CN1743071A - Method for preparing molecular sieve-oxide composite material - Google Patents
Method for preparing molecular sieve-oxide composite material Download PDFInfo
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- CN1743071A CN1743071A CN 200410073635 CN200410073635A CN1743071A CN 1743071 A CN1743071 A CN 1743071A CN 200410073635 CN200410073635 CN 200410073635 CN 200410073635 A CN200410073635 A CN 200410073635A CN 1743071 A CN1743071 A CN 1743071A
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Abstract
The preparation method of molecular sieve-silicon or/and aluminium oxide composite material includes the following steps: uniformly mixing acidic solution or/and sol containing silicon or/and aluminium oxide precursor, urea and molecular sieve slurry which contains 10-50 wt% of molecular sieve and whose pH value is 1-8, ageing at 100-250deg.C for 10 hr-5 days, filtering the obtained gel and drying. In the course of preparation, one or several kinds of elements are selected from IIIB, IVB and La system. Said composite catulytic material has higher alkylation reaction activity and selectivity.
Description
Technical field
The invention relates to a kind of preparation method of molecular sieve-oxide composite material.Specifically, be about a kind of molecular sieve carried in Large ratio surface silicon or/and prepare the method for compound catalyze material on the aluminum oxide carrier, this composite can be used as the catalyst of iso-butane-butene alkylation.
Background technology
For some hydrocarbon conversion process that is subjected to DIFFUSION CONTROLLED, the catalyst with desirable aperture and pore structure will improve the selectivity of himself and reaction to a great extent in life-span.On the Large ratio surface carrier, make a kind of effective ways that molecular sieve/oxide compound catalyze material comes to this molecular sieve carried.For nano level molecular sieve, oxide is dispersing molecule sieve particulate effectively in addition, makes it be difficult for assembling, improving catalytic performance.
People such as Landau are at Chem.Mater 1999, Vol.11, having described a kind of among the P2030-2037 is that the beta-molecular sieve of 10～15nm is stable at the method in the alumina gel with granular size: at first the gel aluminum hydroxide filter cake is scattered in the water, makes the aluminium hydroxide suspension of pH9.05; With its at room temperature with the beta-molecular sieve slurries of pH12.7 according to Al
2O
3The weight ratio of/molecular sieve=1: 1 is mixed to pH11.8 (in the preparation of other two batch samples, aluminium hydroxide suspension mixes the back and adds rare nitric acid and makes the pH of slurries be respectively 11.0 and 10.0 with the beta-molecular sieve slurries); Stirred after 2 hours aged at room temperature 24 hours; Decant is isolated precipitation, and is 70 weight % at 50 ℃ of vacuum drying to water content; Extruder grain and in 120 ℃ of dryings 5 hours, final program intensification roasting.Nano-beta molecular sieve/alumina composite material that this method makes is 2 times of nano-beta molecular sieve aggregation of not load to the catalytic activity of isopropylbenzene.
People such as Bhavana Rakshe have described a kind of Zr-Al-β composite with beta-molecular sieve structure at J.of Catalysis 188 among the 252-260 (1999).This material is preparation like this: with a certain amount of NEt
4The OH aqueous solution slowly joins SiO
2The aqueous solution in, stir the back and drip ZrCl
4The aqueous solution, add Al subsequently more respectively
2(SO
4)
3And the aqueous solution of NaOH; The gained mixed liquor stirred after one hour, and crystallization is 10 days under 413K, and drying, roasting obtain Zr-Al-β composite again.Compare Zr-Al-β composite the acid and isomerization selectivity of meta-xylene all obviously strengthened than the former two with the beta-molecular sieve of beta-molecular sieve that does not contain the Zr element and load Zr compound.
People such as N.Kubicek have described a kind of method that beta-molecular sieve is stable in the amorphous silicon aluminium carrier in Applied Catalysis A:General 175 (1998) 159-171: at first prepare SiO with sol-gel process
2-Al
2O
3Gel mixes with the finished product beta-molecular sieve this gel then in the presence of hyperacoustic, at last with this mixture oven dry, roasting.
US4,800,187 have described the growing method of a kind of MFI structure molecular screen on monolithic honeycomb shape ceramic monolith.Wherein produce stronger adhesion between molecular sieve and the carrier, and be uniformly distributed in the duct of carrier inside.
