CN100441298C - Titanium oxide - aluminum oxide composite carrier, preparation method and application thereof - Google Patents
Titanium oxide - aluminum oxide composite carrier, preparation method and application thereof Download PDFInfo
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- CN100441298C CN100441298C CNB2004100337986A CN200410033798A CN100441298C CN 100441298 C CN100441298 C CN 100441298C CN B2004100337986 A CNB2004100337986 A CN B2004100337986A CN 200410033798 A CN200410033798 A CN 200410033798A CN 100441298 C CN100441298 C CN 100441298C
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 36
- DCRIQAAPAFMPKP-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Al+3].[Ti+4] DCRIQAAPAFMPKP-UHFFFAOYSA-N 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 54
- PHTHEUNUXVDUOD-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[O-2].[Al+3] PHTHEUNUXVDUOD-UHFFFAOYSA-N 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 13
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 241001330002 Bambuseae Species 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 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 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910052594 sapphire Inorganic materials 0.000 abstract 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 13
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 12
- -1 polyethylene Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000000969 carrier Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004566 IR spectroscopy Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- RZXVEFCMTNPIBX-UHFFFAOYSA-G [OH-].[Ti+4].[Al+3].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Ti+4].[Al+3].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] RZXVEFCMTNPIBX-UHFFFAOYSA-G 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910004349 Ti-Al Inorganic materials 0.000 description 1
- 229910004692 Ti—Al Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- AMXBISSOONGENB-UHFFFAOYSA-N acetylene;ethene Chemical group C=C.C#C AMXBISSOONGENB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention discloses a titanium oxide-alumina composite carrier, a preparing method thereof and an application thereof. Titanium oxide accounts for 10 to 50 wt% of the total weight of the composite carrier. The crystal form of the titanium oxide in the composite carrier comprises an anatase form or/and a rutile form, and the crystal form of alumina is alpha-Al2O3. The surface of the composite carrier is weakly acidic, and the total acid amount is from 0.6 to 8 A/g/cm<2>. The preparing method of the composite carrier comprises: titanium tetrachloride solution and AlCl3.6H2O crystals are mixed and diluted by stirring and then are mixed with sodium metaaluminate solution to obtain precipitates of aluminum and titanium hydroxide, and without being aged, the precipitates are filtered, washed, dried, pulverized, kneaded and calcined at 800 to 1200 DEG C to obtain the carrier. The preparing method of the composite carrier has the advantages of simplicity and easy forming. The composite carrier has the advantages of low surface acidity and strong properties of pressure resistance and wear resistance. If used for selective hydrogenation reaction, the composite carrier is favorable for reducing the generation of green oil as a byproduct and extending the service life of a catalyst.
Description
Technical field
The present invention relates to petrochemical catalyst carrier and its production and application, concrete, relate to titanium dioxide-aluminum oxide composite carrier and preparation method thereof and the application in C 2 fraction selective hydrogenation.
Background technology
Ethene is important chemical material, can be used as to produce polyolefinic monomer.Usually contain the acetylene of 0.2%-0.7mol% in the ethene that is obtained by hydrocarbon cracking, if cracking severity is higher, the content of acetylene can be up to more than the 0.9mol%.In the polyethylene building-up process, the existence of acetylene can reduce the activity of polymerization catalyst, make the physics and the chemical property variation of polymer, so the acetylene content in the ethene must be dropped to below the certain value, just can become the monomer of synthetic polymer, low-pressure polyethylene technology for example requires in the ethene acetylene content less than 0.1ppm.Usually adopting the method for catalysis selective hydrogenation to make the acetylene conversion in the ethene is ethene, but in removing acetylene reaction, be adsorbed on acetylene on the catalyst surface be easy to dimerization or with ethene and other unsaturated hydrocarbons polymerization, form high polymer and be commonly called as " green oil ".The existence of green oil can cause the hydrogenation activity of catalyst and selectivity to descend gradually, shortens life cycle, causes catalyst shortening in service life, thereby causes the raising of production cost.
It is to be the loaded catalyst of main active component with palladium or with palladium basically that industrial C 2 fraction selective hydrogenation removes the alkynes catalyst.Carrier has: Al
2O
3(US4404124, US4484015), SiO
2(US5856262), TiO
2(US4839329), calcium aluminium cement (US4329530), molecular sieve, graphite, active carbon, float stone, zeolite, honeycomb cordierite (CN1176291A) etc.
