CN100567461C - Nickel-based hydrogenation catalyst, and preparation method and application thereof - Google Patents
Nickel-based hydrogenation catalyst, and preparation method and application thereof Download PDFInfo
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- CN100567461C CN100567461C CNB2006100649046A CN200610064904A CN100567461C CN 100567461 C CN100567461 C CN 100567461C CN B2006100649046 A CNB2006100649046 A CN B2006100649046A CN 200610064904 A CN200610064904 A CN 200610064904A CN 100567461 C CN100567461 C CN 100567461C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005336 cracking Methods 0.000 claims abstract description 15
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000001556 precipitation Methods 0.000 claims description 19
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 15
- 239000004480 active ingredient Substances 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 14
- 238000007664 blowing Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 claims description 2
- 229940125810 compound 20 Drugs 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 150000005673 monoalkenes Chemical class 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000571 coke Substances 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 48
- 239000000243 solution Substances 0.000 description 44
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 34
- 238000003756 stirring Methods 0.000 description 27
- 235000017550 sodium carbonate Nutrition 0.000 description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 22
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 14
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 14
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 238000013329 compounding Methods 0.000 description 13
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012546 transfer Methods 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 241001269238 Data Species 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- -1 nitrogenous hydrocarbon Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical group [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a nickel hydrogenation catalyst, a preparation method and application thereof. Is prepared with alumina or silica as carrier and through co-precipitation process, and features that the catalyst consists of active components Ni, La and assistant X1And vector X2O, and the weight percentage of the catalyst composition is as follows: contains NiO 40-70% and La2O32～5%，X1O 2～5%，X2O20-50%, wherein X1One or more selected from Cu, Mg and Zr, X2Selected from Al or and Si; the specific surface area is 80-200 m2The specific pore volume is 0.4-0.8 ml/g. The catalyst is suitable for mono-olefin hydrogenation, especially for cracking C9The catalyst has high hydrogenation activity, certain sulfur poisoning resistance and coke resistance, can meet the requirement of hydrogenation of a high colloid raw material, and has high hydrogenation activity and good stability.
Description
Technical field
The present invention relates to a kind of nickel series hydrogenating catalyst and preparation method thereof, use.This catalyzer is applicable to monoolefin hydrogenation, especially is fit to cracking C
9The hydrogenation of cut.
Background technology
Usually contain certain inorganic sulfur, burnt matter in the cracking of ethylene cut, cause the poisoning of catalyst inactivation, in addition, heavier cracking cut is as cracking C
9The hydrogenation degree of depth was not enough when cut fraction hydrogenation was used noble metal catalyst, and hydrogenation temperature is too high during with molybdenum nickel, cobalt-molybdenum catalyst, and coking is serious.Developed a kind of novel nickel catalyst, the hydrogenation of low cracking cut in the application with certain anti-sulphur, anti-burnt matter, higher hydrogenation performance for this reason.
Cracking C
9Fraction is the by product of cracking of ethylene, and its output is 10～20% of ethene ultimate production substantially.Cracking C
9Because the component complexity, the smell is awful, and active constituent is more, and the general at present method of its mixed composition catalyzed polymerization that adopts is earlier produced C
9The aromatic hydrocarbons petroleum resin are used the distillatory method again, obtain the aromatic solvent naphtha of the different trades mark.But the proterties of these solvent oils is relatively poor, and color is dark, and economic worth is not high, and through shortening, the hydrogenated products oil that obtains water-white is done molten Ji Water Oil Or Gas blended oil.
United States Patent (USP) U.S.P 4956328 has studied the mixed aqueous solution of nickel, aluminium, zirconates, be higher than under 60 ℃, the condition of pH value 7～10, use the basic cpd co-precipitation, the preparation catalyzer is applicable to the hydrogenation of aromatic hydrocarbon, nitrogenous hydrocarbon, alkene, and this catalyst activity is not good enough.It is carrier that U.S.P 4307248 has studied with aluminum oxide and diatomite, and the aqueous solution basic cpd co-precipitation with active component nickel and auxiliary agent magnesium, copper makes the hydrogenation that catalyzer is applicable to aromatic hydrocarbon, nitrogenous hydrocarbon, alkene, this poor catalyst stability.
Therefore, need to research and develop a kind of higher hydrogenation activity that both had, have the hydrogenation catalyst of good stability again, suitable cracking C
9The needs of hydrogenation.