That CN1100004C discloses is a kind of preparation method who contains the catalysis material of nano molecular sieve: with pH be 1～4, SiO
2And/or Al
2O
3Content be the acidic silicasol of 10～50 weight % or acidic aluminum sol or acidic silicasol and aluminium colloidal sol mixture with contain 10～50 weight % nano molecular sieves, pH is that 9～14 molecular sieve pulp is according to (SiO
2And/or Al
2O
3The weight ratio of)/molecular sieve=0.2～2 is under agitation mixed, and making the pH that mixes back gained mixture is 7～9.5, thereby forms gel; Then with gained gel drying and pulverizing or moulding.
US6,127,309 disclose a kind of iso-butane-butene alkylation Preparation of catalysts method that is used for.This catalyst is by sulfate or mantoquita and ZrCl
4In stainless steel cauldron, synthesize.
WO03/045548 discloses a kind of with molecular sieve and middle mesoporous inorganic oxide composite methods: earlier the finished product molecular sieve is mixed with the precursor of inorganic oxide, the pH value of mixed liquor is 7, drips a kind of alcohol matter that contains as the template agent subsequently, makes gel; Gel was at room temperature worn out 10～20 hours, then respectively at 98 ℃～100 ℃ and 150 ℃～200 ℃ dry certain hours, after roasting makes composite.
Summary of the invention
The objective of the invention is to provide on the basis of above-mentioned prior art the another kind of new method for preparing the composite of being made up of molecular sieve and Large ratio surface silicon or/and aluminum oxide carrier, this composite can be used as the catalyst of iso-butane-butene alkylation.
Preparation method provided by the invention may further comprise the steps: with silicon or/and the acid solution of aluminum oxide precursor or/and colloidal sol, alkali precipitation agent and contain 10～50 molecular sieve pulps weight % molecular sieve, pH 1～8 and mix, 100～250 ℃ of following ageings 10 hours～5 days, the gained gel after filtration and be drying to obtain molecular sieve-silicon provided by the invention or/and the aluminum oxide composite.
Also can contain one or more in this composite and be selected from IIIB, the element of IVB and La system, when needs add these elements, preparation method provided by the invention may further comprise the steps: with silicon or/and the acid solution of aluminum oxide precursor or/and colloidal sol, contain one or more and be selected from IIIB, acid solution or colloidal sol that the compound of IVB and La series elements forms, alkali precipitation agent and contain 10～50 weight % molecular sieves, the molecular sieve pulp of pH 1～8 mixes, 100～250 ℃ of following ageings 10 hours～5 days, the gained gel after filtration and be drying to obtain molecular sieve-silicon provided by the invention or/and the aluminum oxide composite.
Wherein said silicon is or/and aluminum oxide is meant silica or aluminium oxide or amorphous silicon aluminium.Precursor kind to them in the inventive method does not have particular restriction, can be that various silicon commonly used are or/and the precursor of aluminum oxide in the catalytic field, and for example: the precursor of silica can be sodium metasilicate, sodium metasilicate, Ludox etc.; The precursor of aluminium oxide can be meta-aluminic acid, aluminum sulfate, aluminum nitrate, various hydrated aluminas etc.; The precursor of amorphous silicon aluminium can be the Alusil that makes with various prior aries.
Wherein said acid solution is or/and the pH value of acidic sol all should be 1～6.
Wherein said silicon is dissolved in the solution that forms in the water or/and the acid solution of aluminum oxide precursor is a soluble compound by these precursor.
Wherein said silicon or/and the acidic sol of aluminum oxide precursor can obtain by following several method:
(1) commercially available colloidal sol commodity.For example: Ludox, aluminium colloidal sol, Alusil, not enough as its pH value, the usable acid adjustment.
(2) hydrolysis by organic ester makes.For example Ludox can make by the hydrolysis of organosilicon acid esters, and adoptable organosilicon acid esters comprises methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester etc., and hydrolysising condition can adopt condition well-known to those skilled in the art.For example: a kind of organosilicon acid esters mixed with the alcohols with 1～6 carbon atom make solution, add entry, make that the weight ratio of organosilicon acid esters and alcohol and water is an ester in the gained mixture: alcohol: water=1: (0.1～4.0): (0.1～4), preferred ester: alcohol: water=1: (0.1～2.0): (0.1～3), the gained mixture was at room temperature stirred 0.5～3 hour, with diluted mineral acid its pH is transferred to 1～4 then.
(3) metal and acid reaction make.The metallic aluminium colloidal sol of making as metallic aluminium and hydrochloric acid reaction.
(4) make with sour peptization hydrous oxide.Colloidal sol or the soliquid that obtains after with sour peptization by hydrated alumina for example.