Be carrier with the Alpha-alumina among US4404124 and the US4484015, making with Pd-Ag is the top layer catalyst of active component, and this alpha-alumina supports has low surface (3-7m
2/ g), (pore volume is 0.24～0.34cm to macropore
3/ g, average pore size is 685～2270
) characteristics.Active component Pd mostly is distributed in the 300 μ m on top layer of carrier, and Ag is evenly distributed in carrier.Show that in test this catalyst can be removed to very low concentration to acetylene, the green oil amount of generation is also few, but when containing impurity (as CO, sulfide, water etc.) in the reaction raw materials, life of catalyst reduces.
Be carrier with titanium dioxide among the US4839329, Pd/TiO
2Catalyst is used in the C 2 fraction selective hydrogenation catalytic reaction, with Pd/Al
2O
3Catalyst relatively back is found: Pd/TiO
2Catalyst has very high selectivity and stability, and antibiosis becomes the ability of green oil also apparently higher than Pd/Al
2O
3Catalyst.
Because acetylene content in the ethene is required more and more strictness, therefore, proposed higher requirement to selecting hydrogenation catalyst: catalyst should have good selectivity, activity and stable.As the carrier of active component skeleton, have lower surface acidity simultaneously, could reduce the generation of oligomer (i.e. " green oil "); That is to say that the growing amount of " green oil " is along with the rising of carrier surface acid amount increases.Catalyst also will have proper pore structure and specific surface, also will reach suitable requirement at aspects such as heat endurance, anti-poisoning and mechanical strengths.At present, the industrial Al that generally adopts
2O
3, SiO
2As the selective acetylene hydrocarbon hydrogenation catalyst carrier, but there is unsatisfactory place in these carriers, and are higher as the surface acid amount, promote the generation of " green oil " etc.
Because aluminium oxide is cheap and easy to get, adopts different preparation methods and heat-treat condition can obtain various physical arrangement, and has good heat conductivity, advantages such as processing technology maturation are widely used as catalyst carrier always.Titanium oxide can with metal generation strong interaction (Strong Metal-Support Interaction is SMSI), make titanium oxide bigger resistivity all be arranged to carbon deposit and metal sintering.Therefore, the adding of titanium oxide in the aluminium oxide both can keep the whole skeleton of aluminium oxide, can combine with the good catalytic performance of titanium oxide again, had the physical and chemical performance of many uniquenesses.The aluminium oxide-titanium oxide complex carrier can be taken into account Al
2O
3Excellent catalytic activity and TiO
2Anticaking carbon, anti-ability of poisoning remedy TiO
2The shortcoming of the little and bad mechanical strength of specific surface has better industrial application prospect.
Titanium dioxide-aluminum oxide compound and preparation method thereof has many reports.Traditional preparation method adopts alumina dry glue to add an amount of peptizing agent again with the mixture of titanium oxide and water fully mixes after moulding, drying, roasting make, as EP0199399 etc.; The example of also useful water-soluble titanium salt and sodium aluminate solution prepared by co-precipitation is as EP0339640.
CN1095689C discloses a kind of preparation method of aluminium oxide-titanium oxide bicomponent.This method utilizes the high titanium tetrachloride of relative low price purity to be the titanium source, with titanium tetrachloride with after the aluminum soluble salt crystal mixes, with the sodium aluminate solution prepared by co-precipitation, titanium oxide content is 0.5%-50wt% in the compound that obtains, and the specific area that records with nitrogen adsorption method is 200-400m
2/ g, total pore volume is 0.1-1.5ml/g, average pore size is 2-15nm.Adopt the specific area of Ti-Al bi-component of the identical titanium oxide content of this method preparation to be greatly improved.
CN1361231A discloses a kind of selection catalyst carrier for hydrgenating, and it is combined with each other by aluminium oxide and titanium oxide and forms, and this carrier has following rerum natura: bulk density 0.7-0.9g/ml, pore volume 0.3-0.6ml/g, specific surface are 10-60m
2/ g, average pore size 40-100nm.This carrier adopts following method preparation: under agitation, sodium metaaluminate and titanium tetrachloride solution are mixed, neutralize with aqueous slkali then, generate the co-precipitation of aluminium titanium hydroxide, filtration, drying, form required carrier through roasting then, and this invents to obtaining macropore carrier, under lower temperature, carry out calcination.This carrier mainly is applicable to the front-end hydrogenation technological process.There is following shortcoming in this invention: 1, neutralization reaction is violent, and the temperature of reaction and speed are difficult to control; 2, mix pinch, in the extrusion, neutralization reaction product caking property is too poor, can't moulding; 3, the titanium dioxide-aluminum oxide composite carrier of making does not have intensity substantially, can't reach industrial requirements.
