CN1331605C - Alumina support containing silicon and titanium and preparation method thereof - Google Patents
Alumina support containing silicon and titanium and preparation method thereof Download PDFInfo
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- CN1331605C CN1331605C CNB2004100507169A CN200410050716A CN1331605C CN 1331605 C CN1331605 C CN 1331605C CN B2004100507169 A CNB2004100507169 A CN B2004100507169A CN 200410050716 A CN200410050716 A CN 200410050716A CN 1331605 C CN1331605 C CN 1331605C
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- containing compound
- silicon
- modified aluminas
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000010936 titanium Substances 0.000 title claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 19
- 239000010703 silicon Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 42
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 239000012445 acidic reagent Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000003292 glue Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000002210 silicon-based material Substances 0.000 claims description 11
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 10
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 9
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 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 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 210000002966 serum Anatomy 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 235000019795 sodium metasilicate Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 29
- 239000003054 catalyst Substances 0.000 abstract description 23
- 239000012752 auxiliary agent Substances 0.000 abstract description 19
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 15
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 239000011268 mixed slurry Substances 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 20
- 238000011017 operating method Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- -1 hydrionic compound Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 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 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention discloses a modified alumina supporter containing titanium and silicon auxiliary agents and a preparing method thereof. Silicon auxiliary agents are led into the modified alumina supporter of the present invention during the gel forming process of aluminium hydroxide, so that the specific surface area, pore diameter and pore volume of alumina are increased greatly. After gel forming ends, an acidic reagent and an alkaline reagent are respectively utilized to regulate the pH value of mixed slurry for multiple times to make the pore distribution of obtained aluminium hydroxide concentrated. Titanium auxiliary agents are added after gel forming and before aging to further improve the surface acidic properties of the supporter, and the surface acid amount and the B acid amount of the supporter are increased greatly. In addition, the surface of alumina is decorated by titanium, so that the interaction between active metal and the carrier, which is favorable for the dispersion of active metal constituents in a catalyst. With the modification, the modified alumina supporter containing titanium and silicon auxiliary agents is suitable for being used as catalytic material for petroleum processing catalysts, particularly for being used as a supporter for hydrotreating catalysts and hydrogenation conversion catalysts.
Description
Technical field
The present invention relates to a kind of modified aluminium oxide supports and preparation method thereof, in particular, relate to a kind of alumina support that contains silicon and titanium auxiliary agent simultaneously and preparation method thereof.
Background technology
In general, the used catalyst major part of PETROLEUM PROCESSING is to be carrier with aluminium oxide or the aluminium oxide that contains auxiliary agent, and its basic preparation process is the carrier that preparation earlier has suitable physico-chemical property, the active component by suiting in the suitable method load then.In catalyst preparation process, can in system, introduce auxiliary agent in different phase, auxiliary agent commonly used has one or more among Zr, Si, P, Ti, B, Mg and the F etc.The main purpose that adds these auxiliary agents be acid matter, the pore structure of regulating catalyst and improve active component and carrier between interaction etc.But because catalyst preparation process complexity; the influence that catalyst performance is subjected to various factors is bigger; if in this process, introduce auxiliary agent; usually can cause Preparation of Catalyst too complicated, some unfavorable effects may take place between various auxiliary agents and the active component and the performance of catalyst is reduced.In addition, if in catalyst preparation process, introduce auxiliary agent, because the physico-chemical property of carrier determines that auxiliary agent is very limited to the modulation degree of carrier or catalyst, can not give full play to the effect of auxiliary agent.If these auxiliary agents add in the preparation process of the precursor of carrier, just can be more effectively acid matter, pore structure and other physico-chemical properties of catalyst be carried out modulation, simultaneously can simplify catalyst preparation process, reduce the parameter of catalyst preparation process, improve the repeatability of catalyst.
In the preparation process of aluminum oxide dry glue powder, the method for introducing auxiliary agent in system is more, but generally speaking, two classes is arranged: wherein a class is introduced in the glue process for becoming at aluminium hydroxide; An other class is for to introduce after aluminium hydroxide becomes glue.Can adopt different auxiliary agents and introducing mode as required.
