CN102836738A - Hydrogenation catalyst and preparation method thereof - Google Patents
Hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN102836738A CN102836738A CN2011101702991A CN201110170299A CN102836738A CN 102836738 A CN102836738 A CN 102836738A CN 2011101702991 A CN2011101702991 A CN 2011101702991A CN 201110170299 A CN201110170299 A CN 201110170299A CN 102836738 A CN102836738 A CN 102836738A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 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 description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229910052730 francium Inorganic materials 0.000 claims description 2
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 88
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 abstract description 75
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 10
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 10
- 229910001950 potassium oxide Inorganic materials 0.000 description 10
- 238000007086 side reaction Methods 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 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
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940072033 potash Drugs 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
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a hydrogenation catalyst and a preparation method thereof. The catalyst comprises, by weight, 10.0-80.0% of a ZSM-5 molecular sieve, 0.1-10.0% of an alkali metal, 10.0-80.0% of nickel oxide, 0.5-5.0% of molybdenum trioxide, and the balance of silicon dioxide. The catalyst of the present invention is used in naphthalene hydrogenation reactions, can be used for production of tetrahydronaphthalene and decahydronaphthalene, and has characteristics of good activity and high target product selectivity.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and preparation method thereof.In particular, the present invention relates to a kind of Catalysts and its preparation method that is used for the condensed-nuclei aromatics hydrogenation, particularly naphthalene hydrogenation catalyst and preparation method thereof.
Background technology
Decahydronaphthalene belongs to the condensed ring hydrocarbon, has trans and two kinds of configuration bodies of cis.Decahydronaphthalene all has very extensively and important use in chemical industry, electronics industry (for example the decahydro naphthalene derivatives is good liquid crystal raw material) and pharmaceuticals industry; For example decahydronaphthalene can be used as the solvent of ultra high molecular weight polyethylene, also can be used as the hydrogen storage material etc. of solvent, paint remover and the decentralized fuel cell of lubricant, fat-extraction agent, coating, grease, resin, rubber etc.The production of decahydronaphthalene in the market mainly is the hydrogenation that comes from naphthalene, has stronger practicality and considerable economic value so investigate naphthalene hydrogenation production decahydronaphthalene.
Because the naphthalene hydrogenation is a kind of consecutive reaction, under hydrogenation catalyst, first phenyl ring is at first saturated, and second phenyl ring carries out saturatedly under the comparison exacting terms more then, carries out full hydrogenation generation decahydronaphthalene.And prior art all is that the employing aluminium oxide is a catalyst carrier, transition metal, and for example nickel, molybdenum, tungsten, cobalt etc. are active component; Be active component with precious metals pt, Pd etc. perhaps, exist following problem like this: (1) with the noble metal is active metal component, and is with high costs; Especially in recent years; The noble metal price climbs up and up, and causes the catalyst cost high, has limited it and has used popularization; Have, because noble metal is very responsive to impurity, even a spot of impurity, for example compound such as sulphur, nitrogen just is easy to cause the poisoning of noble metal catalyst again, reduction of service life, causes use cost to raise; (2) the refining catalytic agent carrier major part of using at present is aluminium oxide; Contain elements such as some silicon, titanium simultaneously; Have acidity in various degree on such catalyst, in hydrogenation process, usually cause the side reactions such as cracking of aromatic hydrocarbons, the purpose product selectivity is lower; (3) because the hydrogenation performance of existing catalyst is not high, and the conversion ratio that naphthalene in the process of naphthalene hydrogenation, will occur is low, if improve temperature, side reactions such as cracking will occur, the purpose product selectivity is lower; (4) because the duct of alumina support all is the bigger secondary apertures in aperture, reactant or product are not all had restriction ability, like this, can produce multiple product, the purpose product selectivity is lower; (5) add acid stronger molecular sieve in some catalyst, for example BETA or Y zeolite can cause side reaction to increase like this, and the result has not only reduced the selectivity of naphthane, and make the higher naphthalene of price that significantly loss take place.