In the heat deflection process, the form difference of the preparation method of carrier, initial hydrate, the transition temperature of crystal formation is also different." different preparation conditions and post-processing temperature are to superfine Ti O in " catalytic preparation technical foundation " (publishing house of Hangzhou University, 1997)
2The influence of powder property " point out in the literary composition: at carrier TiO
2Preparation process in, adopt supercritical fluid drying to prepare TiO
2The time, at 650 ℃ of Detitanium-ore-type TiO
2Begin to be transformed into Rutile structure, finish crystal transfer in the time of 850 ℃; " New Chemical Materials " (2000,28 (4), 11-13) " nano-TiO
2The photochemical catalyst of---a kind of function admirable " in to point out to adopt sol-gel (Sol-Gel) rule crystal formation to begin transition temperature be 550 ℃, 800 ℃ changed rutile at 2 o'clock fully into.
In sum, provide that a kind of preparation method is simple, reaction temperature and speed is easily controlled, surface acidity is low, be easy to moulding, the titanium dioxide-aluminum oxide composite carrier of mechanical strength height, economical and energy saving, and be applied to have Practical significance in the C 2 fraction selective hydrogenation reaction.
Summary of the invention
An object of the present invention is to provide a kind of titanium dioxide-aluminum oxide composite carrier.
Another object of the present invention provides a kind of preparation method of complex carrier of the present invention.
A further object of the present invention provides the application of complex carrier of the present invention in preparation C 2 fraction selective hydrogenation catalyst.
In order to achieve the above object, the inventor has carried out intensive research.Found that, adopt method of the present invention, aluminium oxide and two kinds of carriers of titanium oxide are carried out compound, under higher temperature, carrier is carried out roasting and can obtain the carrier that surface acidity is low, mechanical strength is high.According to conventional method with active constituent loading on carrier of the present invention, the selection hydrogenation catalyst of preparation, its hydrogenation performance increases significantly than catalyst in the prior art.
Titanium dioxide-aluminum oxide composite carrier of the present invention, with the total restatement of complex carrier, wherein titanium oxide content is 10-50wt%, preferred 20-35wt%; The crystal formation of titanium oxide comprises anatase or/and rutile-type in the described complex carrier, and the crystal formation of aluminium oxide is α-Al
2O
3Described complex carrier surface is faintly acid, and total acid content is 0.6-8
A/
G/cm2, preferred total acid content is 1.0-4.0
A/
G/cm2
This complex carrier has following rerum natura: specific area is 10-80m
2/ g, preferred 20-40m
2/ g, pore volume are 0.2-0.6cm
3/ g, preferred 0.35-0.5cm
3/ g, average pore size is 30-50nm, preferred 30-40nm.
Preferred complex carrier of the present invention adopts following method preparation, and this method comprises the steps: under agitation, with titanium tetrachloride solution and AlCl
36H
2Behind the O crystal mixed diluting, mix with sodium aluminate solution, the pH value of regulator solution obtains the precipitation of hydroxide of aluminium titanium to 6-11, and without wearing out, after filtration, washing, drying, pulverizing, the kneading, 800-1200 ℃ of roasting obtains described carrier.
The preparation method of titanium dioxide-aluminum oxide composite carrier of the present invention may further comprise the steps:
1) preparation sodium aluminate solution, titanium tetrachloride solution; The concentration of preferred sodium aluminate solution is that 20-30wt% (presses Al
2O
3The weight meter), the concentration of titanium tetrachloride solution is that 3-10wt% (presses TiO
2The amount meter), preferred 5-7wt%;
2) under agitation, with titanium tetrachloride solution and AlCl
36H
2Behind the O crystal mixed diluting, mix with certain proportioning with sodium aluminate solution, the content that makes titanium oxide in the resulting composite is 10-50wt%, and the pH value of regulator solution is preferably used HNO to 6-11
3Or the pH value of ammoniacal liquor regulator solution, obtain the precipitation of hydroxide of aluminium titanium, without aging, filtration washing, 80-120 ℃ of drying, preferred dry 4-6 hour, pulverize, obtain 200～300 powder materials;
3) to step 2) add 1-10wt% field mountain valley with clumps of trees and bamboo powder in the powder that obtains, be after the nitric acid of 1-10% is fully mediated, to dry with concentration, 800-1200 ℃ following roasting 2-8 hour, obtain described titanium dioxide-aluminum oxide composite carrier.