Summary of the invention
The objective of the invention is to develop a kind of nickel catalyst with higher hydrogenation activity and hydrogenation degree of depth.
A kind of nickel series hydrogenating catalyst of the present invention be with aluminum oxide or and silicon oxide be carrier, adopt the method for co-precipitation to make, mainly contain active ingredient Ni, it is characterized in that catalyzer is by activeconstituents Ni, La, auxiliary agent X
1With carrier X
2Oxide compound form the weight percentage of forming in catalyzer: contain NiO40～70%, La
2O
32～5%, X
1Oxide compound 2～5%, X
2Oxide compound 20～50%, X wherein
1Be selected from one or more of Cu, Mg, Zr, X
2Be selected from Al or/and Si; Its specific surface area 80～200m
2/ g, specific pore volume 0.4～0.8ml/g.
In catalyzer of the present invention, the aluminum oxide that provides with the form of aluminum nitrate in the oxide compound of Al preferably accounts for 5～18% of weight percentage that catalyzer forms.
Select auxiliary agent La to improve the stability of activity of such catalysts component nickel among the present invention, reduce reacting initial temperature, improve the nickel reduction degree of catalyzer, select auxiliary agents such as Cu, Mg, Zr to improve the catalyst hydrogenation performance.
The present invention also provides a kind of preparation method of this nickel series hydrogenating catalyst:
The soluble salt of each component is dissolved in water, will add as the oxide compound that contains aluminium and/or silicon or its precursor of carrier, temperature is controlled at 40～115 ℃, adds precipitation agent, and it is precipitated under agitation condition, regulates the pH value 7～10, reacts 1～2 hour; After filtration, washing, moulding, 330～500 ℃ of roastings 3～5 hours, make catalyzer.
Precipitation agent is preferably one or more in aqua ammonia, supercarbonate, the carbonate in the present invention, with the form adding of the aqueous solution.Its add-on depends on the control situation of pH.
Among the present invention, carrier removes Al
2O
3, outside sodium metaaluminate, aluminum nitrate etc. can select for use, can also select active silica, diatomite, silicon sol etc. for use, can be one or more, preferably select diatomite for use; Precipitation agent generally all can be used when coprecipitation method prepares catalyzer, and the precipitation agent that is used to regulate the pH value among the present invention is the aqueous solution etc. of aqua ammonia and supercarbonate, carbonate preferably, the particularly above mixing solutions that adopts three kinds.
Among the present invention, the soluble salt of active component nickel and auxiliary agent Cu, Mg, Zr, La can be nitrate, muriate, also can be their compound complex compound.
Among the present invention, preferably add by the aqueous solution of aluminum nitrate form as a part of Al element of carrier, because this part Al and active component nickel have special textural association, so it plays different effects with Al element that aluminum oxide is provided; Heating temperature is unsuitable too high when adding carrier when the preparation catalyzer, preferably 80 ℃～105 ℃ of precipitation reaction temperature, and the time is unsuitable long, prevents the component hydrolysis, influences the homogeneity that component distributes in the catalyzer.The precipitation agent add-on depends on the pH value of solution in the precipitin reaction.Precipitation process keeps the pH value 7～10, is preferably in 8～9.Catalyzer of the present invention is not limited the shape of catalyzer, and catalyzer shape preferably is the trilobal cross of φ 1.5～2.5 * 3～8mm, can obtain by the extrusion mode.
Nickel series hydrogenating catalyst of the present invention is specially adapted to cracking C
9Cut fraction hydrogenation.
The present invention also provides a kind of this Application of Catalyst method, before being used for hydrogenation reaction, in hydrogen medium, reducing catalyst under 350～450 ℃ of temperature, the recovery time is 12～30 hours, cools to 80 ℃～150 ℃ then, logical nitrogen cools to 33 ℃～60 ℃, feeds CO again
2, progressively strengthen CO
2Measure 70%～90%, stop into nitrogen then, blowing air strengthens air capacity up to complete blowing air, and temperature rise can not surpass 45 ℃ on the whole process beds, and use is provided behind the reducing catalyst.
Be applied to cracking C
9During cut, its catalyzer suitable hydrogenation processing condition are: air speed is not higher than 3h
-1, 30～50 ℃ of reactor inlet temperatures, reaction pressure is not less than 2.7MPa, and hydrogen to oil volume ratio is 100～400 (v/v).