CN200310106565 discloses a kind of synthetic method of decahydronaphthalene; Be to be raw material with the naphthalene; Adopt naphthane as the solvent of solid raw naphthalene material, the nickel catalyst technology of synthetic decahydronaphthalene of a step in the agitated reactor under lower pressure and temperature, its reaction pressure is that 6～12MPa, reaction temperature are 180 ℃～220 ℃, volume space velocity (LHSV) is 0.5～1.0h during liquid
-1, the conversion ratio of naphthalene reaches more than 98%, and the productive rate of decahydronaphthalene reaches 98%, and the side reaction thing is less than 1%.Though this method has obtained result preferably,,, be difficult to satisfy the large-scale market demand so production efficiency is very low owing to be the intermittent operation that in agitated reactor, carries out.CN200510041404.6 discloses a kind of continuous hydrogenation synthesis method of decahydronaphthalene, and this technology is the production method of the synthetic decahydronaphthalene of naphthalene continously hydrogen adding in stable state trickle bed catalytic reactor, under certain pressure and temperature condition.Adopt decahydronaphthalene or naphthane as the solvent of solid raw naphthalene material, adopt catalyst such as platinum aluminium or nickel aluminium, 2～15MPa, 120～280 ℃, volume space velocity (LHSV) is 0.1～5.0h during liquid
-1, the synthetic decahydronaphthalene of continuous hydrogenation under hydrogen-oil ratio 1～3000NL/L condition.The conversion ratio of its naphthalene is 70%～99%, and the side reaction thing is less than 1%.Though this technology can realize continuous production, because poor stability, the operating cost of this technology aspect control is higher, and the activity of catalyst system therefor awaits further to improve.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of high activity that can on fixed bed, use, high stability and hydrogenation catalyst and preparation method thereof cheaply.
Hydrogenation catalyst provided by the invention, the composition of this catalyst: the weight with catalyst is benchmark, and the content of ZSM-5 molecular sieve is 10.0% ~ 80.0%, is preferably 20.0% ~ 70.0%; More preferably 30.0% ~ 60.0%, alkali-metal content is 0.1% ~ 10.0%, is preferably 0.5% ~ 8.0%; More preferably 1.0% ~ 5.0%, the content of nickel oxide is 10.0% ~ 80.0%, is preferably 15.0% ~ 60.0%; More preferably 20.0% ~ 50.0%, the content of molybdenum trioxide is 0.5% ~ 5.0%, and surplus is a silica.
The SO of described ZSM-5 molecular sieve
2/ Al
2O
3Mol ratio is preferably more than 500 greater than 200, more preferably the pure silicon molecular sieve.Described alkali metal is selected from one or more in lithium, sodium, potassium, rubidium, caesium and the francium, is preferably sodium or/and potassium, more preferably potassium.
Hydrogenization catalyst preparation method of the present invention comprises:
(1), ZSM-5 molecular sieve, molybdenum trioxide, alkali metal compound, silica, extrusion aid and water fully mixed pinches into plastic paste, extruded moulding through super-dry and roasting, obtains catalyst carrier;
(2), on the catalyst carrier that Ni is made to step (1),, obtain catalyst of the present invention through super-dry and roasting.
Described silica is silica weight content greater than 99% powdered substance, and the weight content of silica in catalyst is 5% ~ 80%.Described silica is selected from one or more in white carbon, silica gel and the cataloid.Described molybdenum trioxide be purity greater than 99.5wt%, granularity be 300 mesh sieve percent of pass greater than 95%, be preferably more than 98%.Described extrusion aid is the material that helps extruded moulding, can be selected from graphite, starch, cellulose and the sesbania powder one or more, is preferably the sesbania powder, and its addition is 0.5% ~ 10% of a carrier butt weight, is preferably 1% ~ 5%.
