CN101927194B - Preparation method of aluminum hydroxide powder containing lanthanum, phosphorus and titanium elements - Google Patents
Preparation method of aluminum hydroxide powder containing lanthanum, phosphorus and titanium elements Download PDFInfo
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- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 30
- 239000010936 titanium Substances 0.000 title claims abstract description 30
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000011574 phosphorus Substances 0.000 title claims abstract description 21
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 title abstract 5
- 239000000243 solution Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 18
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 18
- DKMRJJKYRLWCRQ-UHFFFAOYSA-N [Ti].[P].[La] Chemical compound [Ti].[P].[La] DKMRJJKYRLWCRQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 210000002966 serum Anatomy 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 23
- 239000011148 porous material Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 2
- 239000011734 sodium Substances 0.000 abstract 2
- 229910052708 sodium Inorganic materials 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000000376 reactant Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 238000005304 joining Methods 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002604 lanthanum compounds Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- FJWPWVRPJYBIFU-UHFFFAOYSA-N [O-2].[Al+3].P.[Ti+4].[La+3] Chemical compound [O-2].[Al+3].P.[Ti+4].[La+3] FJWPWVRPJYBIFU-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- -1 lanthanum-phosphorus-aluminium Chemical compound 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- GZHCNRONBGZNAH-UHFFFAOYSA-N phosphanylidynelanthanum Chemical compound [La]#P GZHCNRONBGZNAH-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The invention relates to a preparation method of aluminum hydroxide powder containing lanthanum, phosphorus and titanium elements, which is characterized by comprising the following steps: preparing a sodium metaaluminate solution; preparing a lanthanum-containing compound aqueous solution; preparing a phosphorus-containing compound aqueous solution; preparing a titanium-containing compound suspension; while stirring, introducing carbon dioxide gas into a mixed solution composed of the sodium metaaluminate solution, the lanthanum-containing compound aqueous solution, the phosphorus-containing compound aqueous solution and the titanium-containing compound suspension for reacting to generate precipitate; and filtering the obtained solid-liquid mixture, and washing, drying and crushing the filtered solid to obtain the aluminum hydroxide powder containing the lanthanum, phosphorus and titanium elements. For the obtained aluminum hydroxide powder containing the lanthanum, phosphorus and titanium elements, as the lanthanum, phosphorus and titanium elements are uniformly combined together, the hydrofining catalyst containing the lanthanum, phosphorus and titanium elements prepared by the aluminum hydroxide powder has better low-temperature catalytic activity, larger pore volume and larger specific surface area compared with the hydrofining catalyst containing no anthanum, phosphorus and titanium elements.
Description
Technical field
The present invention relates to a kind of preparation method who contains lanthanum-phosphorus-titanium elements aluminium hydroxide powder, belong to chemical catalyst area.
Background technology
Fraction in petroleum refining oil Hydrobon catalyst and with the fraction oil Hydrobon catalyst of coal system oil, all adopting activated alumina basically is carrier.Along with the continuous poor qualityization of fraction oil quality to be processed, the restriction of the performance of receptor 1 activity aluminium oxide own, the pure alumina carrier more and more is difficult to satisfy the requirement of all kinds of Hydrobon catalyst properties.Hydrofinishing class catalyst is to have bigger pore volume and specific area to the requirement of carrier; Moderate surface acid intensity and good low-temperature catalytic activity, to satisfy catalyst under harsh service condition, can macrocyclic even running.Because pure alumina carrier heat endurance is poor, under the normal pressure heating status, along with the raising of sintering temperature, its pore volume and specific area can be the trend that comparatively fast reduces along with the raising of temperature.And the alumina support of most of hydrogenation class catalyst all requires through higher temperature roasting, to satisfy catalyst to its carrier surface acid strength and thing requirement mutually, and less pore volume and the specific area of alumina support, bigger again restriction the reactivity of catalyst and operation steady in a long-term.