CN1110304A discloses the preparation method of the siliceous and phosphorus oxidation aluminium of a kind of macropore, in the preparation process of this aluminium oxide, silicon becomes the glue method to add with phosphorus with substep, can make silicon and phosphorus major part be dispersed in alumina surface like this, aluminium oxide aperture and pore volume are improved, but owing to added more phosphorus, B acid amount significantly reduces to make the acid of alumina surface measure particularly, acid strength obviously reduces, and makes its application be subjected to certain restriction.
CN1015638B discloses a kind of method for preparing aluminium hydroxide, and this method is carbon dioxide to be fed prepare aluminium hydroxide in the sodium aluminate solution, and it is simple to have preparation process, the pollution-free and low characteristics of cost.But owing in preparation process, introduce the silica of 1wt%～2wt%, and a part of silica be present in body mutually in, make it very limited to alumina modified effect, its physico-chemical property still can not satisfy the requirement of present poor oil processing to the catalyst physico-chemical property.
CN1184703A discloses a kind of preparation method of siliceous aluminium oxide.Its preparation be a kind of alumina globule that silica is 5wt%～15wt% that contains, its preparation characteristic is that the siliceous aluminium oxide wet bulb after the moulding carries out low temperature drying in containing the atmosphere of ammonia, the character of the alumina balls that obtain has obtained some improvement, but because some defectives of balling-up aspect self, make this forming process complexity, product yield is low, shortcomings such as preparation cost height.
EP0339640 discloses and has a kind ofly prepared the method for titanium-contained aluminum oxide with coprecipitation, because coprecipitation itself exists the problem that body is detained mutually, causes titanium dioxide can not give full play to the facilitation of aluminium oxide.Because co-precipitation requires two kinds or above species co-precipitation under certain condition, this condition to co-precipitation has proposed very harsh requirement, that is to say, even under certain conditions, two kinds of materials can precipitate simultaneously, but this condition may not all be best to two kinds of materials also, and this method has characteristics and the shortcoming of itself thus.
CN1350882A discloses alumina support of a kind of large aperture titaniferous and silicon modified additive and preparation method thereof.Wherein the preparation method of titaniferous, silicon aluminium hydroxide is as follows: sodium aluminate solution, titanium-containing compound slurries, siliceous combined solution and carbon dioxide are reacted into glue, more after filtration, washing, drying obtain titaniferous, silicon aluminium hydrate powder.Titanium in the alumina support of this titaniferous and silicon additive all is to add in becoming the process of glue with the silicon modified additive, the acid amount of carrier surface is higher, as the carrier of catalyst, in the process of hydrocarbon ils, cause the generation of some side reactions (for example cracking etc.) easily.In addition, the irrational distribution of the B of this carrier surface acid and L acid, particularly the ratio of B acid is lower, causes two kinds of character acid amounts not match, and reaction selectivity is reduced.
Summary of the invention
The purpose of this invention is to provide a kind of the have suitable titaniferous of bigger serface, high pore volume, pore distribution concentration and acid matter and alumina support of silicon additive and preparation method thereof.
The modified aluminium oxide supports of titaniferous of the present invention and silicon additive composed as follows: dioxide-containing silica is 0.1wt%～20wt%, and content of titanium dioxide is 0.1wt%～20wt%, and surplus is an aluminium oxide.This aluminium oxide has following character: specific area is 310m
2/ g～380m
2/ g, pore volume are 0.8cm
3/ g～1.2cm
3/ g, the aperture is that 75%85%, 〉=350 ℃ the meleic acid amount that the pore volume of 8nm～15nm accounts for total pore volume is 0.04mmol/g～0.10mmol/g, wherein B acid accounts for 40%～60% of total acid.
In the described modified aluminas, the content of silica is preferably 2wt%～10wt%, is preferably 4wt%～7wt%, and content of titanium dioxide is 2wt%～10wt% more preferably, is preferably 3wt%～6wt%.
