CN100540471C - The method of preparing molecular sieve with EUO structure from silicon aluminum oxide powder - Google Patents
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- CN100540471C CN100540471C CNB2007100618216A CN200710061821A CN100540471C CN 100540471 C CN100540471 C CN 100540471C CN B2007100618216 A CNB2007100618216 A CN B2007100618216A CN 200710061821 A CN200710061821 A CN 200710061821A CN 100540471 C CN100540471 C CN 100540471C
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Abstract
The invention discloses a kind of method of preparing molecular sieve with EUO structure from silicon aluminum oxide powder, this method is solid silicon aluminum oxide powder and alkali, template, crystal seed, promotor and water to be mixed be prepared into initial gel mixture, places the reactor crystallization and obtains the EUO structure molecular screen.It is that the sial raw material prepares the EUO structure molecular screen in dry powder, super dense system that this method adopts the sieve and silica-sesquioxide powder, simplified technological process, shortened crystallization time, single-autoclave yield rate has improved 75%～200%, production cost has reduced by 50%～150%, and prepared Si-Al molecular sieve product performance are stable, degree of crystallinity is high, the silica alumina ratio scope is big, framework aluminum is evenly distributed, heat and hydrothermal stability height, and do not have the mother liquor discharging, effectively solved difficult problems such as the wasting of resources of the prior art and environmental pollution.
Description
Technical field
The invention belongs to the preparation method field of molecular sieve, especially a kind of method of utilizing solid silicon aluminum oxide powder stock to prepare the EUO structure molecular screen.
Background technology
The EUO structure molecular screen is the mesopore high-silica zeolite of a class novelty, has one dimension micropore canals structure, affiliated spacer is Cmma, its skeleton comprises ten Yuans straight-through ducts of ring and 12-membered ring's side pocket (side pocket) structure of vertical UNICOM with it, is a class has characteristics very much on pore passage structure molecular sieve.People such as Briscoe have illustrated the ten-ring duct of its skeleton for being made up of silica and aluminum-oxygen tetrahedron, the ovalize opening, and orifice diameter is 0.41nm * 0.58nm, side pocket is 0.81nm deeply, and the sack diameter is 0.68nm * 0.58nm (" ZEOLITES ", 1988,8,74).
Show excellent catalytic performance in the pour point reactions such as (USP20030127356) because special pore passage structure, EUO structure molecular screen reduce at dimethylbenzene isomery (USP 20010051757), content of wax oil product, have favorable industrial application prospect.
The preparation of EUO structure molecular screen has been studied by the national oil research institute of France (USP6337063, USP 6342200), it is applied to xylene isomerization catalyst as acid constituent element, and adopting the EUO structure molecular screen under identical condition is that the catalyzer of acid constituent element has higher activity and selectivity.
The synthetic work first of EUO structure molecular screen is open in European patent Eur.Pat.Appl.42226 in 1981 by people such as Casci.Comprehensive both at home and abroad about the preparation of this molecular sieve, can reduce two kinds of routes substantially: based on the hydrothermal method of liquid phase conversion mechanism with based on the dry glue process of solid phase converted in-situ mechanism.
Lin Min etc. (CN 1796278A) have reported with fluorochemical as mineralizer, the two ammoniums of dihydroxy-hexane are template, tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters are the silicon source, aluminum isopropylate or isobutanol aluminum are the aluminium source, earlier through catching up with alcohol to make gel mixture, 120 ℃～220 ℃ following crystallization 1～30 day, obtain the method for EUO structure molecular screen.Owing to adopted hydrolysis organo-silicon ester, aluminium ester as silicon and aluminum source, the molecular sieve aluminium atom that makes is evenly distributed in skeleton, has good thermostability, hydrothermal stability and acidity.Its weak point is that used organosilicon aluminum feedstock costs an arm and a leg the product cost height.
(" ZEOLITES ", 1985,5,153) such as Dodwell G W. have studied when alkali free metal ion is arranged the influence to EUO structure molecular screen crystallization product in hydrothermal system.When not adding alkalimetal ion in the system, substitute with ammoniacal liquor, the result shows when initial gel proportioning is suitable, in alkali systems and no alkali systems, all can obtain the EUO structure molecular screen.