Mode of loading on the catalyst carrier that the described Ni of step (2) makes to step (1) can be one or both in ion-exchange, the infusion process; Can adopt the conventional nickeliferous aqueous solution of method preparation; Soon nickel compound containing will be soluble in water makes; Nickel compound containing is selected from one or more in nickel chloride, nickel nitrate, nickelous sulfate and the nickelous carbonate, is preferably nickel nitrate.When adopting ion-exchange or infusion process, the volume of preparing nickeliferous solution is 1 times of catalyst volume ~ 10 times, and nickeliferous solution contacts certain hour with catalyst carrier.When adopting saturated infusion process, the volume of the solution containing nickel of preparation is the catalyst carrier saturated extent of adsorption, directly mixes or sprays on the catalyst carrier.
Drying condition described in step (1) and (2) is normal temperature ~ 300 ℃ maintenance 1h ~ 48h, and step (1) can be identical with (2) described drying condition, also can be different.The roasting condition of step (1) and (2) is 400 ℃ ~ 900 ℃ and keeps 0.5h ~ 10.0h that step (1) can be identical with (2) described roasting condition, also can be different.
Compared with prior art, hydrogenation catalyst of the present invention has following advantage:
(1) adopted the ZSM-5 molecular sieve; A large amount of, suitable place can be provided for the hydrogenation of naphthalene; Because this molecular sieve has bigger surface area; And suitable aperture can let the naphthalene molecule get into wherein, and it is had certain constraint, makes it can in molecular sieve pore passage, have enough room and times to accomplish conversion reaction;
(2) problem that causes side reaction to take place for the acidity that overcomes catalyst, the present invention has used the molecular sieve of high silicon even total silicon, can so just avoid molecular sieve to produce acid centre;
(3) prior art generally is to use aluminium oxide to be binding agent, like this aluminium oxide just maybe with the generation acid centre of having an effect of the silicon in the molecular sieve.For overcoming this phenomenon, oxygen-free aluminium in the catalyst of the present invention, and adopt silicon components, and handle with alkali metal, guarantee that the acidity in the catalyst drops to minimum;
(4) in order to improve activity, contain molybdenum trioxide in the catalyst of the present invention, under reaction condition, the synergy generation takes place between molybdenum, nickel and the sulphur have the active phase of higher hydrogenation activity, improved activity of such catalysts.
Hydrogenation catalyst of the present invention can be used as the condensed-nuclei aromatics hydrogenation catalyst, particularly the naphthalene hydrogenation catalyst.According to practical situations, warp sulfuration before use or reduction, and then carry out the naphthalene hydrogenation reaction.This catalyst is used for the process of the selective hydrogenation production naphthane of naphthalene, can also be used for the full hydrogenation of naphthalene and produce the decahydronaphthalene process, has naphthalene conversion ratio height, the characteristics that the purpose product selectivity is high.
The specific embodiment
Further specify Preparation of catalysts process of the present invention through embodiment below, but invention should not be deemed limited among the following embodiment.Among the present invention, wt% is a mass fraction, and mol% is a molar fraction.
Catalyst of the present invention is to adopt the medium-sized fixed bed reactors of 100ml to estimate; Loaded catalyst is 100ml; Before charging, carry out prereduction to hydrogenation catalyst and handle, condition is following: hydrogen partial pressure 3.0MPa, 480 ℃ of temperature, gas agent volume ratio 800,8 hours time.Appreciation condition is: catalyst runs was carried out constituent analysis to product after 8 hours, calculated the selectivity of the conversion ratio and the decahydronaphthalene of naphthalene, and concrete computational methods are following:
The conversion ratio of naphthalene=[(advance the weight of naphthalene in the reactor feedstocks-go out the weight of naphthalene in the reactor product)/advance the weight of naphthalene in the reactor feedstocks] * 100%
The selectivity of decahydronaphthalene=(going out the molal quantity of molal quantity/naphthalene conversion of decahydronaphthalene in the reactor product) * 100%.