Wherein saidly containing the acid solution that one or more compounds that are selected from IIIB, IVB and La series elements form, is that the soluble-salt by above-mentioned element compound forms.For example: Y (NO
3)
3, Ce (NO
3)
3, Th (NO
3)
3, ZrOCl
2, Zr (NO
3)
4, ethyoxyl zirconium (C
2H
5O)
4Zr, propoxyl group zirconium (C
3H
7O)
4Zr etc.
Wherein saidly contain the acidic sol that one or more compounds that are selected from IIIB, IVB and La series elements form, be meant the inorganic sol of above-mentioned element compound, or the colloidal sol that makes of the hydrolysis by organic ester or oxide and acid reaction.
Said alkali precipitation agent is not alkalescence for do not make solution when normal-temperature dissolution is in the aqueous solution in the inventive method, and in its decomposition temperature or be higher than under the decomposition temperature and decompose the organic or inorganic compound that can make the aqueous solution be alkalescence, urea for example, it is 0.1～1.5 that its consumption should make the weight ratio of molecular sieve and urea.
Said molecular sieve is the various molecular sieves that are applicable to iso-butane-butene alkylation in the inventive method, preferably beta-molecular sieve, Y zeolite, ZSM-5 molecular sieve, modenite and optional mixture in them.These molecular sieves be both commercial goods, also were prepared into according to existing patented technology, and for example, beta-molecular sieve can be by USP3, and the method described in 308,069 makes; Nano-beta molecular sieve can make by the method described in the CN1100004C.It is 10～95 weight % that the consumption of molecular sieve should make the content of molecular sieve in the compound catalyze material.
The molecular sieve pulp that to regulate pH value molecular sieve pulp before can be filtered, directly synthesize; Can be the suspension that above-mentioned dope filtration washing back reslurry forms; Also can be that the finished product molecular sieve is scattered in the suspension that forms in the water; It can also be the mixture of above-mentioned two or three slurries.
The filtration of said jel product and drying in the inventive method all can be operated by prior art.For example, following dry 2～30 hours at 50～250 ℃.
The compound catalyze material of making by the inventive method is as before the catalyst, and the processing that need make the transition that is: is converted to Hydrogen with the sodium type molecular sieve in the composite.Transition, method can be by method operation transition of molecular sieve in the prior art.For example, wash 2 times with 60 ℃ water making beating earlier, use water soluble salt of ammonia according to compound catalyze material again: weight ratio, the compound catalyze material of ammonium salt=2: 1: the liquid-solid ratio of ammonium salt aqueous solution=1: 2 is carried out ion-exchange 4 times, each exchange 2 hours, need filter after each exchange, wash, 110 ℃ of dryings 2 hours, the compound catalyze material after the last exchange was through 550 ℃ of roastings 3 hours.
According to method provided by the invention, in the catalysis material preparation process, be selected from the acid solution of Al, Si, IIIB, IVB and La series elements compound and/or the carrier that the acidic sol precipitation from homogeneous solution forms Large ratio surface, and evenly compound, thereby the catalytic activity of catalysis material and the diffusion of catalyst have been strengthened with molecular sieve; When molecular sieve adopted nano level granular size, the nano molecular sieve in the compound catalyze material that employing the inventive method is made was difficult for assembling, having improved its catalytic performance.
Data show to have higher alkylation activity and selectivity according to method provided by the invention than the compound catalyze material that makes according to art methods, and its life-span improves more than 20% than the latter.
The specific embodiment
The following examples will give further instruction to the present invention, but therefore not limit the present invention.
Employed beta-molecular sieve is according to USP 3,308 in the embodiment of the invention, and embodiment institute describing method is synthetic in 069.Concrete synthesis step is as follows:
Get 26.181g concentration and be 25% TEAOH and add the 1.35g sodium aluminate, stir and add 38.8g Ludox (silica alumina ratio that feeds intake is 30) down; Continue to stir after 1 hour, the 423K crystallization is 3 days in reactor, obtains the slurries that beta-molecular sieve content is 38 weight %.
Get the above-mentioned beta-molecular sieve slurries of part, filter to isolate solid product, with the 1N ammonium chloride solution according to molecular sieve: the liquid-solid ratio of ammonium chloride solution=1: 2 is carried out ammonium exchange 4 times to molecular sieve, each 2 hours, filter each exchange back, washing, 110 ℃ of dryings 2 hours, obtains ammonium type β zeolite powder.Ammonium type β zeolite powder in 550 ℃ of roastings 3 hours, is promptly obtained the Hydrogen beta-molecular sieve.