The EUO structural zeolite of in European patent application EP-A-0042226, describing, be to adopt expensive aerosil, use the degraded product or the described derivative precursor of polymethylene α-ω two ammonium alkyl derivatives or described derivative to be prepared from as template.
(" ZEOLITES ", 1989,9,483) such as Rao G N. have reported the preparation of high silicon EUO type molecular sieve, and template used dose is toluene dimethyl amine (BDMA) and chlorination toluene.When Dodwell and Casci etc. have reported and have prepared the EUO structure with hexamethomium cations, its initial gel 44＜SiO
2/ Al
2O
3, can get pure phase EUO structure at＜120 o'clock; As 120＜SiO
2/ Al
2O
3＜240 o'clock is the mixed crystal of EUO structure and EU-2; SiO
2/ Al
2O
3＞240 o'clock is the EU-2 of pure phase.The problem that this method exists is that template toxicity is bigger and expensive, and product silica alumina ratio scope is narrower.
The preparation of EUO structure molecular screen described above is all adopted in the liquid phase water hot system and is carried out, and follows liquid phase crystallization mechanism, and productive rate is low, and crystallization time is all longer, and the template consumption is big, the preparation cost height.
(" Microporous and Mesoporous Materials " such as Andreas Arnold, 2004,67,205) reported openly and utilized dry glue process preparation [Al] EUO and [Ga] EUO molecular sieve that its preparation process is: (1) is with a certain amount of C6 (HMBr
2) be dissolved in deionized water, add silicon sol then, stirring at room two hours gets a solution; (2) sodium aluminate and sodium hydroxide is soluble in water, get b solution; (3) a and b solution are mixed stirred for several hour after, 80 ℃ of dehydrations obtain the xerogel mixture under agitation condition, are ground into fine powder and are placed in the reactor that has less water, crystallization a couple of days obtains [Al, Ga] EUO structure molecular screen under the certain temperature.
Dry glue process is followed solid phase crystallization mechanism, has overcome the low problem of productive rate in the molecular sieve preparation of liquid phase hydrothermal method to a certain extent, but itself has had device structure and the numerous and diverse defective of preparation process, is difficult for realizing industrialization.
In order to overcome the defective of prior art, realize the high-level efficiency preparation that reduces cost, the industrial applications of promotion EUO.In the present invention, creatively having adopted the sieve and silica-sesquioxide pressed powder is sial raw material synthetic EUO molecular sieve in dry powder system or super dense system, and with crystal seed, promotor technology transplant, be integrated in wherein, developed a kind of high efficiency EUO structure molecular screen preparation method; Wherein when system when to add less water and initial gel mixture be non-current shape dry powder system, crystallization process is mainly followed solid phase in-situ crystallization mechanism; And when the water yield that adds is big, when initial gel mixture is super dense system for the shape that flows, crystallization system, its crystallization mechanism is followed solid, liquid two-phase transformation mechanism; Dry powder system, super dense system are suitable for static state and dynamic crystallization respectively.The all or part of solid phase in-situ crystallization mechanism of following of the crystallization process of molecular sieve in dry powder, the super dense system, by in-situ crystallization process silicon aluminium microsphere in the feature transfer of high dispersing of aluminium atom in molecular sieve structure, so molecular sieve product has uniform framework aluminum and distributes and stability; In-situ crystallization speed is its another characteristics soon in addition, thereby crystallization time obviously shortens.Adopt the dry powder system to prepare MOR, ZSM-5 equimolecular sieve (" chemistry of fuel journal ", 1997,10,410-414 at present; " Chinese J Chem.Eng. ", 2003,11 (6), 656-659), then do not see any report with pressed powder sial raw material synthetic EUO molecular sieve in super dense system.