In addition, when catalyst keeps higher catalytic activity, wish that more catalyst has good low-temperature catalytic activity.The pure alumina carrier is to be difficult to satisfy catalyst to the requirement of carrier property.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method who contains lanthanum-phosphorus-titanium elements aluminium hydroxide powder is provided, in course of reaction, introduced a certain amount of lanthanum element P elements and titanium elements, made the surface acid intensity of its tool by good heat endurance and appropriateness; Bigger pore volume and specific area; Good low-temperature catalyzed reactivity and selectivity.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method who contains lanthanum-phosphorus-titanium elements aluminium hydroxide powder is provided, and its feature may further comprise the steps:
(1) compound concentration is 10～45gAl
2O
3The sodium aluminate solution of/l;
(2) preparation contains the compound water solution that contains lanthanum element that lanthanum element concentration is 0.1～10gLa/l;
(3) preparation phosphorus element-containing concentration is the compound water solution of the phosphorus element-containing of 0.1～10gP/l;
(4) preparation titaniferous concentration of element is the titanium-containing compound suspension of 5～15gTi/l;
(5) under stirring condition, carbon dioxide is fed sodium aluminate solution, contains in the compound water solution of compound water solution, phosphorus element-containing of lanthanum element and the common mixed solution of forming of titanium-containing compound suspension and react, generate sediment, this sediment is consisting of of benchmark: Al with the product
2O
368～95.6wt%, La
2O
30.2-6.0wt%, P
2O
52～9wt%, TiO
22～17wt%, in the course of reaction, feeding the carbon dioxide volumetric concentration is 10～40%, and after reaction finished, the pH value of mixed liquor was 8～12, and it is 5～40 ℃ that entire reaction course keeps reaction temperature;
(6) solid-liquid mixtures that produces in the step (5) is filtered, and wash leaching solid, dry, pulverize, make and contain lanthanum-phosphorus-titanium elements aluminium hydroxide powder.
The compound water solution that contains lanthanum element in the described step (2) is sulfate, nitrate, acetate or the muriatic aqueous solution that contains lanthanum element.
The compound water solution of the phosphorus element-containing in the described step (3) is the phosphatic aqueous solution.
Titanium-containing compound suspension in the described step (4) is the suspension of titanium oxide or metatitanic acid.Wherein preferred metatitanic acid, metatitanic acid should use colloid mill to grind before being mixed with the titanium-containing compound suspension of desired concn, makes the granularity of titanium-containing compound cross 800 mesh sieves.Because it is acid that the titanium-containing compound suspension shows, before joining reactant liquor, using basic solution is adjusted its pH value, and pH value is adjusted between 7～12, preferably pH value is adjusted between 9～10.The alkaline solution of adjusting pH value can be the aqueous solution such as NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, ammoniacal liquor, the aqueous solution of wherein preferred sodium acid carbonate and ammoniacal liquor.
Describedly contain the compound water solution of lanthanum element, the compound water solution and the titanium-containing compound suspension of phosphorus element-containing is to join in the sodium aluminate solution in carbon dioxide feeding process, wherein titanium-containing compound suspension joins in the reaction mixed serum at last.The adding that contains lanthanum compound solution is carried out joining in the reaction solution in the process in reaction, preferably reacting mid-term, joins in the reaction solution.Phosphorus-containing compound solution carries out joining in the reaction solution in the process in reaction, preferably add contain lanthanum compound solution after, then join in the reaction solution and go.The adding of titanium-containing compound suspension is carried out joining in the reaction solution in the process in reaction, preferably joins in the reaction solution in the reaction later stage.
The compound water solution that contains lanthanum element in the described step (2) is made benchmark with product, and the content of lanthanum element calculates according to lanthana, accounts for 0.2～6.0% of gross mass.Wherein lanthanum element content is preferably between 0.3～4%.
The compound water solution of phosphorus element-containing is made benchmark with product in the described step (3), and the content of P elements calculates according to phosphorus pentoxide, accounts for 2～9% of gross mass.Wherein the content of P elements is preferably 3～6%.
Titanium-containing compound suspension liquid in the described step (4) is made benchmark with product, and the content of titanium elements calculates according to titanium dioxide, accounts for 2～17% of gross mass.Wherein the content of titanium elements is preferably 4～12%.
Wash temperature in the described step (6) is 50～80 ℃, and the sodium oxide content in the product of washing back is less than 0.2wt%.
Wherein preferred wash temperature is 60～75 ℃, and sodium oxide content is preferably 0.03～0.1wt%.
Drying mode in the described step (6) is that normal pressure is dynamically dry, and baking temperature is 50～150 ℃, and be 0.5～1.5 hour drying time, and pulverize to air-flow and pulverize, and pulverizing the back product granularity is 80～300 orders.
Above-mentioned preferred baking temperature is 100～130 ℃, and be 0.4～2.0 hour preferred drying time, and the preferred product granularity is 120～200 orders.