Employed nano-beta molecular sieve is synthetic according to 7 describing methods of embodiment among the CN1100004C in the embodiment of the invention.Concrete synthesis step is as follows:
Boehmite (is contained Al
2O
356.6 weight %, Zhou village catalyst plant product), NaOH (chemical pure, Beijing Chemical Plant's product), tetraethyl ammonium hydroxide solution (2.633N goes in in a big way emerging good fortune fine chemistry industry research institute) adds deionized water, heating for dissolving stirs, and makes working solution; With granularity is that 80～120 purpose silochroms (igloss 3.7%, Haiyang Chemical Plant, Qingdao) mix with above-mentioned working solution, makes the silica gel surface wetting by working solution, obtains reactant mixture, and wherein the mol ratio of each component is SiO
2/ Al
2O
3=30, Na
2O/SiO
2=0.075, TEAOH/SiO
2=0.09, H
2O/SiO
2=6.5, (wherein SY1634-70 is a kind of commercially available pumping fluid to add weight ratio then and be 1: 1 additive SY1634-70 and Tween-65, Dalian Petrochemical Industry Company's seven factory's products, molecular weight 800-1000,25% of polyoxyethylene fiduciary point polyalkylene ether weight wherein; Tween-65 is a kind of polyol-based non-ionic surfactant, Farco company commodity, and molecular weight 800～1000, HLB=10.5) and stir additive/SiO
2Weight ratio is 2.5.With this reactant mixture 120 ℃ of crystallization 24 hours in autoclave,, promptly get the slurries that nano-beta molecular sieve content is 38 weight % after being cooled to room temperature again 140 ℃ of crystallization 48 hours.
Get the above-mentioned nano-beta molecular sieve slurries of part, filter to isolate solid product, with the 1N ammonium chloride solution according to molecular sieve: the liquid-solid ratio of ammonium chloride solution=1: 2 is carried out ammonium exchange 4 times to molecular sieve, each 2 hours, filter each exchange back, washing, 110 ℃ of dryings 2 hours, obtains the former powder of ammonium type nano-beta molecular sieve.The former powder of ammonium type nano-beta molecular sieve is promptly obtained the Hydrogen nano-beta molecular sieve in 3 hours in 550 ℃ of roastings, be designated as BEA.
Embodiment 1
The explanation of this example prepares beta-molecular sieve/SiO with the inventive method
2Compound catalyze material.
At USP 3,308, add the hydrochloric acid solution that concentration is 30 heavy % in the 4.84g beta-molecular sieve slurries of the filtered that 069 method synthesizes (molecular sieve concentration be 30 heavy %), the pH value of slurries is transferred to 1.5.The acidic silicasol of above-mentioned slurries and pH1.6 (Changhong chemical plant, Beijing commodity, SiO
2Content is 25.9 weight %, down with) 22.5g and 5.0g urea (and Beijing Yili Fine Chemicals Co., Ltd., AR, down with) mix, at room temperature strong agitation is 30 minutes.
Above-mentioned solution is placed the 250ml autoclave, be warmed up to 150 ℃ under airtight and intensively stirred condition, the ageing mother liquor is 22 hours under 150 ℃ and self-generated pressure.This moment the gel mother liquor pH=9.4.
With gained gel filtration after the ageing, 200 ℃ dry 2 hours down, obtain the beta-molecular sieve/SiO of beta-molecular sieve content 20%
2Compound catalyze material.Note is made sample A.
Embodiment 2
The explanation of this example prepares nano-beta molecular sieve/SiO with the inventive method
2-Al
2O
3Compound catalyze material.
The beta-molecular sieve dope filtration that will synthesize according to the CN1100004C method, with after the deionized water making beating washing three times, gained filter cake reslurry, and be that the hydrochloric acid solution of 30 heavy % transfers to 7.5 to the pH value of slurries with concentration.
20.8g ethyl orthosilicate (Beijing chemical reagents corporation produce, analyzes pure) is dissolved in the 5.76g absolute ethyl alcohol (Beijing Chemical Plant analyzes pure), and stirring time is added dropwise to it in 0.01M hydrochloric acid of 100ml, obtains clear sol after the estersil hydrolysis, pH2.With the above-mentioned Ludox of 3.06g and 5.8g acidic aluminum sol (Qilu Petrochemical company catalyst plant commodity, wherein Al
2O
3Content is 35 weight %, pH1.5, down with) at room temperature mix the silicon-aluminum sol that obtains pH3.7.
Above-mentioned 25g beta-molecular sieve slurries (molecular sieve concentration is 30 heavy %) are mixed with above-mentioned silicon-aluminum sol and 15.0g urea, and at room temperature strong agitation is 30 minutes.