The preparation method of modified aluminas of the present invention may further comprise the steps:
(1) prepares aluminum contained compound solution, silicon-containing compound solution and titanium-containing compound solution respectively;
(2) under stirring condition, aluminum contained compound solution and silicon-containing compound solution are mixed, add the precipitating reagent aqueous solution then and be reacted into glue;
(3) after the cemented into bundles, the pH value that adds acid reagent adjusting slurries in step (2) in the mixture that obtains is 2～4, adds the pH value 9.0～10.5 that alkaline reagent is regulated slurries again, repeats above-mentioned adjusting pH value step (being the swing of pH value) 1～3 time then;
(4) add titanium-containing compound solution in the system of step (3), constant temperature is aging then;
(5) mixed serum after aging filters with step (4), and filter cake obtains the dried glue of modified aluminas through washing, drying, passes through high-temperature roasting again, just can obtain modified aluminas of the present invention.
In the modified aluminas of the present invention, auxiliary agents of silicon is to add in the process that becomes glue, the body that is present in aluminium oxide mutually in, it mainly is the pore structure of improving aluminium oxide, specific area, aperture and the pore volume of aluminium oxide are improved greatly, in addition, the heat endurance of this catalysis material is improved, has guaranteed the long-term operation of catalyst under hot conditions.After cemented into bundles, the pH value of usefulness acid reagent and alkaline reagent adjusting aluminum hydroxide slurry repeatedly makes the aluminium hydroxide pore size distribution that obtains more concentrated respectively.The auxiliary agent titanium after becoming glue, aging before adding, mainly make titanium be distributed in the surface of aluminium oxide, purpose is when keeping aluminium oxide high-specific surface area, large pore volume and high thermal stability, further improve the surface acid property of carrier, make carrier surface acid amount and B acid amount suitable, this hydrotreatment and hydroconversion reactions to petroleum distillate all is very favourable.In addition, alumina surface is modified with titanium, has weakened reactive metal and carrier interactions, is favourable to the dispersion of active metal component in the catalyst.Therefore, modified aluminas of the present invention is particularly suitable for doing the carrier of hydrotreatment and hydrogenation conversion catalyst.
The specific embodiment
The concrete preparation process of modified aluminas of the present invention is as follows:
Silicon-containing compound described in the step (1) can be organic matter or inorganic matter, be preferably inorganic matter, more preferably sodium silicate solution (waterglass) or silicon sol solution, silica in the silicon-containing compound solution (in silica) content is generally 5～40 grams per liters, be preferably 10～30 grams per liters, more preferably 15～25 grams per liters; Described aluminum contained compound can be in the strong acid salt of meta-aluminate or aluminium one or more, is preferably sodium metaaluminate and aluminum sulfate, and alumina content is (with Al in the sodium aluminate solution
2O
3Meter) be generally 20～80 grams per liters, be preferably 30～70 grams per liters, 40～60 grams per liters more preferably, alumina content is (with Al in the aluminum sulfate solution
2O
3Meter) is generally 5～40 grams per liters, is preferably 10～20 grams per liters; Described titanium-containing compound can be preferably titanium sulfate or titanium tetrachloride for all solubility titanium-containing compounds, titanium sulfate more preferably, and the content of titanium oxide is (with TiO in the solution
2Meter) is generally 1～50 grams per liter, is preferably 5～20 grams per liters.
Said one-tenth glue process in the step (2), can adopt one-tenth gluing method conventional in the prior art, specifically can adopt following method: the aluminum contained compound solution for preparing is mixed placing in the glue jar earlier with silicon-containing compound solution, the addition of silicon-containing compound solution is according to the requirement decision of product, mixture is warmed up to 50～95 ℃ of constant temperature, under stirring condition, neutralize with containing the precipitating reagent aqueous solution, when reaching 7.5～8.5, the pH value that contains aluminum hydroxide slurry stops to add, be controlled at 0.5～1.0 hour with the time in whole, continue constant temperature and stir.Described precipitating reagent is can react with aluminum contained compound to generate all substances of aluminium hydroxide gel, for example aluminum contained compound is a sodium metaaluminate, precipitating reagent can be selected from hydrolysis can produce hydrionic all compounds, is preferably carbon dioxide or aluminum sulfate, more preferably aluminum sulfate.When being aluminum sulfate as aluminum contained compound, precipitating reagent can be selected from all compounds that hydrolysis can produce hydroxide ion, is preferably potassium hydroxide, NaOH, sodium carbonate, ammoniacal liquor and sodium metaaluminate etc., more preferably sodium metaaluminate.