In an optimal technical scheme of the present invention, step 2) weight and the AlCl of titanium oxide in the titanium tetrachloride solution described in
36H
2The weight ratio of O crystal is 2-6, uses AlCl
36H
2The 2-5 of O crystal weight times of deionized water dilution; And described titanium tetrachloride solution and AlCl
36H
2The O crystal descends and flows and mix at 20-80 ℃ with sodium aluminate solution, and flow velocity is 20-30ml/min.
In a specific embodiment of the present invention, can adopt following method to prepare carrier:
(1) NaAlO
2The preparation of solution
Powdered aluminium hydroxide and sodium hydroxide solution according to a certain ratio 105 ℃-110 ℃ reactions 3-5 hour down, are added an amount of deionized water then and adjust solution concentration, remove by filter raw material while hot and carry into impurity secretly, during filtrate is and the NaAlO of gained
2Solution;
(2) be neutralized into glue
With TiCl
4Solution and AlCl
36H
2The O crystal is pressed the weight and the AlCl of titanium oxide in the titanium tetrachloride solution
36H
2The weight ratio 2-6 of O crystal is behind the mixed diluting, with NaAlO
2Solution is with certain proportioning (TiO
2Content is 10-50wt%) at 25-70 ℃ of following and stream mixing, flow velocity 20-30ml/min; Fully stir simultaneously, use HNO
3Or ammoniacal liquor regulate in and the pH value during terminal point to 6-11, the aluminium titanium precipitation of hydroxide that obtains without aging, is directly used the deionized water filtration washing, cleans Cl wherein
-Ion, then with aluminium titanium hydroxide under 80-120 ℃, in baking oven dry 4-6 hour, be ground into the tiny powder of 200～300 purposes;
(3) kneaded and formed
In powder, add 1-2wt% field mountain valley with clumps of trees and bamboo powder, with concentration is after the nitric acid of 1-2.5% is fully mediated, with the twin-screw banded extruder hydroxide to be made the rectangular of φ 3mm, after the oven dry, under 800-1200 ℃ in Muffle furnace roasting 2-8 hour, obtain titanium dioxide-aluminum oxide composite carrier of the present invention.
The present invention uses cheap titanium tetrachloride to be the titanium source, after the aluminium chloride crystal mixes, with the sodium aluminate solution reaction, has not only avoided violent exothermic reaction again, and the reaction temperature, the speed that make into glue are easy to control, and the preparation method is simple and convenient.Utilize nitrogen adsorption, mercury injection method, X-ray diffraction method (XRD), Pyridine-TPD and infrared absorption spectroscopy (IR) characterize carrier of the present invention, find that titanium dioxide-aluminum oxide composite carrier of the present invention has following characteristics:
1) complex carrier of the present invention has lower acidity, based on the weak acid center.Aluminium oxide, titanium oxide and titanium dioxide-aluminum oxide composite carrier have only the L acid site, and do not have the B acid site.The acidity of aluminium oxide is the strongest, and titanium oxide takes second place, and titanium dioxide-aluminum oxide composite carrier acidity is the most weak.Use the TiO of low surface acidity
2-Al
2O
3Complex carrier is used for selective hydrogenation reaction, helps reducing the generation of accessory substance " green oil ", prolongs catalyst service life.
2) method of the present invention prepares titanium dioxide-aluminum oxide composite carrier, in kneaded and formed process, need not to add binding agent, as alumina dry glue etc., only need to add certain density nitric acid and field mountain valley with clumps of trees and bamboo powder is fully mediated just extrusion molding smoothly of back, it is rectangular not easily broken that extrudate is, at a certain temperature after the roasting, its withstand voltage properties and anti-wear performance are all very strong, and mechanical strength reaches 70-120N/, has reached industrial requirements.
3) TiO in the complex carrier of the present invention
2Existence, quickened Al
2O
3The transformation of crystal formation 1000 ℃ of sintering temperatures, α-Al just occurs
2O
3, than low 100 ℃ of pure alumina crystal transfer temperature; Opposite, the existence of aluminium oxide has improved TiO in the titanium oxide
2The crystal transfer temperature makes TiO
2Heat endurance be improved.