Above-mentioned solution is placed the 250ml autoclave, be warmed up to 110 ℃ under airtight and intensively stirred condition, the ageing mother liquor is 72 hours under 110 ℃ and self-generated pressure.This moment the gel mother liquor pH=10.4.
With gained gel filtration after the ageing, 80 ℃ dry 10 hours down, obtain the nano-beta molecular sieve/SiO of beta-molecular sieve content 65%
2-Al
2O
3Compound catalyze material.Note is made sample B.
Embodiment 3
The explanation of this example prepares beta-molecular sieve/SiO with the inventive method
2-Al
2O
3-ZrO
2Compound catalyze material.
Will be according to US3, the finished product beta-molecular sieve that 308,069 method the synthesizes dispersion of in deionized water, pulling an oar, and be that the hydrochloric acid solution of 30 heavy % transfers to 4.0 to the pH value of slurries with concentration.
With 15g propoxyl group zirconium (C
3H
7O)
4-Zr is dissolved in the 150ml distilled water, be stirred to solution fully limpid after, being made into concentration is the propoxyl group zirconium solution of 0.3 mol.
Ludox 3.06g among the embodiment 2 and acidic aluminum sol 2.9g are at room temperature mixed the silicon-aluminum sol that obtains pH4.5.
Above-mentioned 4.84g beta-molecular sieve slurries (molecular sieve concentration is 30 heavy %) are mixed with above-mentioned silicon-aluminum sol, propoxyl group zirconium solution and 20.0g urea, and at room temperature strong agitation is 30 minutes.
Above-mentioned solution is placed the 250ml autoclave, be warmed up to 130 ℃ under airtight and intensively stirred condition, the ageing mother liquor is 52 hours under 130 ℃ and self-generated pressure.This moment the gel mother liquor pH=11.2.
With gained gel filtration after the ageing, 55 ℃ dry 30 hours down, obtain the beta-molecular sieve/SiO of beta-molecular sieve content 65%
2-Al
2O
3-ZrO
2Compound catalyze material.Note is made sample C.
Embodiment 4
The explanation of this example prepares beta-molecular sieve/SiO with the inventive method
2-Al
2O
3-Y
2O
3-Ce
2O
3Compound catalyze material.
With 40g Y (NO
3)
36H
2O (Beijing Chemical Plant, AR, down together) be dissolved in the 50ml distilled water, it is limpid fully to be stirred to solution, obtains Y (NO
3)
3Solution.With 40gCe (NO
3)
33H
2O (Beijing Chemical Plant, AR, down together) be dissolved in the 50ml distilled water, it is limpid fully to be stirred to solution, obtains Ce (NO
3)
3Solution.
With the Ludox 1.53g among the embodiment 2, Y (NO
3)
3Solution 1.05g, Ce (NO
3)
3Solution 2.05g and 2.9g aluminium colloidal sol at room temperature mix the silicon-aluminum sol that contains Y, Ce that obtains pH4.0.
10g beta-molecular sieve slurries (molecular sieve concentration is 30 heavy %, and the preparation method is identical with embodiment 3) are mixed with above-mentioned silicon-aluminum sol and 5.0g urea, and at room temperature strong agitation is 30 minutes.
Above-mentioned solution is placed the 250ml autoclave, be warmed up to 135 ℃ under airtight and intensively stirred condition, the ageing mother liquor is 70 hours under 135 ℃ and self-generated pressure.This moment the gel mother liquor pH=11.4.
With gained gel filtration after the ageing, 100 ℃ dry 20 hours down, obtain the beta-molecular sieve/SiO of beta-molecular sieve content 65%
2-Al
2O
3-Y
2O
3-Ce
2O
3Compound catalyze material.Note is made sample D.
Embodiment 5
The explanation of this example prepares Y molecular sieve/SiO with the inventive method
2Compound catalyze material.
10g ammonium Y zeolite finished product (China Petrochemical Industry's Chang Ling catalyst plant commodity) is scattered in the 23ml deionized water, fully stirs and make Y zeolite slurries (molecular sieve concentration is 30 heavy %).The hydrochloric acid solution that with concentration is 30 heavy % transfers to 3.0 to the pH value of slurries.
Above-mentioned slurries are mixed with acidic silicasol 12.5g and the 5.0g urea of pH1.6, and at room temperature strong agitation is 30 minutes.
Above-mentioned solution is placed the 250ml autoclave, be warmed up to 150 ℃ under airtight and intensively stirred condition, the ageing mother liquor is 22 hours under 150 ℃ and self-generated pressure.This moment the gel mother liquor pH=10.4.