No matter the characteristics of method described in the invention are from the complexity of crystallization apparatus, crystallization process and whether be easy to realize that aspect such as industrialization all is better than the method that foregoing hydrothermal method and dry glue process prepare the EUO structure molecular screen.Especially with crystal seed, promotor technology transplant in preparation system of the present invention, shortened crystallization time more, enlarged synthetic phase region.The existing report (CN1796278A, USP 6342200) that adds crystal seed of EUO structure molecular screen preparation, but all be in the hydrothermal preparation system, and the mechanism of action of crystal seed in different systems is discrepant.The present invention also introduces the promotor method in the described method, and promotor prepares the EUO molecular sieve and briefly touches upon in article (" NATURE ", 1996,381,298), but any detailed substantial explanation is not arranged.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparing molecular sieve with EUO structure from silicon aluminum oxide powder, with solve crystallization process process complexity of the prior art, crystallization time is long, single-autoclave yield rate is low, cost is high and framework aluminum skewness and the defective of the product performance poor stability that causes.
The method of preparing molecular sieve with EUO structure from silicon aluminum oxide powder of the present invention, this preparation method is dissolved in the water alkali, template, crystal seed and promotor earlier, after stirring, add the sieve and silica-sesquioxide powder after being pre-mixed evenly again, stirring obtains initial gel mixture, and its mol ratio is: (0.52～20) template: (2～50) M
2O: (25～400) SiO
2: Al
2O
3: (25～3000) H
2O places closed reaction kettle crystallization under 140 ℃～220 ℃ temperature to obtain EUO structure molecular screen crystal powder after 24～168 hours then.
In the method provided by the invention, described sieve and silica-sesquioxide powder is silicon aluminium microsphere, white carbon black and silica gel, can use silicon aluminium microsphere separately, perhaps silicon aluminium microsphere and white carbon black, or silicon aluminium microsphere and silica gel mix use.
In the method provided by the invention, described alkali is oxide compound or the oxyhydroxide of Na, K or Li, oxide compound or the oxyhydroxide of preferred Na.
In the method provided by the invention, described template is C6, pentamethonium or phenylbenzene Dimethyl Ammonium, preferred C6.
In the method provided by the invention, described crystal seed is the molecular sieve crystal seed, it can be heterogeneous or the homogeneity crystal seed, the homogeneity crystal seed is the EUO structure, heterogeneous crystal seed can be Y, MOR, ZSM-5, β, L, X, MCM-22, ZSM-11, ZSM-12, ZSM-22, ZSM-35 or the ZSM-48 that structure differs from the EUO structure molecular screen, addition accounts for 0.1%～25% (wt%) of sieve and silica-sesquioxide pressed powder raw material, preferred 2.5%～10% (wt%).
In the method provided by the invention, described promotor is nitrate, phosphoric acid salt, perchlorate or vitriol, preferably nitrate; Its addition accounts for 0.01%～10% (wt%) of sieve and silica-sesquioxide pressed powder raw material, preferred 0.1%～5%.
In the method provided by the invention, use can be used or mix to described crystal seed and promotor respectively separately.
In the method provided by the invention, the optimum ratio of described initial gel mixture is: (1.0～10) template: (3～20) M
2O: (30～80) SiO
2: Al
2O
3: (35～600) H
2O, static crystallization.
In the method provided by the invention, the optimum ratio of described initial gel mixture is: (1.0～10) template: (3～20) M
2O: (30～80) SiO
2: Al
2O
3: (600～3000) H
2O, crystallization under the agitated conditions.
A kind of method of utilizing solid silicon aluminum oxide powder stock to prepare the EUO structure molecular screen provided by the invention, overcome the shortcoming of prior art, it is the sial raw material that its main innovative point is to adopt the sieve and silica-sesquioxide pressed powder, at dry powder, prepared the EUO structure molecular screen in the super dense system, simplified technological process, shortened crystallization time, single-autoclave yield rate has improved 75%～200%, production cost has reduced by 50%～150%, and prepared Si-Al molecular sieve product performance are stable, the degree of crystallinity height, the silica alumina ratio scope is big, framework aluminum is evenly distributed, heat and hydrothermal stability height, and do not have the mother liquor discharging, solved difficult problems such as the wasting of resources of the prior art and environmental pollution effectively.
