas phase condition.Be preferably before use and in reaction mass, add sulfur compound by reaction conditions, as: disulphide, organic mercaptan, thioether, hydrogen sulfide etc.Its condition and range can be close with operation condition, or carry out under fierce slightly condition.Curing temperature can be at 150～400 ℃, and gas flow rate is with 0.5～3h
-1Be advisable.
The characteristics of the preferred application example of catalyzer of the present invention are that also it is to the pollution of some impurity or exist insensitive.Should be known in owing in the chemical feedstocks of technical grade, necessarily have more impurity.Usually produce various catalyst prod owing to catalyst plant in addition, thereby make catalyzer contaminated easily in manufacturing processed.This catalyzer can be tolerated some impurity of existence, but generally should account for the 0.5%(weight of finished catalyst) below.Catalyzer can have trace iron to exist preferably, also can have other micro-basic metal to exist.The alkaline-earth metal and the existence haloid of same trace do not produce toxic action to this catalyzer.
The better characteristics of another of catalyzer of the present invention are not contain precious metal or platinum metals, i.e. platinum, palladium, rhodium, iridium.
The feature of a better application examples of this catalyzer is the selective hydrogenation catalyst that can be used as diolefin, and it does not contain precious metal.This catalyzer comprises a kind of alumina supporter, has less than 100m
2The total surface area of/g and be lower than 1.0cm
3The total pore volume of/g also comprises 5～20%(weight simultaneously) nickel and 0.5～3%(weight) sodium and 1～5%(weight) sulphur.
Its high-performance of catalyzer of the present invention can be found out from figure (1)～figure (3).The raw material that carries out selective hydrogenation is C
9To C
13The hydrocarbon mixture that hydrocarbon is generated through the full scale plant dehydrogenation.Wherein contain: % aromatic hydrocarbons 1.69(mol), saturated alkane 87.67(mol) %, monoolefine 9.62(mol) %, diolefin 0.56(mol) %, all the other are naphthenic hydrocarbon.Experiment is at 200 ℃ of temperature, pressure 0.7MPa, liquid hourly space velocity 7h
-1Condition under carry out.Monoolefine when figure (1) shows that with figure (2) four kinds of catalyzer stand different hydrogenation time in the raw material and the concentration %(weight of diolefin).Figure (3) has shown monoolefine when different hydro and diolefin mol ratio and the concentration %(weight of diolefin).Four kinds of selectivity of catalyst hydrogenation of presentation of results feature of figure (1) and figure (2) is more or less the same.Promptly all can make diolefin be lower than 0.04%(weight), and monoolefine reaches 10%(weight) about.From figure (3) though can see that at hydrogen and diolefin ratio the concentration of monoolefine still can reach 10%(weight greatly the time).This is the prominent feature of catalyzer of the present invention just.
Four kinds of catalyzer that carry out above-mentioned experiment form and physico-chemical property is listed in the table 1.Catalyst A, B, C, D have less specific surface area and less pore volume.Nickel content is from 6.8%(weight) fade to 15.3%(weight), the content of sulphur is from 1.8%(weight) be changed to 3.0%(weight) more than, the monoolefine change in concentration is little in the material behind selective hydrogenation, and the concentration of diolefin all is reduced to lower degree; Stability and the selectivity of introducing the alkali metallic sodium rear catalyst all improve significantly.
Several catalyzer physico-chemical properties of table 1.
Catalyst A B C D
Alumina catalyst support aluminum oxide aluminum oxide aluminum oxide
Nickel (Wt) % 9.9 9.7 15.3 6.8
Sodium (Wt) % 0.17 0 1.1 0.52
Sulphur (Wt) % 2.1 1.8 3.4 3.1
Surface-area m
2/ g 87 95 73 89
Pore volume cm
3/ g 0.28 0.24 0.77 0.22
Claims (2)
1, a kind of diolefin is converted into the catalyzer of monoolefine by selective hydrogenation, forms by nickel, sodium, sulphur and alumina supporter; It is characterized in that;
A. alumina supporter is the solid matter based on amorphous phase, and its surface-area is lower than 100m
2/ g, total pore volume is less than 1.0cm
2/ g,
B. the content of nickel is 5～20% (weight), and the content of sodium is 0.5～3% (weight), and the content of sulphur is 1～5% (weight).
2, catalyzer according to claim 1 is characterized in that: the content of nickel is 10～15%(weight), the content of sodium is 0.5～1.0%(weight), the content of sulphur shows 2～3%(weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91103617 CN1024903C (en) | 1991-06-07 | 1991-06-07 | Nickel-sodium-sulfur/alumina catalyst for selective hydrogenation of diolefin to mono-olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91103617 CN1024903C (en) | 1991-06-07 | 1991-06-07 | Nickel-sodium-sulfur/alumina catalyst for selective hydrogenation of diolefin to mono-olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1056068A CN1056068A (en) | 1991-11-13 |
| CN1024903C true CN1024903C (en) | 1994-06-08 |
Family
ID=4906175
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91103617 Expired - Fee Related CN1024903C (en) | 1991-06-07 | 1991-06-07 | Nickel-sodium-sulfur/alumina catalyst for selective hydrogenation of diolefin to mono-olefin |
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| Country | Link |
|---|---|
| CN (1) | CN1024903C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2316962B1 (en) * | 2006-03-07 | 2014-07-09 | Cargill, Incorporated | Aldolases, nucleic acids encoding them and methods for making and using them |
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1991
- 1991-06-07 CN CN 91103617 patent/CN1024903C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1056068A (en) | 1991-11-13 |
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