It is specific as follows to regulate the pH process behind the described one-tenth glue of step (3): add acid reagent earlier, make the pH value of aluminium hydroxide slurries be reduced to 2～4, kept 5～10 minutes, add alkaline reagent then, make the pH value of aluminium hydroxide slurries be elevated to 9.5～10.5, kept repetitive operation 1～3 time 5～10 minutes.Described acid reagent can be selected from one or more that can produce hydrionic compound after organic acid, inorganic acid and the dissolving, be preferably in inorganic acid or the organic acid one or more, one or more in sulfuric acid, nitric acid and the acetic acid more preferably, its consumption are to reach the pH value decision of defined; Described alkaline reagent can be selected from one or more of compound that dissolving back generates hydroxide ion, is preferably one or more of inorganic compound, more preferably one or more in sodium metaaluminate, NaOH and the ammoniacal liquor.
The described method of step (4) adds titanium-containing compound solution in the solution after the cemented into bundles, addition is adjusted as required, and adding speed is controlled to add in 5～30 minutes and finishes, and aging temperature is controlled at 50～95 ℃, aging 1～3 hour of constant temperature.
The described filtration of step (5), washing, drying and roasting can be adopted method commonly used, for example suction filtration, 80～120 ℃ of dryings obtained modified aluminum hydroxide solid elastomer in 2～20 hours, and dried glue obtained modified aluminas of the present invention in 0.5～8 hour through 400～800 ℃ of roastings.
The invention provides and utilize cheap raw material to come the catalysis material of production function admirable, be significant improving end product quality and reducing catalyst cost aspect.In addition, the inventive method is suitable for the preparation method of aluminium oxide such as carbonizatin method, aluminum nitrate method and alchlor process equally.
The specific area of product of the present invention and pore volume are to adopt ASAP2400, and cryogenic nitrogen absorption (77K) calculates according to BET formula.Acid amount and acid matter adopt infrared spectrometer to record, and the adsorbent that uses is pyridine.SiO
2And TiO
2Content adopt gravimetric method and AAS to record respectively.
Further specify technical scheme of the present invention below in conjunction with specific embodiment.
Embodiment 1
Prepare modified aluminas according to method provided by the invention.
Adding 10L concentration in 100 liters of one-tenth glue jars is 40g Al
2O
3The sodium aluminate solution of/L and 2L concentration are 15g SiO
2/ L sodium silicate solution fully mixes, and temperature is elevated to 75 ℃, and adding concentration then gradually is 20g Al
2O
3/ L, temperature is 75 ℃ a aluminum sulfate solution, when being 8.0, the pH of slurries value stops to add aluminum sulfate solution, continuing constant temperature stirred 5 minutes, add the dilute nitric acid solution that concentration is 5wt% then, the pH value of adjusting slurries is 2.5, constant temperature stirred 5 minutes, the sodium aluminate solution that then adds above-mentioned character, adjusting slurry pH value is 9.0, continues constant temperature and stirs 5 minutes, repeats to regulate twice of pH value with dilute nitric acid solution and sodium aluminate solution, the last pH value of regulating slurries is 9.0, and adding 2L concentration then is 8g TiO
2The titanium sulfate solution of/L, adding speed is controlled to add in 10 minutes and finishes, and keeps temperature to be 75 ℃ and wears out 3 hours, filters to isolate solid product, solid product is through deionized water washing 4 times, 110 ℃ of dryings 6 hours are ground into 120 orders, obtain the modified aluminum hydroxide solid elastomer powder, the modified aluminum hydroxide solid elastomer powder was through 550 ℃ of roastings 4 hours, obtain modified aluminas, be numbered E-1, its physico-chemical property sees Table 1
Embodiment 2
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, difference is: become glue temperature and aging temperature to be 50 ℃, becoming glue pH value is 7.5, and rest materials, material consumption and operating procedure and condition obtain modified aluminas with embodiment 1, are numbered E-2, and its physico-chemical property sees Table 1.