Embodiment 1
Present embodiment Preparation of catalysts step is following:
(1), gets 60 gram pure silicon ZSM-5 molecular sieves; 2 gram molybdenum trioxides (purity is that 300 mesh sieve percent of pass are greater than 95wt% greater than 99.5wt%, granularity), 6 gram potassium hydroxide, 15 gram white carbons; 6 gram sesbania powder fully mix with an amount of water and pinch into plastic paste; Extruded moulding (1.5 millimeters of diameters) through 120 ℃ of dryings 8 hours and 550 ℃ of roastings 3 hours, obtains catalyst carrier;
(2) get 78 grams, six water nickel nitrates and be dissolved into 100 grams and be mixed with nickel nitrate solution in the water, the carrier of step (1) preparation is fully mixed with above-mentioned solution, be evaporated to no open fire; 130 ℃ of dryings 8 hours; 500 ℃ of roastings made catalyst after 4 hours, and it consists of: nickel oxide/ZSM-5 molecular sieve/molybdenum trioxide/potassium oxide/silica=20/60/2/5/13 (weight); Be numbered E-1, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Embodiment 2
Present embodiment Preparation of catalysts method is with embodiment 1; Difference is that the compound of employed potassium is a potash; Catalyst is formed different; Consisting of of the catalyst that obtains: nickel oxide/ZSM-5 molecular sieve/molybdenum trioxide/potassium oxide/silica=12/30/1/2/55 (weight), be numbered E-2, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Embodiment 3
Present embodiment Preparation of catalysts method is with embodiment 1; Difference is that employed alkali metal is sodium; Catalyst is formed different; Consisting of of the catalyst that obtains: nickel oxide/ZSM-5 molecular sieve/molybdenum trioxide/sodium oxide molybdena/silica=30/30/4/1/35 (weight), be numbered E-3, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Embodiment 4
Present embodiment Preparation of catalysts method is with embodiment 1; Difference is to substitute white carbon with silica gel; Catalyst is formed different; Consisting of of the catalyst that obtains: NiO/ZSM-5 molecular sieve/molybdenum trioxide/potassium oxide/silica=40/30/3/2/25 (weight), being numbered E-4, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Embodiment 5
Present embodiment Preparation of catalysts method is with embodiment 1; Difference is to substitute white carbon with cataloid; Catalyst is formed different; Consisting of of the catalyst that obtains: NiO/ZSM-5 molecular sieve/molybdenum trioxide/potassium oxide/silica=50/20/3/2/25 (weight), being numbered E-5, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Embodiment 6
Present embodiment Preparation of catalysts method is with embodiment 1; Difference is that the catalyst composition is different; Consisting of of the catalyst that obtains: NiO/ZSM-5 molecular sieve/molybdenum trioxide/potassium oxide/silica=60/20/3/2/15 (weight); Be numbered E-6, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Embodiment 7
Present embodiment Preparation of catalysts method is with embodiment 1; Difference is that the catalyst composition is different; Consisting of of the catalyst that obtains: NiO/ZSM-5 molecular sieve/molybdenum trioxide/potassium oxide/silica=65/15/1/1/18 (weight); Be numbered E-7, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Embodiment 8
Present embodiment Preparation of catalysts method is with embodiment 1; Difference is that the catalyst composition is different; Consisting of of the catalyst that obtains: NiO/ZSM-5 molecular sieve/molybdenum trioxide/potassium oxide/silica=10/15/3/2/70 (weight); Be numbered E-8, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Embodiment 9