With gained gel filtration after the ageing, 100 ℃ dry 10 hours down, obtain the Y molecular sieve/SiO2 compound catalyze material of molecular sieve content 75%.Note is made sample E.
Embodiment 6
The explanation of this example prepares modenite/SiO with the inventive method
2Compound catalyze material.
10g ammonium type modenite finished product (China Petrochemical Industry's Chang Ling catalyst plant commodity) is scattered in the 23ml deionized water, fully stirs and make modenite slurries (zeolite concentration is 30 heavy %).The hydrochloric acid solution that with concentration is 30 heavy % transfers to 1.5 to the pH value of slurries.
Above-mentioned slurries are mixed with acidic silicasol 34.1g and the 5.0g urea of pH1.6, and at room temperature strong agitation is 30 minutes.
Above-mentioned solution is placed the 250ml autoclave, be warmed up to 150 ℃ under airtight and intensively stirred condition, the ageing mother liquor is 22 hours under 150 ℃ and self-generated pressure.This moment the gel mother liquor pH=9.4.
With gained gel filtration after the ageing, 150 ℃ dry 20 hours down, obtain the modenite/SiO2 compound catalyze material of molecular sieve content 50%.Note is made sample F.
Embodiment 7
The explanation of this example prepares ZSM-5 molecular sieve/SiO with the inventive method
2Compound catalyze material.
10g ammonium type ZSM-5 molecular sieve finished product (China Petrochemical Industry's Chang Ling catalyst plant commodity) is scattered in the 23ml deionized water, fully stirs and make ZSM-5 molecular sieve pulp (molecular sieve concentration is 30 heavy %).The hydrochloric acid solution that with concentration is 30 heavy % transfers to 5.0 to the pH value of slurries.
Above-mentioned slurries are mixed with acidic silicasol 38.6g and the 8.0g urea of pH1.6, and at room temperature strong agitation is 30 minutes.
Above-mentioned solution is placed the 250ml autoclave, be warmed up to 150 ℃ under airtight and intensively stirred condition, the ageing mother liquor is 22 hours under 150 ℃ and self-generated pressure.This moment the gel mother liquor pH=10.7.
With gained gel filtration after the ageing, 100 ℃ dry 20 hours down, obtain the ZSM-5 molecular sieve/SiO2 compound catalyze material of molecular sieve content 50%.Note is made sample G.
Comparative Examples 1
This Comparative Examples illustrates prior art for preparing beta-molecular sieve/SiO routinely
2-Al
2O
3Compound catalyze material.
The beta-molecular sieve dope filtration that will synthesize according to 7 describing methods of embodiment among the CN1100004C with deionized water making beating washing three times, gained filter cake reslurry at last and add a little ammoniacal liquor, obtains the nano molecular sieve slurries of 50 weight %, pH11.
The silicon-aluminum sol of the pH3.7 that will make according to embodiment 2 methods and above-mentioned gained molecular sieve pulp are according to Al
2O
3The weight ratio of/molecular sieve=0.05 is under agitation mixed, and making the pH that mixes back gained mixture is 9, thereby forms gel.Gel in 80 ℃ times dry 20 hours, is obtained the beta-molecular sieve/SiO of molecular sieve content 65%
2-Al
2O
3Composite.
Sample is ground, sieve is got 40～60 purpose particles, hot water making beating washing secondary with 60 ℃, use the 1N ammonium chloride solution according to molecular sieve again: the liquid-solid ratio of ammonium chloride solution=1: 2 is carried out ammonium exchange 4 times, filter each exchange 2 hours, exchange back, washing, 110 ℃ of dryings 2 hours, exchanges the composite that back 550 ℃ of roastings obtained Hydrogen in 3 hours for the last time.Note is made sample H.
Comparative Examples 2
The explanation of this Comparative Examples prepares Y molecular sieve/SiO according to the method for WO03/045548
2Composite.
10g ammonium Y zeolite finished product (China Petrochemical Industry's Chang Ling catalyst plant commodity) is scattered in the 23ml deionized water, mix with the 6.6g ethyl orthosilicate then, stir and add the 4.2g triethanolamine after 0.5 hour, stirring and be added dropwise to 4.5g concentration after 0.5 hour in mixed liquor is 35% tetraethyl ammonium hydroxide, stir after 2 hours, form gel.
The gained gel is at room temperature aging after 17 hours, in 100 ℃ of air atmospheres dry 28 hours, 170 ℃ dry 17.5 hours down, after 600 ℃ of roastings 10 hours, obtain the Y molecular sieve/SiO2 composite of molecular sieve content 75%.Note is made sample I.