4) for obtaining identical specific area, aperture, the sintering temperature of titanium dioxide-aluminum oxide composite carrier of the present invention is lower than Al
2O
3Carrier has been saved the energy greatly.
TiO of the present invention
2-Al
2O
3Complex carrier is mainly used in the hydrogenation reaction, particularly in the C 2 fraction selective hydrogenation course of reaction, but does not limit its application in other reaction.
TiO of the present invention
2-Al
2O
3Complex carrier can be used for preparation and select hydrogenation catalyst, especially can be used to prepare the catalyst of C 2 fraction selective hydrogenation, and the catalyst that makes comprises:
(1) active component: be Metal Palladium, content is the 0.01-0.05% of catalyst weight.
(2) carrier: be titanium dioxide-aluminum oxide composite carrier of the present invention, the content of titanium oxide is 10-50wt%.
Can select hydrogenation catalyst by preparing carriers of the present invention by the following method: catalyst activity component palladium can adopt conventional method such as infusion process to load on the complex carrier that adopts the preceding method preparation.
At 120～140 ℃ of reaction temperatures, hydrogen alkynes than 1.20-1.65, pressure 0.2Mpa, during air speed 10000
-1Process conditions under, use above-mentioned catalyst, C-2-fraction carries out selective hydrogenation reaction.
Use above-mentioned catalyst, acetylene content is about 0.25% in 120～140 ℃ of reaction temperatures, C-2-fraction raw material, hydrogen alkynes is than 1.36, when pressure 0.2Mpa, air speed 10000
-1Process conditions under, carry out selective hydrogenation reaction, catalyst selectivity is all greater than 82%, conversion of alkyne reaches more than 90%.
Complex carrier of the present invention has the following advantages:
1, complex carrier preparation method of the present invention is simple, becomes reaction temperature, the speed of glue to be easy to control.
2, complex carrier withstand voltage properties of the present invention and anti-wear performance are all very strong, the mechanical strength height.
3, complex carrier surface acidity of the present invention is low, is used to prepare the selective hydrogenation reaction catalyst, helps reducing the generation of selective hydrogenation reaction accessory substance " green oil ", prolongs catalyst service life.
The specific embodiment
The preparation of embodiment 1 titanium dioxide-aluminum oxide composite carrier
1) preparation NaAlO
2Solution: weighing sodium hydroxide 171.25 grams, after adding water 237.5 gram dilutions, with 192.5 the gram aluminium hydroxides in there-necked flask, reacted 3-5 hour down in 105 ℃-110 ℃, add deionized water then and be made into 500ml solution, concentration is 25wt%, removes by filter raw material while hot and carries into impurity secretly, and filtrate is NaAlO
2Solution.
2) with TiCl
4Solution 22ml (TiO
2Concentration: 25g/100ml) and AlCl
36H
2O crystal 123g mixes, and adds deionized water and is diluted to 333ml; With 93.5ml NaAlO
2Solution adds deionized water and is diluted to 333ml; Under agitation, with titanium aluminum solutions and NaAlO
2Solution with flow velocity 20ml/min, and carries out coprecipitation reaction in the stream adding four-hole boiling flask under 40 ℃ of temperature.Reaction finishes the back and adds ammoniacal liquor adjusting terminal point pH to 9, and without aging, directly filtering and washing is washed Cl off
-Back 120 ℃ of dryings 4 hours in baking oven are ground into the tiny powder of 200～300 purpose aluminium titanium hydrogen hydroxide.
3) getting above-mentioned powder 100 grams and 1 gram field mountain valley with clumps of trees and bamboo powder and concentration is that 2.5% aqueous solution of nitric acid fully mixes and pinches, the column type that is extruded into φ 3mm on the twin-screw banded extruder is rectangular, oven dry back in Muffle furnace 1050 ℃ of following roastings 4 hours, obtain the titanium dioxide-aluminum oxide composite carrier that titanium oxide content is 10wt%, the called after carrier A.