Nickel series hydrogenating catalyst of the present invention has the characteristics of higher hydrogenation activity, and has certain sulfur poisoning-resistant, anti-burnt matter performance, can adapt to the requirement of higher colloid raw material hydrogenation, the catalyst hydrogenation activity height, and stability is good.
Embodiment
Embodiment 1
70.5g nickelous nitrate, 7.5g aluminum nitrate, 4.5g zirconium nitrate, 3.5g lanthanum nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50～55 ℃.15g bicarbonate of ammonia, 30g salt of wormwood are dissolved in the 300g water, as precipitation agent.Under fully stirring, precipitant solution slowly is added in active ingredient, the compounding agent solution, add 10g diatomite again.Continue this mixing solutions to 85 of heating ℃, transfer pH value under 8.5 conditions with wet chemical, stirring reaction 1.5 hours.Filter, the elimination mother liquor is used the distilled water wash filter cake 3～5 times repeatedly.The oven dry filter cake, extruded moulding, 350 ℃ of roastings make catalyzer.
Before being used for hydrogenation, in hydrogen medium, under 425 ℃ of temperature, keep 15 hours reducing catalysts, cool to 100 ℃ then, logical nitrogen cools to 35 ℃, logical again 20%CO
2, progressively strengthen CO
2Measure 70%, stop into nitrogen then, blowing air slowly strengthens air capacity up to complete blowing air.Temperature rise can not surpass 45 ℃, the catalyzer after obtaining reducing on the whole process catalyzer.
Comparative Examples 1
70.5g nickelous nitrate, 4.5g magnesium nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50 ℃.All the other methods are with embodiment 1.
Comparative Examples 2
70.5g nickelous nitrate, 2.5g zirconium nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50 ℃.All the other methods are with embodiment 1.
Comparative Examples 3
70.5g nickelous nitrate, 9.5g aluminum nitrate, 3.5g zirconium nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50 ℃.All the other methods are with embodiment 1.
Comparative Examples 4,
70.5g nickelous nitrate, 5.5g aluminum nitrate, 2.5g lanthanum nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50～55 ℃.All the other methods are with embodiment 1.
Table 1, stock oil and character thereof
| Project | Iodine value */g | Diene * */g | Colloid/(mg * L -1) | Sulphur content/ppm | Density/(kg * L -1) | Boiling range/℃ |
| C 9Raw material | 246.1 | 12.37 | 4939.2 | 234.5 | 0.948 | 142～218 |
*: iodine value adopts halogenation iodine method to measure, show with the gram numerical table of the 100g oil iodine that consumed, under together; * diene value adopts apple acid anhydrides method to measure, and the mass conversion of the apple acid anhydrides that is consumed with 100g oil becomes the gram numerical table of iodine to show, down with.
Adopt 100ml adiabatic reactor evaluating apparatus in this experiment, cracking C
9The hydrogenation technique condition of cut is: air speed 2.0h
-1, 30 ℃ of reactor inlet temperatures, reaction pressure is 2.8MPa, hydrogen-oil ratio 350 (v/v).Each catalyst sample is estimated 96 hours, and per 6 hours sampling analysis are got the analysis mean value of 16 samples.
Table 2, embodiment 1 and Comparative Examples catalyst sample evaluating data thereof
Embodiment 2
60.5g nickelous nitrate, 7.5g aluminum nitrate, 2.5g magnesium nitrate, 5.2g lanthanum nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50 ℃.80ml ammoniacal liquor, 10g bicarbonate of ammonia, 20g yellow soda ash are dissolved in the 300g water, as precipitation agent.Under fully stirring, precipitant solution is slowly added in active ingredient, the compounding agent solution, add 10g diatomite again.Continue this mixing solutions to 90 of heating ℃, transfer pH value under 9.0 conditions with aqueous sodium carbonate, stirring reaction 1.5 hours.All the other methods are with embodiment 1.Filter, the elimination mother liquor is used the distilled water wash filter cake 3～5 times repeatedly.The oven dry filter cake, extruded moulding, 420 ℃ of roastings make catalyzer.
Before being used for hydrogenation, in hydrogen medium, under 415 ℃ of temperature, keep 16 hours reducing catalysts, cool to 100 ℃ then, logical nitrogen cools to 35 ℃, logical again 20%CO
2, progressively strengthen CO
2Measure 70%, stop into nitrogen then, blowing air slowly strengthens air capacity up to complete blowing air.Temperature rise can not surpass 45 ℃, the catalyzer after obtaining reducing on the whole process catalyzer.