The concentration of above-mentioned sodium aluminate solution is 10～45gAl
2O
3/ l is preferably 15～35gAl
2O
3/ l.
Above-mentioned carbon dioxide volumetric concentration is 10～40%, wherein is preferably 15～35%.
It is 5～40 ℃ that entire reaction course keeps reaction temperature, wherein is preferably 15～30 ℃, and the pH value of reaction end is controlled at 8～12, is preferably 9～11.
The invention has the beneficial effects as follows: introducing contains lanthanum, phosphorous, titanium-containing compound in sodium aluminate solution and carbon dioxide reaction process, and preparation process technology is simple, and easy operating does not have contaminant exclusion, non-environmental-pollution; Manufacturing contain lanthanum-phosphorus-titanium elements aluminium hydroxide powder because lanthanum-phosphorus-aluminium element combination very even makes the Hydrobon catalyst of making that contains lanthanum-phosphorus-titanium elements have better low-temperature catalytic activity than the Hydrobon catalyst that does not contain lanthanum-phosphorus-titanium elements; Have bigger pore volume and specific area.
The specific embodiment
Embodiment 1
In reactor, add 10gAl
2O
3The sodium aluminate solution of/l is controlled at 40 ℃ with solution temperature.Stir down, (carbon dioxide v) reacts to lead to into concentration and be 10%.When the pH value of reactant liquor to 12 the time, adding concentration is the lanthanum acetate aqueous solution of 0.1gLa/l.After adding the lanthanum acetate aqueous solution, then add the ammonium dihydrogen phosphate aqueous solution that concentration is 10gP/l.After adding ammonium dihydrogen phosphate aqueous solution, then adding concentration is 5gTi/l, the metatitanic acid suspension of pH value 10.
Continue to lead to into that carbon dioxide reacts, when the pH value of reactant liquor to 8 the time, stop reaction.The sediment that generates is consisting of of benchmark: Al with the product
2O
388.8wt%, La
2O
30.2wt%, P
2O
59wt%, TiO
22wt% filters sediment, 50 ℃ of washings, washs the sodium oxide content 0.03wt% in the product of back with deionized water.Under the temperature with 50 ℃ in dynamic drier, dry 1.5 hours.Dried product is crushed to 300 orders with airslide disintegrating mill, has both obtained product of the present invention.
Embodiment 2
In reactor, add 45gAl
2O
3The sodium aluminate solution of/l is controlled at 5 ℃ with solution temperature.Stir down, leading to into, concentration is that (carbon dioxide v) reacts 4O%.When the pH value of reactant liquor to 11 the time, adding concentration is the lanthanum nitrate aqueous solution of 10gLa/l.After adding lanthanum nitrate aqueous solution, then add the ammonium dibasic phosphate aqueous solution that concentration is 0.1gP/l.After adding ammonium dibasic phosphate aqueous solution, then adding concentration is 17gTi/l, the titanium oxide suspension of pH value 10.
Continue to lead to into that carbon dioxide reacts, when the pH value of reactant liquor to 10 the time, stop reaction.The sediment that generates is consisting of of benchmark: Al with the product
2O
375wt%, La
2O
36wt%, P
2O
52wt%, TiO
217wt%.The sediment that generates is filtered, 80 ℃ of washings, wash the sodium oxide content 0.2wt% in the product of back with deionized water.Under the temperature with 150 ℃ in dynamic drier, dry 0.5 hour.Dried product is crushed to 80 orders with airslide disintegrating mill, has both obtained product of the present invention.
Embodiment 3
In reactor, add 30gAl
2O
3The sodium aluminate solution of/l is controlled at 30 ℃ with solution temperature.Stir down, (carbon dioxide v) reacts to lead to into concentration and be 30%.When reacting the beginning back in the time of about 20 minutes, adding concentration is the lanthanum chloride solution of 4gLa/l.After adding lanthanum chloride solution, then add the ammonium dihydrogen phosphate that concentration is 6gP/l.After adding ammonium dihydrogen phosphate, then adding concentration is 10gTi/l, the titanium oxide suspension of pH value 11.
Continue to lead to into that carbon dioxide reacts, when the pH value of reactant liquor to 12 the time, stop reaction.The sediment that generates is consisting of of benchmark: Al with the product
2O
378wt%, La
2O
33wt%, P
2O
57wt%, TiO
212wt% filters sediment, and 70 ℃ of washings, the sodium oxide content in the product of washing back is less than 0.08wt% with deionized water.Under the temperature with 120 ℃ in dynamic drier, dry 1 hour.Dried product is crushed to 120 orders with airslide disintegrating mill, has both obtained product of the present invention.