Embodiment 3
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, difference is: become glue temperature and aging temperature to be 90 ℃, the amount that adds sodium silicate solution is 0.1L, the amount of titanium sulfate solution is 15L, rest materials, material consumption and operating procedure and condition are with embodiment 1, obtain modified aluminas, be numbered E-3, its physico-chemical property sees Table 1.
Embodiment 4
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, difference is: the amount that adds sodium silicate solution is 10L, and the amount of titanium sulfate solution is 0.1L, and rest materials, material consumption and operating procedure and condition obtain modified aluminas with embodiment 1, are numbered E-4, and its physico-chemical property sees Table 1.
Embodiment 5
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, difference is: becoming the glue temperature is 60 ℃, and aging temperature is 80 ℃, and rest materials, material consumption and operating procedure and condition obtain modified aluminas with embodiment 1, are numbered E-5, and its physico-chemical property sees Table 1.
Embodiment 6
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, difference is: the pH value that replaces rare nitric acid to adjust slurries with dilute sulfuric acid is 2.0, the pH value of adjusting slurries with NaOH is 10.0, rest materials, material consumption and operating procedure and condition are with embodiment 1, obtain modified aluminas, be numbered E-6, its physico-chemical property sees Table 1.
Embodiment 7
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, difference is: the amount that adds sodium silicate solution is 5L, and the amount of titanium sulfate solution is 5L, and rest materials, material consumption and operating procedure and condition obtain modified aluminas with embodiment 1, are numbered E-7, and its physico-chemical property sees Table 1.
Embodiment 8
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, difference is: with embodiment 1, different is the pH value of regulating slurries with the aqueous ammonia to replace sodium aluminate solution, pH value swing 2 times, rest materials, material consumption and operating procedure and condition are with embodiment 1, obtain modified aluminas, be numbered E-8, its physico-chemical property sees Table 1.
Embodiment 9
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, difference is: pH value swing 1 time, and rest materials, material consumption and operating procedure and condition obtain modified aluminas with embodiment 1, are numbered E-9, and its physico-chemical property sees Table 1.
Embodiment 10
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, difference is: the pH value of adjusting slurries with acetic acid is 4.0, and becoming the glue temperature is 85 ℃, aging temperature is 70 ℃, and rest materials, material consumption and operating procedure and condition obtain modified aluminas with embodiment 1, be numbered E-10, its physico-chemical property sees Table 1.
Comparative Examples 1
The preparation of reference modified aluminas.
Compare with embodiment 1, difference is: add sodium silicate solution and titanium sulfate solution in becoming the glue process, rest materials, material consumption and operating procedure and condition obtain the reference modified aluminas with embodiment 1, are numbered C-1, and its physico-chemical property sees Table 1.
Comparative Examples 2
The preparation of reference modified aluminas.
Compare with embodiment 1, difference is: with embodiment 1, different is to add sodium silicate solution and titanium sulfate solution in ageing process, rest materials, material consumption and operating procedure and condition are with embodiment 1, obtain the reference modified aluminas, be numbered C-2, its physico-chemical property sees Table 1.
Comparative Examples 3
The preparation of reference modified aluminas.
Compare with embodiment 1, difference is: do not carry out the swing of pH value after becoming glue, rest materials, material consumption and operating procedure and condition obtain the reference modified aluminas with embodiment 1, are numbered C-3, and its physico-chemical property sees Table 1.