Comparative Examples 5
With 40.5.g nickelous nitrate, 2.5g magnesium nitrate, the 2.5g lanthanum nitrate dissolves in the 300g water, prepares mixed aqueous solution, is heated to 50 ℃.80ml ammoniacal liquor, 8g bicarbonate of ammonia, 25g yellow soda ash are dissolved in the 300g water, as precipitation agent.Under fully stirring, precipitant solution is slowly added in active ingredient, the compounding agent solution, add 10g diatomite, 3g pseudo-boehmite again.Continue this mixing solutions to 90 of heating ℃, transfer pH value under 9.0 conditions with aqueous sodium carbonate, stirring reaction 1.5 hours.All the other methods are with embodiment 1.
Comparative Examples 6
With 40.5g nickelous nitrate, 2.5g magnesium nitrate, the 2.2g lanthanum nitrate dissolves in the 300g water, prepares mixed aqueous solution, is heated to 50 ℃.Prepare and contain Al
2O
330% sodium aluminate solution 10ml.80ml ammoniacal liquor, 18g bicarbonate of ammonia, 32g yellow soda ash are dissolved in the 300g water, as precipitation agent.Under fully stirring, in the very long adding active ingredient of precipitant solution, compounding agent solution, under fully stirring, will contain Al again
2O
3Sodium aluminate solution add, add 10g diatomite again.Continue this mixing solutions to 90 of heating ℃, transfer pH value under 9.0 conditions with aqueous sodium carbonate, stirring reaction 1.5 hours.All the other methods are with embodiment 1.
Catalyst sample evaluation stock oil and appreciation condition are with embodiment 1.
Table 3, embodiment 2 and Comparative Examples catalyst sample evaluating data thereof
Embodiment 3
60.5g nickelous nitrate, 7.5g aluminum nitrate, 4.5g cupric nitrate, 3.5g magnesium nitrate, 2.5g lanthanum nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50 ℃.50ml ammoniacal liquor, 5g bicarbonate of ammonia, 30g yellow soda ash are dissolved in the 300g water, as precipitation agent.Under fully stirring, precipitant solution is slowly added in active ingredient, the compounding agent solution, add 10g diatomite again.Continue this mixing solutions to 80 of heating ℃, transfer pH value under 8.5 conditions with aqueous sodium carbonate, stirring reaction 1.5 hours.Filter, the elimination mother liquor is used the distilled water wash filter cake 3～5 times repeatedly.The oven dry filter cake, extruded moulding, 390 ℃ of roastings make catalyzer.
Before being used for hydrogenation, in hydrogen medium, under 385 ℃ of temperature, keep 25 hours reducing catalysts, cool to 80 ℃ then, logical nitrogen cools to 35 ℃, logical again 20%CO
2, progressively strengthen CO
2Measure 70%, stop into nitrogen then, blowing air slowly strengthens air capacity up to complete blowing air.Temperature rise can not surpass 45 ℃, the catalyzer after obtaining reducing on the whole process catalyzer.
Embodiment 4
53.5g nickelous nitrate, 2.5g lanthanum nitrate, 4.5g zirconium nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50 ℃.70g yellow soda ash is dissolved in the 300g water, as precipitation agent.Under fully stirring, precipitant solution is slowly added in active ingredient, the compounding agent solution, add 10g diatomite, 3gAl again
2O
3Continue this mixing solutions to 80 of heating ℃, transfer pH value under 8.5 conditions with aqueous sodium carbonate, stirring reaction 1.5 hours.All the other methods are with embodiment 1.
Embodiment 5
60.5g nickelous nitrate, 7.5g aluminum nitrate, 2.5g lanthanum nitrate, 8.5g magnesium nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50 ℃.15g bicarbonate of ammonia, 55g yellow soda ash are dissolved in the 300g water.Under fully stirring, precipitant solution is slowly added in active ingredient, the compounding agent solution, add 10g diatomite again.Continue this mixing solutions to 80 of heating ℃, transfer pH value under 8.5 conditions with aqueous sodium carbonate, stirring reaction 1.5 hours.All the other methods are with embodiment 1.