Embodiment
Embodiment 1
Dissolve in a certain amount of water of sodium hydroxide (96%) adding with 0.6g earlier, add C6 2.5g more successively, EUO molecular screen primary powder 0.25g, 50 ℃～85 ℃ heated and stirred are fully dissolved and dispersion, are cooled to room temperature; Then with 1.8g silicon aluminium microsphere (SiO
2/ Al
2O
3=10) and the pre-composition of the white carbon black of 3.2g add in the above-mentioned solution and stir; Put into stainless steel cauldron at last in 150 ℃～180 ℃ reactions 64 hours, get EUO structure molecular screen (SiO
2/ Al
2O
3=30) former powder;
Embodiment 2
Dissolve in sodium hydroxide (96%) the adding 4g water with 0.8g earlier, add C6 3.2g more in order, 1.0% (wt%) magnesium nitrate solution 5ml fully dissolves in 50 ℃～85 ℃ heated and stirred, is cooled to room temperature; Then the pre-composition of 1.4g silicon aluminium microsphere (with example 1) and the white carbon black of 3.6g is added in the above-mentioned solution and stir; Put into stainless steel cauldron at last in 180 ℃ of reactions 48 hours, get EUO structure molecular screen (SiO
2/ Al
2O
3=40) former powder;
Embodiment 3
Dissolve in sodium hydroxide (96%) the adding 6g water with 1.2g earlier, add C6 2.5g successively, 1.0% (wt%) iron nitrate solution 5ml, the former powder of EUO structure molecular screen of 0.125g, and even in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 1.8g silicon aluminium microsphere (with example 1) and the white carbon black of 3.2g is added in the above-mentioned solution and mix; Put into stainless steel cauldron at last in 180 ℃ of reactions 64 hours, get the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=30);
Embodiment 4
Dissolve in sodium hydroxide (96%) the adding 6g water with 1.5g earlier, add C6 3.5g successively, 1.0% (wt%) magnesium nitrate solution 5ml, the former powder of EUO structure molecular screen of 0.125g, and even in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 0.36g silicon aluminium microsphere (with example 1) and the white carbon black of 4.64g is added in the above-mentioned solution and mix; Put into stainless steel cauldron at last in 175 ℃ of reactions 48 hours, get the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=160);
Embodiment 5
Dissolve in sodium hydroxide (96%) the adding 6g water with 1.5g earlier, add C6 1.5g successively, 1.0% (wt%) potassium sulfate solution 10ml, the former powder of ZSM-5 structure molecular screen of 0.15g, and even in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 0.36g silicon aluminium microsphere (with example 1) and 4.64g macroporous silica gel is added in the above-mentioned solution and mix; Put into stainless steel cauldron at last in 170 ℃ of reactions 76 hours, get the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=160);
Embodiment 6
Dissolve in sodium hydroxide (96%) the adding 6g water with 0.8g earlier, add pentamethonium 3.2g more in order, 1.0% (wt%) magnesium nitrate solution 5ml fully dissolves in 50 ℃～85 ℃ heated and stirred, is cooled to room temperature; Then the pre-composition of 1.4g silicon aluminium microsphere (with example 1) and the white carbon black of 3.6g is added in the above-mentioned solution and stir; Put into stainless steel cauldron at last in 185 ℃ of reactions 96 hours, get the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=40);
Embodiment 7
Dissolve in the lithium hydroxide adding 6g water with 1.0g earlier, add C6 1.5g successively, 0.25g MOR molecular screen primary powder, and even in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 0.36g silicon aluminium microsphere (with example 1) and 4.64g macroporous silica gel is added in the above-mentioned solution and mix; Put into stainless steel cauldron at last in 160 ℃ of reactions 72 hours, get the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=160);
Embodiment 8
Dissolve in sodium hydroxide (96%) the adding 6g water with 0.8g earlier, add pentamethonium 1.5g successively, 1.0% (wt%) magnesium nitrate solution 10ml, the MOR molecular screen primary powder of 0.125g, and even in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 0.72g silicon aluminium microsphere (with example 1) and the white carbon black of 4.28g is added in the above-mentioned solution and mix; Put into stainless steel cauldron at last in 180 ℃ of reactions 72 hours, get the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=80).