The surface area that records carrier A with nitrogen adsorption (BET) method is 21m
2/ g, total pore volume that mercury injection method is surveyed is 0.38cm
3/ g, average pore size is 32.8nm, mechanical strength is 98N/.Adopt infrared absorption spectrometry surface acid type, carrier has only L acid, does not have B acid, and total acid content is 0.9
A/
G/cm2, it is α-Al that XRD surveys the carrier crystal formation
2O
3, Detitanium-ore-type TiO
2
Embodiment 2
Use the method identical, get TiCl with embodiment 1
4Solution 48.7ml changes titanium oxide content, and the preparation titanium dioxide-aluminum oxide composite carrier obtains the carrier B that titanium oxide content is 20wt%, and its physical parameter is as follows: surface area is 23m
2/ g, total pore volume is 0.40cm
3/ g, average pore size is 34.5nm, mechanical strength is 85N/.Carrier has only L acid, does not have B acid, and total acid content is 1.2
A/
G/cm2, it is α-Al that XRD surveys the carrier crystal formation
2O
3, Detitanium-ore-type TiO
2
Embodiment 3
Use the method identical, get TiCl with embodiment 1
4Solution 83ml changes titanium oxide content, and the preparation titanium dioxide-aluminum oxide composite carrier obtains the support C that titanium oxide content is 30wt%, and its physical parameter is as follows: surface area is 20m
2/ g, total pore volume is 0.48cm
3/ g, average pore size is 46.5nm, mechanical strength is 80N/.Carrier has only L acid, does not have B acid, and total acid content is 1.4
A/
G/cm2, it is α-Al that XRD surveys the carrier crystal formation
2O
3, Detitanium-ore-type and rutile TiO
2
Embodiment 4
Use the method identical, get TiCl with embodiment 1
4Solution 130ml changes titanium oxide content, the preparation titanium dioxide-aluminum oxide composite carrier, and obtaining titanium oxide content is the carrier D of 40wt%, its physical parameter is as follows: surface area is 19m
2/ g, total pore volume is 0.50cm
3/ g, average pore size is 39.4nm, mechanical strength is 78N/.Carrier has only L acid, does not have B acid, and total acid content is 3.1
A/
G/cm2, it is α-Al that XRD surveys the carrier crystal formation
2O
3, Detitanium-ore-type and rutile TiO
2
Embodiment 5
Use the carrier of embodiment 1-4, use immersion process for preparing C 2 fraction selective hydrogenation catalyst: measure the water absorption rate of titanium dioxide-aluminum oxide, take by weighing carrier 20 grams, get the PdCl that concentration is 4.132mg/ml
2Solution 1.00ml adds deionized water and is diluted to 10ml, and the titanium dioxide-aluminum oxide carrier is immersed wherein, takes out oven dry after 20 minutes, 450 ℃ of following roastings in the Muffle furnace, and palladium becomes oxidation state, and Pd content is 0.02wt%.The catalyst called after Cat-A, B, C, the D that make.
Embodiment 6
In the acetylene selective hydrogenation reaction, adopt micro fixed-bed reactor and online gas-chromatography coupling technology to estimate.Reactor is Φ 12 * 3mm, and high 40mm, reactor adopt the tile heating of twining heating wire, add heat-preservation cotton and reach insulation effect.There is point for measuring temperature the reaction bed upper, middle and lower.With inlet temperature (on) as control object.
Take by weighing the Pd/TiO of certain amount of alumina ball and embodiment 5 preparations
2-Al
2O
3Catalyst (1ml) is packed in the reactor successively, the top quartz sand of packing into.Tighten, leak test.Use N earlier
2The purging process pipeline is used H then at a certain temperature
2Reduction feeds unstripped gas at last and reacts.The variation of unstripped gas before and after the reaction of different temperature points sample analysis, since 60 ℃, per 20 ℃ of points until 140 ℃, are measured selection of catalysts and conversion ratio under the different temperature points, and reaction result is listed in table 2.
Reaction condition is: acetylene content 0.25% in the raw material, hydrogen alkynes ratio: 1.36, and pressure: 0.2Mpa, air speed: 10000 o'clock
-1
Reaction result shows, with TiO of the present invention
2-Al
2O
3Composite oxides are that the catalyst of preparing carriers has good hydrogenation performance, and selectivity is better than alumina support greatly, and surface acidity is low, help reducing the growing amount of " green oil ", prolong the life cycle of catalyst.