Embodiment 4
In reactor, add 20gAl
2O
3The sodium aluminate solution of/l is controlled at 15 ℃ with solution temperature.Stir down, (carbon dioxide v) reacts to lead to into concentration and be 25%.When the pH value of reactant liquor to 12 the time, adding concentration is the lanthanum acetate aqueous solution of 2gLa/l.After adding lanthanum chloride solution, then add the ammonium dibasic phosphate solution that concentration is 2gP/l.After adding ammonium dibasic phosphate solution, then adding concentration is 4gTi/l, the metatitanic acid suspension of pH value 12.
Continue to lead to into that carbon dioxide reacts, when the pH value of reactant liquor to 11 the time, stop reaction.The sediment that generates is consisting of of benchmark: Al with the product
2O
386wt%, La
2O
32wt%, P
2O
54wt%, TiO
28wt%.Sediment is filtered, and 65 ℃ of washings, the sodium oxide content in the product of washing back is less than 0.12wt% with deionized water.Under the temperature with 110 ℃ in dynamic drier, dry 0.7 hour.Dried product is crushed to 200 orders with airslide disintegrating mill, has both obtained product of the present invention.
Comparative Examples 1
In embodiment 3, except that do not phosphorate, lanthanum, titanium elements compound, other course of reaction and controlled condition all remain unchanged.
Adopt the pure cerium hydroxide aluminium powder body that contains lanthanum-phosphorus-titanium aluminium hydroxide powder and Comparative Examples 1 preparation of embodiment 1～4 preparation respectively, be prepared into the alumina support sample.Take by weighing oxide weight respectively and be the aluminium hydroxide powders of 100 grams, add 4 gram sesbania powder, 3 gram glacial acetic acid and proper amount of deionized water, after mediating, cylindrical little of extrusion Φ 2.0.Little 120 ℃ of dryings placed 750 ℃ of roastings of Muffle furnace 4 hours after 4 hours.Have a power failure, reduce to normal temperature naturally, corresponding making contains lanthanum-phosphorus or pure alumina support sample.Under the same conditions, measure acid strength, pore volume and the specific area of these samples, the result lists in the table 1.
Table 1: the acid strength of alumina support, pore volume and specific area
| Sample number into spectrum | Total acid strength, mmolpy/g | Pore volume, ml/g | Specific area, m2/g |
| Embodiment 1 | 0.316 | 0.724 | 356 |
| Embodiment 2 | 0.272 | 0.658 | 295 |
| Embodiment 3 | 0.305 | 0.685 | 312 |
| Embodiment 4 | 0.292 | 0.705 | 331 |
| Comparative Examples 1 | 0.125 | 0.604 | 278 |
As can be seen from Table 1, under identical preparation condition, the present invention preparation contain lanthanum-phosphorus-titanium elements aluminium hydroxide powder production contain lanthanum-phosphorus-titanium aluminum oxide carrier, have bigger total acid strength, pore volume and specific area than pure alumina carrier.
Adopt infusion process, under the identical operations condition, on the alumina support of embodiment 1 and Comparative Examples 1, load 12 gram molybdenum oxides, 20 gram tungsten oxides and 4 gram nickel oxide are prepared into two coal tar distillate Hydrobon catalysts respectively.With the high temperature coal-tar fraction is raw material, in the hydrogen dividing potential drop of 15Mpa, and liquid air speed 0.3 o'clock
-1, hydrogen-oil ratio (v/v) 1500, process conditions under carry out the hydrofinishing catalytically active assessment.The desulfurization degree of embodiment 1 catalyst when 360 ℃ of reaction temperatures is 99.3%, and denitrification percent is 84%; Comparative Examples 1 catalyst is at the desulfurization degree of 385 ℃ of reaction temperatures only 85%, and denitrification percent only is 81%.Evaluation result shows that embodiment 1 catalyst is under the situation of reaction temperature than low 25 ℃ of the reaction temperature of Comparative Examples 1 catalyst, its hydrodesulfurization rate and hydrodenitrogeneration rate are still than the hydrodesulfurization rate and the hydrodenitrogeneration rate height of Comparative Examples catalyst, the catalyst that lanthanum-phosphorus-the titanium elements aluminium hydroxide powder is made that contains of the present invention is adopted in this explanation, has good low-temperature catalytic activity really.