Embodiment 6
60.5g nickelous nitrate, 7.0g aluminum nitrate, 2.1g lanthanum nitrate, 7.5g magnesium nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50 ℃.70g yellow soda ash is dissolved in the 300g water, as precipitation agent.Under fully stirring, precipitant solution is slowly added in active ingredient, the compounding agent solution.Continue this mixing solutions to 80 of heating ℃, with the aqueous sodium carbonate adjust pH under 8.5 conditions, stirring reaction 1.5 hours.All the other methods are with embodiment 1.
Adopt 100ml adiabatic reactor evaluating apparatus in this experiment, cracking C
9The hydrogenation technique condition of cut is: air speed 3.0h
-1, 45 ℃ of reactor inlet temperatures, reaction pressure is 3.5MPa, hydrogen-oil ratio 400 (v/v).Each catalyst sample is estimated 96 hours, and per 6 hours sampling analysis are got the analysis mean value of 16 samples.
Table 4, embodiment 3,4,5,6 catalyst sample evaluating datas
Embodiment 7
With 67.5g nickelous nitrate, 7.5g aluminum nitrate, 3.5g cupric nitrate, the 3.5g lanthanum nitrate dissolves in the 300g water, prepares mixed aqueous solution, is heated to 50 ℃.50ml ammoniacal liquor, 15g bicarbonate of ammonia, 30g yellow soda ash are dissolved in the 300g water, as precipitation agent.Under fully stirring, precipitant solution is added in active ingredient, the compounding agent solution, add 10g diatomite again.Continue this mixing solutions to 85 of heating ℃, with the aqueous sodium carbonate adjust pH under 8.5 conditions, stirring reaction 1.5 hours.Filter, the elimination mother liquor is used the distilled water wash filter cake 3～5 times repeatedly.The oven dry filter cake, extruded moulding, 420 ℃ of roastings make catalyzer.
Before being used for hydrogenation, in hydrogen medium, under 400 ℃ of temperature, keep 19 hours reducing catalysts, cool to 60 ℃ then, logical nitrogen cools to 35 ℃, logical again 20%CO
2, progressively strengthen CO
2Measure 70%, stop into nitrogen then, blowing air slowly strengthens air capacity up to complete blowing air.Temperature rise can not surpass 45 ℃, the catalyzer after obtaining reducing on the whole process catalyzer.
Comparative Examples 7
With 67.5g nickelous nitrate, 7.5g aluminum nitrate, 3.5g cupric nitrate, the 3.5g lanthanum nitrate dissolves in the 300g water, prepares mixed aqueous solution, is heated to 50 ℃.80ml ammoniacal liquor, 5g bicarbonate of ammonia, 38g yellow soda ash are dissolved in the 300g water,, be heated to 60 ℃ as precipitation agent.Under fully stirring, precipitant solution slowly is added in active ingredient, the compounding agent solution, add 10g diatomite again.Continue this mixing solutions to 85 of heating ℃, transfer pH value under 6.5 conditions with aqueous sodium carbonate, stirring reaction 1.5 hours.All the other methods are with embodiment 1.When throw out is filtered, 1% nickel, 0.5% bronze medal are arranged in the filtrate.
Comparative Examples 8
With 67.5g nickelous nitrate, 7.5g aluminum nitrate, 3.5g cupric nitrate, the 3.5g lanthanum nitrate dissolves in the 300g water, prepares mixed aqueous solution, is heated to 50 ℃.50ml ammoniacal liquor, 5g bicarbonate of ammonia, 15g yellow soda ash are dissolved in the 300g water,, be heated to 60 ℃ as precipitation agent.Under fully stirring, precipitant solution is added in active ingredient, the compounding agent solution, add 10g diatomite again.Continue this mixing solutions to 85 of heating ℃, transfer pH value under 11.0 conditions with aqueous sodium carbonate, stirring reaction 1.5 hours.All the other methods are with embodiment 1.
Catalyst sample evaluation stock oil and appreciation condition are with embodiment 1.
Table 4, embodiment 4 and Comparative Examples catalyst sample evaluating data thereof
Embodiment 8
60.5g nickelous nitrate, 7.5g aluminum nitrate, 2.5g lanthanum nitrate, 4.5g cupric nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50 ℃.15g bicarbonate of ammonia, 55g yellow soda ash are dissolved in the 300g water.Under fully stirring, precipitant solution is slowly added in active ingredient, the compounding agent solution, add 30ml silicon sol (containing silicon-dioxide 32%) again.Continue this mixing solutions to 80 of heating ℃, transfer pH value under 8.0 conditions with aqueous sodium carbonate, stirring reaction 1.0 hours.All the other methods are with embodiment 1.