Embodiment 9
Dissolve in the potassium hydroxide adding 4.5g water with 1.2g earlier, add the 20ml dehydrated alcohol again as solubility promoter, then add C6 5.2g in order, 1.0% (wt%) magnesium nitrate solution 2ml, fully dissolve in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 0.8g silicon aluminium microsphere (with example 1) and the white carbon black of 4.2g is added in the above-mentioned solution and stir; Put into stainless steel cauldron at last in 200 ℃ of reactions 120 hours, get EUO structure molecular screen (SiO
2/ Al
2O
3=80) former powder.
Embodiment 10
Dissolve in the water of elder generation with sodium hydroxide (96%) adding 4.0 of 0.64g, add C6 2.5g more successively, ZSM-5 molecular screen primary powder 0.25g, 50 ℃～85 ℃ heated and stirred are fully dissolved and dispersion, are cooled to room temperature; (dealuminzation is to SiO in advance with the 5g silicon aluminium microsphere then
2/ Al
2O
3=35) stir in the above-mentioned solution of adding; Put into stainless steel cauldron at last in 150 ℃～180 ℃ static reactions 48 hours, EUO structure molecular screen (SiO
2/ Al
2O
3=30) former powder;
Embodiment 11
Dissolve in the lithium hydroxide adding 16g water with 0.73g earlier, add C6 3.2g more in order, 1.0% (wt%) ammonium dihydrogen phosphate 5ml fully dissolves in 50 ℃～85 ℃ heated and stirred, is cooled to room temperature; Then the pre-composition of 1.4g silicon aluminium microsphere (with example 1) and the white carbon black of 3.6g is added in the above-mentioned solution and stir; Put into stainless steel cauldron at last in the reaction 48 hours down of 180 ℃, agitation condition, EUO structure molecular screen (SiO
2/ Al
2O
3=30) former powder;
Embodiment 12
Dissolve in sodium hydroxide (96%) the adding 6g water with 1.2g earlier, add pentamethonium 2.5g successively, 1.0% (wt%) sodium radio-phosphate,P-32 solution 10ml, the former powder of MOR structure molecular screen of 0.20g, and even in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 2.0g silicon aluminium microsphere (with example 1) and the white carbon black of 3.5g is added in the above-mentioned solution and mix; Put into stainless steel cauldron at last in 180 ℃ of static reactions 64 hours, the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=30);
Embodiment 13
Dissolve in sodium hydroxide (96%) the adding 6g water with 1.5g earlier, add C6 3.5g successively, 1.0% (wt%) magnesium nitrate solution 5ml, the former powder of EUO structure molecular screen of 0.125g, and even in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 0.38g silicon aluminium microsphere (with example 1) and the white carbon black of 4.62g is added in the above-mentioned solution and mix; Put into stainless steel cauldron at last in 175 ℃ of static reactions 48 hours, the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=160);
Embodiment 14
Dissolve in sodium hydroxide (96%) the adding 26g water with 1.5g earlier, add C6 1.5g successively, 1.0% (wt%) ammoniumsulphate soln 10ml, the former powder of EUO structure molecular screen of 0.158g, and even in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 0.36g silicon aluminium microsphere (with example 1) and 4.64g macroporous silica gel is added in the above-mentioned solution and mix; Put into stainless steel cauldron at last in 170 ℃ of stirring reactions 76 hours, the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=160);
Embodiment 15
Dissolve in sodium hydroxide (96%) the adding 25g water with 0.85g earlier, add pentamethonium 3.2g more in order, 1.0% (wt%) ammonium nitrate solution 5ml fully dissolves in 50 ℃～85 ℃ heated and stirred, is cooled to room temperature; Then the pre-composition of 1.4g silicon aluminium microsphere (with example 1) and the white carbon black of 3.6g is added in the above-mentioned solution and stir; Put into stainless steel cauldron at last in 180 ℃ of stirring reactions 96 hours, the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=40);
Embodiment 16
Dissolve in sodium hydroxide (96%) the adding 24g water with 1.5g earlier, add phenylbenzene Dimethyl Ammonium 2.5g successively, 0.25g MOR molecular screen primary powder, and even in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 0.36g silicon aluminium microsphere (with example 1) and 4.64g macroporous silica gel is added in the above-mentioned solution and mix; Put into stainless steel cauldron at last in 160 ℃ of stirring reactions 72 hours, the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=160);
Embodiment 17
Dissolve in sodium hydroxide (96%) the adding 18g water with 0.8g earlier, add C6 1.5g successively, 1.0% (wt%) magnesium nitrate solution 10ml, the MOR molecular screen primary powder of 0.125g, and even in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 0.74g silicon aluminium microsphere (with example 1) and the white carbon black of 4.8g is added in the above-mentioned solution and mix; Put into stainless steel cauldron at last in 180 ℃ of stirring reactions 72 hours, the former powder (SiO of EUO structure molecular screen
2/ Al
2O
3=80).