Present embodiment Preparation of catalysts method is with embodiment 1; The drying that difference is to be adopted in the preparation process is different with the temperature and time of roasting, and actual conditions is: the treatment conditions of step (1) sample are 200 ℃ of dryings 2 hours, 380 ℃ of roastings 8 hours; The treatment conditions of step (2) are room temperature ℃ 48 hours, 420 ℃ roastings of placement 8 hours; Make catalyst; It consists of: nickel oxide/ZSM-5 molecular sieve/molybdenum trioxide/potassium oxide/silica=20/60/2/5/13 (weight); Be numbered E-9, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Comparative Examples 1
This Comparative Examples Preparation of catalysts method is with embodiment 1, and difference is that employed ZSM-5 molecular sieve silica alumina ratio is 30, and binding agent is an aluminium oxide, not trioxygen-containing molybdenum and potassium oxide.Make consisting of of catalyst: nickel oxide/ZSM-5 molecular sieve/aluminium oxide=20/60/20 (weight), be numbered C-1, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Comparative Examples 2
This Comparative Examples Preparation of catalysts method is with embodiment 1, and difference is that employed molecular sieve is 12 BETA zeolite for the silica alumina ratio mole, and binding agent is an aluminium oxide, not trioxygen-containing molybdenum and potassium oxide.Make consisting of of catalyst: nickel oxide/BETA Zeolite/alumina=20/60/20 (weight), be numbered C-2, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
Comparative Examples 3
This Comparative Examples Preparation of catalysts method is with embodiment 1, and difference is with SB powder substituted molecule sieve, not trioxygen-containing molybdenum.Make consisting of of catalyst: nickel oxide/alumina/silica=20/60/20 (weight), being numbered C-3, its reaction result of producing decahydronaphthalene at the naphthalene hydrogenation is seen table 1.
The evaluation result of table 1 different catalysts
| ? | The catalyst numbering | The naphthalene conversion ratio, wt% | The decahydronaphthalene selectivity, mol% |
| Embodiment 1 | E-1 | 98.5 | 99.3 |
| Embodiment 2 | E-2 | 99.2 | 99.1 |
| Embodiment 3 | E-3 | 99.6 | 98.8 |
| Embodiment 4 | E-4 | 99.7 | 98.5 |
| Embodiment 5 | E-5 | 99.9 | 98.3 |
| Embodiment 6 | E-6 | 99.9 | 98.4 |
| Embodiment 7 | E-7 | 98.6 | 99.3 |
| Embodiment 8 | E-8 | 99.1 | 99.0 |
| Embodiment 9 | E-9 | 98.5 | 99.3 |
| Comparative Examples 1 | C-1 | 99.3 | 79.8 |
| Comparative Examples 2 | C-2 | 99.1 | 64.5 |
| Comparative Examples 3 | C-3 | 88.2 | 98.4 |
Can find out that from the result of table 1 catalyst of the present invention is produced in the reaction of decahydronaphthalene at the naphthalene hydrogenation, compares with Comparative Examples, when the naphthalene conversion ratio was suitable, the decahydronaphthalene selectivity of catalyst of the present invention was high more than 20%; And when the decahydronaphthalene selectivity is suitable, more than the high 10wt% of naphthalene conversion ratio of catalyst of the present invention.The result shows that catalyst of the present invention has remarkable advantages in the reaction of naphthalene hydrogenation production decahydronaphthalene.
Claims (17)
1. hydrogenation catalyst, the composition of this catalyst: the weight with catalyst is benchmark, and the content of ZSM-5 molecular sieve is 10.0% ~ 80.0%; Alkali-metal content is 0.1% ~ 10.0%; The content of nickel oxide is 10.0% ~ 80.0%, and the content of molybdenum trioxide is 0.5% ~ 5.0%, and surplus is a silica.
2. according to the described catalyst of claim 1, it is characterized in that in the described hydrogenation catalyst that the content of ZSM-5 molecular sieve is 20.0% ~ 70.0%.
3. according to the described catalyst of claim 1, it is characterized in that in the described hydrogenation catalyst that the content of ZSM-5 molecular sieve is 30.0% ~ 60.0%.
4. according to the described catalyst of claim 1, it is characterized in that in the described hydrogenation catalyst that alkali-metal content is 0.5% ~ 8.0%.
5. according to the described catalyst of claim 1, it is characterized in that in the described hydrogenation catalyst that alkali-metal content is 1.0% ~ 5.0%.