Comparative Examples 1
With TiCl
4Solution 100ml and ammoniacal liquor 40 ℃ down and stream mixes, stir, conditioned reaction terminal point pH=9, washing is filtered, drying, methods such as moulding get carrier TiO with embodiment 1
2Carrier does not have intensity, and it is rutile-type that XRD surveys crystal formation.Infrared absorption spectrometry surface acid type, carrier has only L acid, does not have B acid, and total acid content is 3.9
A/
G/cm2
Comparative Examples 2
Adopt existing commercial Al
2O
3Carrier 1050 ℃ of following roastings, adopts with quadrat method and immerses same amount active component Pd, and with embodiment 5, catalyst called after Cat-E carries out micro anti-evaluation under the same conditions, measures selection of catalysts and conversion ratio under the different temperature points.The surface area that records this carrier with nitrogen adsorption (BET) method is 70.25m
2/ g, total pore volume that mercury injection method is surveyed is 0.14cm
3/ g, average pore size 36.2nm, mechanical strength is 90N/.Adopt infrared absorption spectrometry surface acid type, carrier has only L acid, does not have B acid, and total acid content is 10.3
A/
G/cm2, it is θ-Al that XRD surveys the carrier crystal formation
2O
3
Comparative Examples 3
The titanium dioxide-aluminum oxide composite carrier that obtains among the embodiment 3 is changed its sintering temperature, 600 ℃ of following roastings, obtain carrier F, its physical parameter is as follows: surface area is 276m
2/ g, total pore volume is 0.4155cm
3/ g, average pore size is 6.9nm, mechanical strength is 97N/.Total acid content is 22.9
A/
G/cm2, it is Al that XRD surveys the carrier crystal formation
2O
3And TiO
2Be unformed.Carrier F is adopted with quadrat method immersion same amount active component Pd, and with embodiment 5, catalyst called after Cat-F carries out micro anti-evaluation under the same conditions, measures selection of catalysts and conversion ratio under the different temperature points.
Comparative Examples 4
Prepare titanium dioxide-aluminum oxide compound (TiO by the CN1361231A disclosed method
2Content: 30wt%).Specific as follows: under agitation, with NaAlO
2Solution (80 grams are dissolved in 200ml water) and 86 milliliters of TiCl
4Solution (250 gram TiO
2/ liter) mix down at 40 ℃, reaction end back adds NaOH solution and regulates terminal point pH to neutrality, stirs after 24 hours the titanium aluminium hydroxide that generates is spent deionised water, flush away Cl
-, mixture is ground into 120-180 purpose powder 120 ℃ of dryings, adds aluminium glue and mediates back extruded moulding on the twin-screw banded extruder, and the 900 ℃ of roastings 2 hours in Muffle furnace of dry back obtain the titanium dioxide-aluminum oxide carrier, called after carrier G.Measure the crystal formation and the acid of this carrier and measure and compare, the different carriers rerum natura is listed in table 1 with the present invention.With embodiment 5, carrier G is adopted with quadrat method immersion same amount active component Pd, catalyst called after Cat-G.With embodiment 6 the same terms under carry out micro anti-evaluation, measure selection of catalysts and conversion ratio under the different temperature points, reaction result is listed in table 2.
Comparative Examples 5
According to the method identical, with TiCl with Comparative Examples 4
4The consumption of solution is changed into 200 milliliters, preparation TiO
2The titanium dioxide-aluminum oxide compound of content: 50wt%, called after carrier H.Measure the crystal formation and the acid of this carrier and measure and compare, the different carriers rerum natura is listed in table 1 with the present invention.
From the carrier physical data shown in the table 1 as can be seen, the surface acid amount is not only relevant with titanium oxide content, and relevant with preparation method and sintering temperature.The complex carrier of identical titanium oxide content, sintering temperature is low, and the surface acid amount of the complex carrier that obtains is very big.
The contrast of the different titanium oxide content carrier of table 1 rerum natura
Catalyst selectivity is with active under table 2 different temperatures
Claims (9)
1, a kind of complex carrier that is used in the titanium dioxide-aluminum oxide in the preparation C 2 fraction selective hydrogenation catalyst, with the total restatement of complex carrier, wherein titanium oxide content is 20-35wt%; The crystal formation of titanium oxide comprises anatase or/and rutile-type in the described complex carrier, and the crystal formation of aluminium oxide is α-Al
2O
3Described complex carrier surface is faintly acid, and total acid content is 0.6-8A/ (g/cm
2).
2, complex carrier according to claim 1, the total acid content that it is characterized in that described complex carrier surface is 1.0-4.0A/ (g/cm
2).