The physico-chemical property of each embodiment product of table 1
| Numbering | SiO 2， wt％ | TiO 2， wt％ | Specific area, m 2/g | Pore volume, cm 3/g | 8～15nm pore volume integration rate, % | 〉=350 ℃ of acid matter | |
| The acid amount, mmol/g | B acid ratio, % | ||||||
| E-1 | 4.2 | 2.7 | 337 | 0.92 | 81 | 0.05 | 48 |
| E-2 | 4.1 | 2.5 | 380 | 0.88 | 83 | 0.06 | 52 |
| E-3 | 0.2 | 20 | 310 | 0.80 | 75 | 0.04 | 42 |
| E-4 | 20 | 0.1 | 378 | 1.20 | 85 | 0.08 | 48 |
| E-5 | 4.2 | 2.6 | 358 | 1.04 | 82 | 0.06 | 50 |
| E-6 | 4.4 | 3.1 | 366 | 0.96 | 84 | 0.07 | 53 |
| E-7 | 10.3 | 6.6 | 375 | 1.12 | 83 | 0.10 | 60 |
| E-8 | 4.2 | 2.6 | 342 | 0.86 | 78 | 0.05 | 49 |
| E-9 | 4.2 | 2.7 | 355 | 0.90 | 75 | 0.06 | 50 |
| E-10 | 4.2 | 2.8 | 337 | 0.84 | 80 | 0.05 | 51 |
| C-1 | 4.1 | 2.7 | 352 | 1.02 | 77 | 0.03 | 28 |
| C-2 | 4.5 | 3.0 | 240 | 0.62 | 49 | 0.02 | 46 |
| C-3 | 4.2 | 2.6 | 342 | 0.86 | 64 | 0.05 | 51 |
From the result of table 1 as can be seen, the modified aluminas of each embodiment preparation is compared with the reference aluminium oxide, has characteristics such as bigger pore volume, concentrated pore size distribution and moderate acid amount and the shared ratio height of B acid simultaneously.
Claims (9)
1, the modified aluminas of a kind of titaniferous and silicon additive is characterized in that consisting of of this modified aluminas: dioxide-containing silica is 0.1wt%～20wt%, and content of titanium dioxide is 0.1wt%～20wt%, and surplus is an aluminium oxide; This modified aluminas has following character: specific area is 310m
2/ g～380m
2/ g, pore volume are 0.8cm
3/ g～1.2cm
3/ g, the aperture is that 75%～85%, 〉=350 ℃ the meleic acid amount that the pore volume of 8nm～15nm accounts for total pore volume is 0.04mmol/g～0.10mmol/g, wherein B acid accounts for 40%～60% of total acid.
2, modified aluminas according to claim 1 is characterized in that in the described modified aluminas that dioxide-containing silica is 2wt%～10wt%, and content of titanium dioxide is 2wt%～10wt%.
3, modified aluminas according to claim 1 is characterized in that in the described modified aluminas that dioxide-containing silica is 4wt%～7wt%, and content of titanium dioxide is 3wt%～6wt%.
4, the preparation method of the arbitrary described modified aluminas of claim 1～3 comprises the steps:
(1) prepares aluminum contained compound solution, silicon-containing compound solution and titanium-containing compound solution respectively;
(2) under stirring condition, aluminum contained compound solution and silicon-containing compound solution are mixed, add the precipitating reagent aqueous solution then and be reacted into glue; Being controlled to the glue temperature is 50～95 ℃, stops to add the precipitating reagent aqueous solution when the pH of mixed serum value reaches 7.5～8.5;
(3) after the cemented into bundles, adding acid reagent in the mixed serum that obtains in step (2), to regulate the pH value of slurries be 2～4, adds the pH value 9.0～10.5 of alkaline reagent adjusting slurries again, repeats above-mentioned adjusting pH value step 1～3 times then;
(4) add titanium-containing compound solution in the mixed serum of step (3), constant temperature is aging then, and wherein aging temperature is 50～95 ℃;
(5) mixed serum after aging filters with step (4), and filter cake obtains modified aluminas through washing, drying and roasting.