Claims (7)
1. preparation method who contains lanthanum-phosphorus-titanium elements aluminium hydroxide powder, its feature may further comprise the steps:
(1) compound concentration is 10～45g Al
2O
3The sodium aluminate solution of/l;
(2) preparation contains the compound water solution that contains lanthanum element that lanthanum element concentration is 0.1～10gLa/l;
(3) preparation phosphorus element-containing concentration is the compound water solution of the phosphorus element-containing of 0.1～10gP/l;
(4) preparation titaniferous concentration of element is the titanium-containing compound suspension of 5～15gTi/l;
(5) under stirring condition, carbon dioxide is fed sodium aluminate solution, contains in the compound water solution of compound water solution, phosphorus element-containing of lanthanum element and the common mixed solution of forming of titanium-containing compound suspension and react, generate sediment, this sediment is consisting of of benchmark: Al with the product
2O
368～95.6wt%, La
2O
30.2-6.0wt%, P
2O
52～9wt%, TiO
22～17wt%, in the course of reaction, feeding the carbon dioxide volumetric concentration is 10～40%, and after reaction finished, the pH value of mixed liquor was 8～12, and it is 5～40 ℃ that entire reaction course keeps reaction temperature;
(6) solid-liquid mixtures that produces in the step (5) is filtered, and wash leaching solid, dry, pulverize, make and contain lanthanum-phosphorus-titanium elements aluminium hydroxide powder.
2. the preparation method who contains lanthanum-phosphorus-titanium elements aluminium hydroxide powder according to claim 1 is characterized in that the compound water solution that contains lanthanum element in the described step (2) is sulfate, nitrate, acetate or the muriatic aqueous solution that contains lanthanum element.
3. the preparation method who contains lanthanum-phosphorus-titanium elements aluminium hydroxide powder according to claim 1, the compound water solution that it is characterized in that the phosphorus element-containing in the described step (3) is the phosphatic aqueous solution.
4. the preparation method who contains lanthanum-phosphorus-titanium elements aluminium hydroxide powder according to claim 1 is characterized in that the titanium-containing compound suspension in the described step (4) is the suspension of titanium oxide or metatitanic acid.
5. the preparation method who contains lanthanum-phosphorus-titanium elements aluminium hydroxide powder according to claim 1, it is characterized in that describedly containing the compound water solution of lanthanum element, the compound water solution and the titanium-containing compound suspension of phosphorus element-containing is to join in the sodium aluminate solution in carbon dioxide feeding process, wherein titanium-containing compound suspension joins in the reaction mixed serum at last.
6. the preparation method who contains the lanthanum element aluminium hydroxide powder according to claim 1 is characterized in that the wash temperature in the described step (6) is 50～80 ℃, and the sodium oxide content in the product of washing back is less than 0.2wt%.
7. the preparation method who contains the lanthanum element aluminium hydroxide powder according to claim 1, it is characterized in that the drying mode in the described step (6) is that normal pressure is dynamically dry, baking temperature is 50～150 ℃, be 0.3～1.5 hour drying time, and pulverize to air-flow and pulverize, pulverizing the back product granularity is 80～300 orders.
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| CN103055924B (en) * | 2011-10-21 | 2015-02-25 | 中国石油化工股份有限公司 | Preparation method of bulk phase hydrocracking catalyst |
| CN103055925B (en) * | 2011-10-21 | 2015-04-01 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst composition |
| CN103055926B (en) * | 2011-10-21 | 2015-04-01 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst composition |
| CN103055922B (en) * | 2011-10-21 | 2015-05-13 | 中国石油化工股份有限公司 | Preparation method of bulk phase hydrocracking catalyst |
| CN103055923B (en) * | 2011-10-21 | 2015-04-01 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN103055927B (en) * | 2011-10-21 | 2015-02-25 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN103372441B (en) * | 2012-04-13 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of methanol synthesis catalyst |
| CN103372440B (en) * | 2012-04-13 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of methanol synthesis catalyst |
| CN103657688B (en) * | 2012-09-12 | 2015-09-23 | 安徽迪诺环保新材料科技有限公司 | A kind ofly add tungsten type nanometer titanium dioxide Catalysts and its preparation method for denitrating flue gas |
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