Comparative Examples 3
The explanation of this Comparative Examples prepares modenite/SiO according to the method for WO03/045548
2Composite.
10g ammonium type modenite finished product (China Petrochemical Industry's Chang Ling catalyst plant commodity) is scattered in the 17ml deionized water, mixes with the 20.32g ethyl orthosilicate then, stir adding 9.33g triethanolamine after 0.5 hour.Stirring and be added dropwise to 4.02g concentration after 0.5 hour in mixed liquor is 35% tetraethyl ammonium hydroxide, stirs after 2 hours, forms gel.
The gained gel is at room temperature aging after 17 hours, in 100 ℃ of air atmospheres dry 28 hours, 170 ℃ dry 17.5 hours down, after 600 ℃ of roastings 10 hours, obtain the modenite/SiO of molecular sieve content 50%
2Composite.Note is made sample J.
Comparative Examples 4
The explanation of this Comparative Examples prepares ZSM-5 molecular sieve/SiO by the WO03/045548 method
2Composite.
10g ammonium type ZSM-5 molecular sieve finished product (China Petrochemical Industry's Chang Ling catalyst plant commodity) is scattered in the 17ml deionized water, mix with the 20.32g ethyl orthosilicate then, stir and add the 9.33g triethanolamine after 0.5 hour, stirring and be added dropwise to 4.02g concentration after 0.5 hour in mixed liquor is 35% tetraethyl ammonium hydroxide, stirs and forms gel after 2 hours.
The gained gel is at room temperature aging after 17 hours, in 100 ℃ of air atmospheres dry 28 hours, 170 ℃ dry 17.5 hours down, after 600 ℃ of roastings 10 hours, obtain the ZSM-5 molecular sieve/SiO of molecular sieve content 50%
2Composite.Note is made sample K.
Embodiment 8
The compound catalyze material that the present embodiment explanation makes by the method for the invention provides has bigger specific surface.
Respectively the compound catalyze material sample that makes among molecular sieve BEA, the embodiment 1～7 is ground, sieve is got 40～60 purpose particles, hot water making beating washing secondary with 60 ℃, use the 1N ammonium chloride solution according to molecular sieve again: the liquid-solid ratio of ammonium chloride solution=1: 2 is carried out ammonium exchange 4 times, filter each exchange 2 hours, exchange back, washing, 110 ℃ of dryings 2 hours, exchanges the compound catalyze material that back 550 ℃ of roastings obtained Hydrogen in 3 hours for the last time.
Specific area measuring adopts N2 absorption static capacity method, carries out on the automatic physical adsorption appearance of Micromeritics ASAP2400.Measurement result is listed in table 1.
For comparison purpose, the comparative sample that makes in each Comparative Examples has also been carried out same specific surface mensuration, one is listed in table 1 as a result.
Table 1
| Sample number into spectrum | Example number | Sample component | Specific surface, m 2/g | ||
| S Always | S In | S Outward | |||
| BEA A B C D E F G H I J K | 1234567 contrasts, 1 contrast, 2 contrasts, 3 contrasts 4 | Nano-beta molecular sieve beta-molecular sieve/SiO 2Nano-beta molecular sieve/SiO 2-Al 2O 3Beta-molecular sieve/SiO 2-Al 2O 3-ZrO 2Beta-molecular sieve/SiO 2-Al 2O 3-Y 2O 3-Ce 2O 3Y molecular sieve/SiO 2Modenite/SiO 2ZSM-5 molecular sieve/SiO 2Nano-beta molecular sieve/SiO 2-Al 2O 3Y molecular sieve/SiO 2Modenite/SiO 2ZSM-5 molecular sieve/SiO 2 | 554 599 598 596 598 592 604 599 549 502 496 480 | 494 519 542 517 518 523 535 531 482 417 417 411 | 59 80 56 79 80 60 65 66 67 75 72 70 |
Embodiment 9
Present embodiment explanation the inventive method has better iso-butane/butene alkylation performance than the prepared catalysis material of art methods.
To be converted into the compound catalyze material sample that makes among molecular sieve BEA, the embodiment 1～7 of Hydrogen among the embodiment 8 respectively, sieve is got its 40～60 purpose particle and is packed into and carry out the alkylated reaction evaluation in the reaction tube of fixed bed reactors.Catalysis material sample loading amount is 5 grams.
Before the reaction earlier with sample at N
2In 300 ℃ of activation 2.0 hours, use N then under purging
2Adjust reaction pressure to 2.1Mpa.The raw materials components mole ratio of raw material iso-butane/butylene is 11,1-butylene mass space velocity WHSV=1.3h
-1, reaction temperature is 80 ℃.