Embodiment 9
60.5g nickelous nitrate, 2.5g lanthanum nitrate, 5.5g cupric nitrate are dissolved in the 300g water, prepare mixed aqueous solution, be heated to 50 ℃.15g bicarbonate of ammonia, 55g yellow soda ash are dissolved in the 300g water.Under fully stirring, precipitant solution is slowly added in active ingredient, the compounding agent solution, add 12gAL again
2O
3, the 11ml sodium aluminate solution (contains AL
2O
330%) continues this mixing solutions to 80 of heating ℃, transfer pH value under 8.0 conditions with aqueous sodium carbonate, stirring reaction 1.0 hours.All the other methods are with embodiment 1.
Catalyst sample evaluation stock oil and appreciation condition are with embodiment 1.
Table 5, embodiment 8 and 9 catalyst sample evaluating datas
The catalyst sample of embodiment 4 is carried out long period evaluation in 800 hours, and evaluation result sees Table 5.In 800 hours operation process that drop into carbon nine raw materials, the colloid of reaction raw materials is always at 5000/ (mg * L
-1) about, and the iodine value of hydrogenated products and diene value remain on lower level always, and this proves absolutely that embodiment 4 catalyzer have good resistive connection colloidality energy, can adapt to the requirement of higher gelationus raw material hydrogenation, catalyst stability is good, the hydrogenation activity height.
800 hours evaluating datas of the catalyst sample of table 6, embodiment 4
Claims (9)
1. a nickel series hydrogenating catalyst is with aluminum oxide or/and silicon oxide is a carrier, adopts the method for co-precipitation to make, and mainly contains active ingredient Ni, it is characterized in that catalyzer is by activeconstituents Ni, La, auxiliary agent X
1With carrier X
2Oxide compound form the weight percentage of forming in catalyzer: contain NiO 40～70%, La
2O
32～5%, X
1Oxide compound 2～5%, X
2Oxide compound 20～50%, X wherein
1Be selected from one or more of Cu, Mg, Zr, X
2Be selected from Al or/and Si; Its specific surface area 80～200m
2/ g, specific pore volume 0.4～0.8ml/g.
2. nickel series hydrogenating catalyst according to claim 1 is characterized in that X
2When containing Al, the aluminum oxide that provides with the form of aluminum nitrate in the oxide compound of Al accounts for 5～18% of weight percentage that catalyzer forms.
3. the preparation method of the described nickel series hydrogenating catalyst of claim 1, it is characterized in that the soluble salt of each component is dissolved in water, to add as the oxide compound that contains aluminium and/or silicon or its precursor of carrier again, temperature is controlled at 40～115 ℃, add precipitation agent, it is precipitated under agitation condition, regulate the pH value, reacted 1～2 hour 7～10; After filtration, washing, moulding, 330～500 ℃ of roastings 3～5 hours, make catalyzer.
4. according to the described Preparation of catalysts method of claim 3, it is characterized in that the pH value is 8～9.
5. according to the described Preparation of catalysts method of claim 3, temperature is controlled at 80～105 ℃ when it is characterized in that adding precipitation agent.
6. according to the described Preparation of catalysts method of claim 3, it is characterized in that the oxide precursor thing of aluminium is meant aluminum nitrate.
7. according to the described Preparation of catalysts method of claim 3, it is characterized in that the oxide precursor thing of silicon is meant diatomite.
8. the application method of the described nickel series hydrogenating catalyst of claim 1 is characterized in that being applied to cracking C
9During cut fraction hydrogenation, the hydrogenation technique condition of the catalyzer after its reduction is: air speed is not higher than 3h
-1, 30～50 ℃ of reactor inlet temperatures, reaction pressure is lower than 2.7MPa, hydrogen to oil volume ratio 100～400.
9. the application method of described nickel series hydrogenating catalyst according to Claim 8, it is characterized in that before being used for hydrogenation reaction, in hydrogen medium, reducing catalyst under 350～450 ℃ of temperature, recovery time is 12～30 hours, cool to 80 ℃～150 ℃ then, logical nitrogen cools to 33 ℃～60 ℃, feeds CO again
2, progressively strengthen CO
2Measure 70%～90%, stop into nitrogen then, blowing air strengthens air capacity up to complete blowing air, and temperature rise can not surpass 45 ℃ on the whole process beds, will provide use after the catalyst reduction.
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