Embodiment 18
Dissolve in sodium hydroxide (96%) the adding 6.5g water with 1.2g earlier, add the 30ml dehydrated alcohol again as solubility promoter, then add C6 5.2g in order, 1.0% (wt%) magnesium nitrate solution 2ml, fully dissolve in 50 ℃～85 ℃ heated and stirred, be cooled to room temperature; Then the pre-composition of 0.8g silicon aluminium microsphere (with example 1) and the white carbon black of 4.2g is added in the above-mentioned solution and stir; Put into stainless steel cauldron at last in 200 ℃ of stirring reactions 120 hours, EUO structure molecular screen (SiO
2/ Al
2O
3=80) former powder.
Claims (5)
1. the method for preparing molecular sieve with EUO structure from silicon aluminum oxide powder, it is characterized in that this preparation method is earlier with alkali, template, crystal seed and nitrate promotor, or phosphoric acid salt promotor, or perchlorate promotor, or vitriol promotor is dissolved in the water, after stirring, add silicon aluminium microsphere again, or silicon aluminium microsphere and white carbon black, or silicon aluminium microsphere and the silica gel sieve and silica-sesquioxide powder after being pre-mixed evenly, stirring obtains initial gel mixture, and its mol ratio is: (0.52～20) template: (4～100) alkali: (25～400) SiO
2: Al
2O
3: (25～3000) H
2O, described alkali are the oxyhydroxide of Na, K or Li; Place closed reaction kettle crystallization under 140 ℃～220 ℃ temperature to obtain the former powder of EUO structure molecular screen crystal after 24～168 hours then.
2. the method for preparing molecular sieve with EUO structure from silicon aluminum oxide powder as claimed in claim 1 is characterized in that template is C6, pentamethonium or phenylbenzene Dimethyl Ammonium.
3. the method for preparing molecular sieve with EUO structure from silicon aluminum oxide powder as claimed in claim 1, it is characterized in that crystal seed is the molecular sieve crystal seed, it is heterogeneous or the homogeneity crystal seed, the homogeneity crystal seed is the EUO structure, heterogeneous crystal seed is Y, MOR, ZSM-5, β, L, X, MCM-22, ZSM-11, ZSM-12, ZSM-22, ZSM-35 or the ZSM-48 that structure differs from the EUO structure molecular screen, and addition accounts for 0.1%～25% (wt%) of sieve and silica-sesquioxide powder stock.
4. the method for preparing molecular sieve with EUO structure from silicon aluminum oxide powder as claimed in claim 1 is characterized in that the addition of nitrate promotor, phosphoric acid salt promotor, perchlorate promotor or vitriol promotor accounts for 0.01%～10% (wt%) of sieve and silica-sesquioxide powder stock.
5. as the method for claim 1,5 or 6 described preparing molecular sieve with EUO structure from silicon aluminum oxide powder, it is characterized in that crystal seed and promotor uses or mix use respectively separately.
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| CN109772447B (en) * | 2019-01-18 | 2022-04-12 | 太原大成环能化工技术有限公司 | Composite molecular sieve catalyst for isomerization of carbon octa-arene and preparation method thereof |
| CN110496643B (en) * | 2019-09-03 | 2022-04-12 | 太原大成环能化工技术有限公司 | Auxiliary preparation method of carbon octa-arene isomerization catalyst seed crystal |
| CN115072736B (en) * | 2021-03-12 | 2023-11-10 | 中国科学院大连化学物理研究所 | Preparation method of EUO molecular sieve |
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