5, method according to claim 4 is characterized in that the silicon-containing compound described in the step (1) is sodium metasilicate or silicon sol solution, and dioxide-containing silica is 5～40gSiO in the silicon-containing compound solution
2/ l; Described aluminum contained compound is sodium metaaluminate or aluminum sulfate, and alumina content is 20～80gAl in the sodium aluminate solution
2O
3/ l, alumina content is 5～40gAl in the aluminum sulfate solution
2O
3/ l; Described titanium-containing compound is titanium sulfate or titanium tetrachloride, and the content of titanium oxide is 1～50gTiO in the titanium-containing compound solution
2/ l.
6, method according to claim 4 is characterized in that dioxide-containing silica is 10～30gSiO in the silicon-containing compound solution described in the step (1)
2/ l; Alumina content is 40～60gAl in the described sodium aluminate solution
2O
3/ l, alumina content is 10～20gAl in the aluminum sulfate solution
2O
3/ l; The content of titanium oxide is 5～20gTiO in the described titanium-containing compound solution
2/ l.
7, method according to claim 4 is characterized in that becoming the glue reaction time to be controlled at 0.5～1.0 hour described in the step (2).
8, method according to claim 4 is characterized in that the joining day of the described titanium-containing compound solution of step (4) was controlled at 5～30 minutes, and ageing time is 1～3 hour.
9, method according to claim 4 is characterized in that the described drying condition of step (5) is: 80～120 ℃ of dryings 2～20 hours; Roasting condition is: 400～800 ℃ of roastings 0.5～8 hour.
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| CN102069016B (en) * | 2009-11-19 | 2012-11-21 | 中国石油化工股份有限公司 | Aluminum oxide carrier and preparation method thereof |
| CN102451675B (en) * | 2010-10-15 | 2013-07-24 | 中国石油化工股份有限公司 | Preparation method of alumina containing titanium and silicon |
| CN104445317B (en) * | 2014-11-12 | 2016-09-14 | 中国海洋石油总公司 | A kind of preparation method of modified boehmite |
| CN108295826B (en) * | 2017-01-12 | 2020-02-14 | 中国石油化工股份有限公司 | Modified alumina dry glue powder and preparation method and application thereof |
| CN107266049A (en) * | 2017-07-11 | 2017-10-20 | 芜湖市宝艺游乐科技设备有限公司 | High wall-flow honeycomb ceramic filter of a kind of filter efficiency and preparation method thereof |
| EP3513872A1 (en) * | 2018-01-22 | 2019-07-24 | SASOL Germany GmbH | Catalyst support comprising homogeneously distributed titanium dioxide and method for production |
| CN113086999A (en) * | 2021-04-15 | 2021-07-09 | 天津凯文特科技有限公司 | Novel preparation method of titanium modified activated alumina dry glue |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033285A (en) * | 1987-11-22 | 1989-06-07 | 齐鲁石油化工公司研究院 | Low-voltage hydrogenation denitrification catalyst and uses thereof |
| EP0339640A1 (en) * | 1988-04-28 | 1989-11-02 | The Harshaw Chemical Company | Alumina-titania composition |
| CN1114485A (en) * | 1993-12-22 | 1996-01-03 | 松下电器产业株式会社 | Video signal compressing device |
| JP2007122043A (en) * | 2005-09-30 | 2007-05-17 | Fujifilm Corp | Optical film, polarizing plate using same, and liquid crystal display device |
-
2004
- 2004-10-29 CN CNB2004100507169A patent/CN1331605C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033285A (en) * | 1987-11-22 | 1989-06-07 | 齐鲁石油化工公司研究院 | Low-voltage hydrogenation denitrification catalyst and uses thereof |
| EP0339640A1 (en) * | 1988-04-28 | 1989-11-02 | The Harshaw Chemical Company | Alumina-titania composition |
| CN1114485A (en) * | 1993-12-22 | 1996-01-03 | 松下电器产业株式会社 | Video signal compressing device |
| JP2007122043A (en) * | 2005-09-30 | 2007-05-17 | Fujifilm Corp | Optical film, polarizing plate using same, and liquid crystal display device |
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