Listed the time required when the 1-butene conversion reduces to 90% in the table 2, and the selectivity of the target product trimethylpentane (TMP) of synchronization.
For comparison purpose, the comparative sample that makes in each Comparative Examples has also been carried out same alkylation properties evaluation, one is listed in table 2 as a result.
Can find out that by data in the table Comparative Examples of the alkylated reaction life-span of the catalysis material that makes by the inventive method than prior art exceeds more than 20%, and selectivity is more excellent.
Table 2
| Sample number into spectrum | Example number | Time, minute | The TMP yield, % |
| BEA A B C D E F G H I J K | 1234567 contrasts, 1 contrast, 2 contrasts, 3 contrasts 4 | 11.1 27.3 29.9 52.4 32.7 26.3 38.5 41.7 28.6 21.7 17.4 15.9 | 23.9 25.2 35.6 37.3 35.4 36.7 34.8 38.5 20.9 14.6 13.4 13.0 |
Claims (9)
1, a kind of molecular sieve-silicon is or/and the preparation method of aluminum oxide composite, may further comprise the steps: with silicon or/and the acid solution of aluminum oxide precursor or/and colloidal sol, urea and contain 10～50 molecular sieve pulps weight % molecular sieve, pH1～8 and mix, 100～250 ℃ of following ageings 10 hours～5 days, with gained gel filtration, drying.
2, a kind of molecular sieve-silicon is or/and the preparation method of aluminum oxide composite, may further comprise the steps: with silicon or/and the acid solution of aluminum oxide precursor or/and colloidal sol, contain acid solution that one or more compounds that are selected from IIIB, IVB and La series elements form or/and colloidal sol, urea and contain 10～50 molecular sieve pulps weight % molecular sieve, pH1～8 and mix, 100～250 ℃ of following ageings 10 hours～5 days, with gained gel filtration, drying.
3, according to the preparation method of claim 1 or 2, wherein said silicon is or/and aluminum oxide is meant silica or aluminium oxide or amorphous silicon aluminium.
4, according to the preparation method of claim 1 or 2, wherein said acid solution is or/and the pH value of colloidal sol is 1～6.
5, according to the preparation method of claim 1 or 2, wherein should to make the weight ratio of molecular sieve and urea be 0.1～1.5 to the consumption of said urea.
6, according to the preparation method of claim 1 or 2, wherein said molecular screening is from beta-molecular sieve, Y zeolite, ZSM-5 molecular sieve, modenite and optional mixture in them.
7, according to the preparation method of claim 2, wherein saidly contain the acid solution that one or more compounds that are selected from IIIB, IVB and La series elements form, be that the soluble-salt by above-mentioned element compound forms.
8, according to the preparation method of claim 2, the wherein said acidic sol that contains one or more compounds that are selected from IIIB, IVB and La series elements formation, be meant the inorganic sol of above-mentioned element compound, or the colloidal sol that makes of the hydrolysis by organic ester or oxide and acid reaction.
9, according to the preparation method of claim 1 or 2, the content of molecular sieve is 10～95Wt% in the wherein said compound catalyze material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102451745A (en) * | 2010-10-14 | 2012-05-16 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing Y-type molecular sieve/amorphous silica-alumina and preparation method thereof |
| CN102451740A (en) * | 2010-10-14 | 2012-05-16 | 中国石油天然气股份有限公司 | Preparation method of nano Y-shaped molecular sieve/amorphous silica-alumina composite material |
| CN114350182A (en) * | 2021-12-17 | 2022-04-15 | 沈阳市津浩科技有限公司 | Preparation method of modified zeolite for environment-friendly high-performance interior wall coating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451745A (en) * | 2010-10-14 | 2012-05-16 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing Y-type molecular sieve/amorphous silica-alumina and preparation method thereof |
| CN102451740A (en) * | 2010-10-14 | 2012-05-16 | 中国石油天然气股份有限公司 | Preparation method of nano Y-shaped molecular sieve/amorphous silica-alumina composite material |
| CN102451745B (en) * | 2010-10-14 | 2013-10-16 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing Y-type molecular sieve/amorphous silica-alumina and preparation method thereof |
| CN102451740B (en) * | 2010-10-14 | 2013-10-16 | 中国石油天然气股份有限公司 | Preparation method of nano Y-shaped molecular sieve/amorphous silica-alumina composite material |
| CN114350182A (en) * | 2021-12-17 | 2022-04-15 | 沈阳市津浩科技有限公司 | Preparation method of modified zeolite for environment-friendly high-performance interior wall coating |
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