3, complex carrier according to claim 1, it is characterized in that described complex carrier has following rerum natura: specific area is 10-80m
2/ g, pore volume are 0.2-0.6cm
3/ g, average pore size is 30-50nm.
4, according to the described complex carrier of one of claim 1-3, it is characterized in that described complex carrier adopts following method preparation, this method comprises the steps: under agitation, with titanium tetrachloride solution and AlCl
36H
2Behind the O crystal mixed diluting, mix with sodium aluminate solution, the pH value of regulator solution obtains the precipitation of hydroxide of aluminium titanium to 6-11, and without wearing out, after filtration, washing, drying, pulverizing, the kneading, 800-1200 ℃ of roasting obtains described carrier.
5, each method of system of the described complex carrier of one of claim 1-4 is characterized in that described method may further comprise the steps:
1) preparation sodium aluminate solution, titanium tetrachloride solution;
2) under agitation, with titanium tetrachloride solution and AlCl
36H
2Behind the O crystal mixed diluting, mix with certain proportioning with sodium aluminate solution, the content that makes titanium oxide in the final complex carrier is 20-35wt%, the pH value of regulator solution obtains the precipitation of hydroxide of aluminium titanium to 6-11, without aging, filtration washing, 80-120 ℃ of drying, pulverizing obtain powder;
3) to step 2) add 1-10wt% field mountain valley with clumps of trees and bamboo powder in the powder that obtains, be the nitric acid of 1-10% with concentration, after fully mediating, dry, 800-1200 ℃ following roasting 2-8 hour, obtain described complex carrier.
6, the preparation method of complex carrier according to claim 5 is characterized in that the concentration of the described sodium aluminate solution of step 1) is 20-30wt%, presses Al
2O
3The weight meter; The concentration of titanium tetrachloride solution is 3-10wt%, presses TiO
2The amount meter.
7, the preparation method of complex carrier according to claim 5 is characterized in that step 2) described in titanium tetrachloride solution in the weight and the AlCl of titanium oxide
36H
2The weight ratio of O crystal is 2-6, uses AlCl
36H
2The 2-5 of O crystal weight times of deionized water dilution.
8, the preparation method of complex carrier according to claim 5 is characterized in that step 2) described in titanium tetrachloride solution and AlCl
36H
2The O crystal descends and flows and mix at 20-80 ℃ with sodium aluminate solution, and flow velocity is 20-30ml/min.
9, the application of the described titanium dioxide-aluminum oxide composite carrier of one of claim 1-4 in preparation C 2 fraction selective hydrogenation catalyst.
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| CN102909026A (en) * | 2011-08-04 | 2013-02-06 | 中国石油化工股份有限公司 | Hydrogenating activated protective agent using titanium oxide-alumina as carrier and preparation and application of hydrogenating activated protective agent |
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| CN100363298C (en) * | 2006-04-11 | 2008-01-23 | 浙江大学 | Process for preparing aluminum titanium composite oxide with high specific surface |
| CN101244381B (en) * | 2008-03-07 | 2010-06-09 | 东南大学 | Process for producing TiO2-Al2O3composite nano-powder body material |
| CN102553589B (en) * | 2010-12-29 | 2015-06-10 | 中国石油化工股份有限公司 | Alumina support, preparation method of alumina support, silver catalyst prepared by alumina support, and use of silver catalyst |
| CN102908972B (en) * | 2011-08-04 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of titanium dioxide-aluminum oxide article shaped and preparation method thereof |
| CN103923691B (en) * | 2013-01-14 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of hydroprocessing process of heavy raw oil of high asphalt content |
| US9657236B2 (en) | 2012-03-31 | 2017-05-23 | China Petroleum & Chemical Corporation | Process for hydrotreating heavy raw oils |
| CN103374389B (en) * | 2012-04-13 | 2015-07-29 | 中国石油化工股份有限公司 | The hydroprocessing process of a kind of iron and the high mink cell focus of calcium contents |
| CN103555001B (en) * | 2013-10-31 | 2015-07-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for coating titanium dioxide |
| KR101785268B1 (en) * | 2013-12-10 | 2017-10-16 | 삼성에스디아이 주식회사 | Negative active material and lithium battery including the material, and method for manufacturing the material |
| CN109179566A (en) * | 2018-09-29 | 2019-01-11 | 青岛亿天环保科技有限公司 | A kind for the treatment of method of printing and dying wastewater |
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