6. according to the described catalyst of claim 1, it is characterized in that in the described hydrogenation catalyst that the content of nickel oxide is 15.0% ~ 60.0%.
7. according to the described catalyst of claim 1, it is characterized in that in the described hydrogenation catalyst that the content of nickel oxide is 20.0% ~ 50.0%.
8. according to the arbitrary described catalyst of claim 1 ~ 7, it is characterized in that the SO of described ZSM-5 molecular sieve
2/ Al
2O
3Mol ratio is greater than 200.
9. according to the arbitrary described catalyst of claim 1 ~ 7, it is characterized in that described ZSM-5 molecular sieve is the pure silicon molecular sieve.
10. according to the arbitrary described catalyst of claim 1 ~ 7, it is characterized in that described alkali metal is selected from one or more in lithium, sodium, potassium, rubidium, caesium and the francium.
11., it is characterized in that described alkali metal is that sodium is or/and potassium according to the arbitrary described catalyst of claim 1 ~ 7.
12. the arbitrary said hydrogenization catalyst preparation method of claim 1 ~ 11 comprises:
(1), ZSM-5 molecular sieve, molybdenum trioxide, alkali metal compound, silica, extrusion aid and water fully mixed pinches into plastic paste, extruded moulding through super-dry and roasting, obtains catalyst carrier;
(2), on the catalyst carrier that Ni is made to step (1),, obtain described hydrogenation catalyst through super-dry and roasting.
13. according to the described method of claim 12, it is characterized in that described silica is silica weight content greater than 99% powdered substance, be selected from white carbon, silica gel and the cataloid one or more.
14., it is characterized in that described molybdenum trioxide is that purity is that 300 mesh sieve percent of pass are greater than 95% greater than 99.5wt%, granularity according to the described method of claim 12.
15. according to the described method of claim 12, it is characterized in that described extrusion aid is to be selected from graphite, starch, cellulose and the sesbania powder one or more, its addition is 0.5% ~ 10.0% of a carrier butt weight.
16., it is characterized in that the described mode of loading of step (2) is one or both in ion-exchange, the infusion process according to the described method of claim 12.
17., it is characterized in that the drying condition described in step (1) or (2) is normal temperature ~ 300 ℃ maintenance 1h ~ 48h according to the described method of claim 12; The roasting condition of step (1) or (2) is 400 ℃ ~ 900 ℃ roasting 0.5h ~ 10.0h.
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| CN104193578A (en) * | 2014-08-21 | 2014-12-10 | 邯郸惠达化工有限公司 | Method for producing decahydronaphthalene and tetrahydronaphthalene by naphthalene hydrogenation |
| CN107790135A (en) * | 2017-10-31 | 2018-03-13 | 西南化工研究设计院有限公司 | How Hydrogenation is for catalyst of decahydronaphthalene and its preparation method and application for a kind of tetrahydrochysene |
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| US5146034A (en) * | 1991-11-18 | 1992-09-08 | Arco Chemical Technology, L.P. | Conversion of paraffins to olefins |
| CN101143333A (en) * | 2006-09-15 | 2008-03-19 | 中国石油化工股份有限公司 | Hydrogenating and pour point depressing catalyst and its preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5146034A (en) * | 1991-11-18 | 1992-09-08 | Arco Chemical Technology, L.P. | Conversion of paraffins to olefins |
| CN101143333A (en) * | 2006-09-15 | 2008-03-19 | 中国石油化工股份有限公司 | Hydrogenating and pour point depressing catalyst and its preparing method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193578A (en) * | 2014-08-21 | 2014-12-10 | 邯郸惠达化工有限公司 | Method for producing decahydronaphthalene and tetrahydronaphthalene by naphthalene hydrogenation |
| CN107790135A (en) * | 2017-10-31 | 2018-03-13 | 西南化工研究设计院有限公司 | How Hydrogenation is for catalyst of decahydronaphthalene and its preparation method and application for a kind of tetrahydrochysene |
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