CN103172083B - Comprehensive utilization method of silicon-aluminum-phosphorus molecular sieve synthesis liquid - Google Patents

Comprehensive utilization method of silicon-aluminum-phosphorus molecular sieve synthesis liquid Download PDF

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CN103172083B
CN103172083B CN201110440343.6A CN201110440343A CN103172083B CN 103172083 B CN103172083 B CN 103172083B CN 201110440343 A CN201110440343 A CN 201110440343A CN 103172083 B CN103172083 B CN 103172083B
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吴宗斌
王凤
韩光荣
相海青
邓忠华
李丽
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CHIA TAI ENERGY MATERIALS (DALIAN) Co Ltd
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Abstract

The invention relates to a method for preparing SAPO-34, SAPO-11, SAPO-35, SAPO-5 and SAPO-56 molecular sieves from a liquid (S liquid) generated in a synthesis process of silicon-phosphorus-aluminum molecular sieves synthesized from a silicon source, an aluminum source, a phosphorus source and a template by hydrothermal crystallization. The method comprises the following steps: proportionally and evenly mixing S powder or S liquid with small amounts of silicon source, aluminum source, phosphorus source, template and deionized water used as raw materials, crystallizing at 150-250 DEG C for 12-48 hours to obtain an SAPO molecular sieve liquid, washing and drying to obtain the SAPO molecular sieve raw powder. Compared with the prior art, the invention uses the liquid containing the aluminum source, silicon source and phosphorus source, which is generated in the SAPO molecular sieve synthesis process, as the raw material to reduce the addition amounts of the raw material aluminum source, silicon source and phosphorus source in synthesis, thereby implementing reutilization of the molecular sieve liquid, lowering the production cost and saving the cost for environment-friendly treatment of the liquid.

Description

A kind of method of sial phosphorus molecular sieve synthetic fluid comprehensive utilization
Technical field
Patent relates to during sial phosphorus molecular sieve that a kind of utilization synthesized by silicon source, aluminium source, phosphorus source and template hydrothermal crystallizing synthesizes the method that the liquid produced prepares SAPO molecular sieve analog.
Background technology
LOK in 1984 etc. are at AlPO 4si element is introduced in Series Molecules sieve, develop a series of silicoaluminophosphamolecular molecular sieves (SAPO-n, n is model), the skeleton of this microporous type molecular sieve is electronegativity, there is tradable medium Bronsted acidity and positively charged ion, be widely used in petrochemical industry, especially the commercial applications effect of SAPO-11 and SAPO-34 is paid close attention to widely.
A part of liquid can be produced in production SAPO molecular sieve process, detect by analysis, containing components such as silicon, aluminium, phosphorus, sulphur, sodium, chlorine, iron, calcium, nickel elements in liquid.Main component is silicon oxide, aluminum oxide and Vanadium Pentoxide in FLAKES, massfraction is 0.15% ~ 1.20%, 1% ~ 8.50%, 1.00% ~ 12.00%, solid content is 2.25.00% ~ 21.7.00%, usually after biochemistry, the process of physics and chemistry method being carried out to this liquid, fall as discharge of wastewater, cause the waste of resource like this, also increase production cost, so recycle it, there is very large economy and social value.
Summary of the invention
The object of the invention is to reclaim the method fully utilizing and prepared SAPO molecular sieve analog by the liquid produced in silicon source, aluminium source, phosphorus source and template hydrothermal crystallizing synthesis SAPO molecular sieve process.S liquid directly can use synthesis of molecular sieve; Or through making S powder, or by after the roasting of S powder for the synthesis of molecular sieve.Namely with S liquid or S powder and a small amount of silicon source, aluminium source, phosphorus source, template does and deionized water is raw material, mix according to a certain percentage, at 150 ~ 250 DEG C, crystallization obtains SAPO molecular sieve analog liquid for 12 ~ 48 hours, more after filtration, washing and drying obtain the former powder of SAPO molecular sieve analog.
The present invention is the method that the liquid produced in a kind of SAPO of utilization Zeolite synthesis prepares SAPO molecular sieve analog.The concrete technology of the method is as follows:
(1) measure the solid content of S liquid, measure silicon oxide, aluminum oxide and the phosphorus pentoxide content in S liquid, the solid matter content in S powder, and calculate silicon oxide, aluminum oxide and phosphorus pentoxide content in S powder.Proportioning raw materials according to synthesis SAPO molecular sieve analog: mol ratio: (0.05-2) SiO 2: (0.2-3) Al 2o 3: (0.2-3) P 2o 5: (20-100) H 2o: (0.5-10) template, in S liquid, aluminum oxide serves as the aluminium source of 1% ~ 40%, and in S powder, aluminum oxide serves as the aluminium source of 1% ~ 100%, calculate need to add silicon source, aluminium source, phosphorus source, the amount of deionized water and the template of interpolation amount;
(2) directly use S liquid: according to the proportioning in step 1, take a certain amount of S liquid, template, deionized water and the silicon source added, aluminium source, phosphorus source, by each mixing of materials, fully stir, mix;
(3) utilize the S powder made of S liquid drying: according to the proportioning in step 1, take a certain amount of S powder, template, deionized water and the silicon source added, aluminium source, phosphorus source, by each mixing of materials, fully stir, mix;
(4) mixed solution of step 2 or 3 is moved in reactor, agingly under whipped state is no less than 6 hours, crystallization 12-48 hour at 150-250 DEG C;
(5) reaction terminates the cooling of rear reactor by material releasing, and molecular sieve liquid carries out washing and drying, obtains the former powder of SAPO molecular sieve analog;
The once washing liquid that described S liquid produces when being and producing SAPO-34, SAPO-11, SAPO-35, SAPO-5, SAPO-56;
The phosphorus source that described S liquid and S powder synthesis SAPO molecular sieve analog are added can adopt phosphoric acid, aluminum phosphate, phosphite etc. (when using aluminum phosphate for phosphorus source, wherein aluminium serves as a part of aluminium source, according to alumina content, if need add, then add other aluminium sources);
The silicon source that described S liquid and S powder synthesis SAPO molecular sieve analog are added can adopt silicon sol, silicic acid, tetraethoxy, positive silicic acid propyl ester, active silica (place of production: Jinyang chemical industry) etc.;
The aluminium source that described S liquid and S powder synthesis SAPO molecular sieve analog are added can adopt pseudo-boehmite, γ-Al 2o 3, δ-Al 2o 3, ρ-Al 2o 3, Al (OH) 3, aluminum phosphate, aluminum isopropylate, AlOOH (use aluminum phosphate for aluminium source time, wherein phosphorus is phosphorus source, according to phosphorus oxide content, if need add, then adds other phosphorus sources);
Described template can adopt mixture, the N of morphine beautiful jade, tetraethyl-aqua ammonia (TEAOH), triethylamine, diethylamine, diethylamine and triethylamine, N, N ', the mixture etc. of N '-tetramethyl--1,6-hexanediamine (TMHD), vulkacit H, di-n-propylamine, di-n-propylamine and Diisopropylamine;
Adopt conventional prior art to use the S liquid produced during the SAPO Zeolite synthesis synthesized by silicon source, aluminium source, phosphorus source and template crystallization or the S powder be dried to, may be used for synthesizing different SAPO molecular sieve, there is versatility.
The maturing temperature 350 ~ 650 DEG C of described roasting S powder.
The invention has the advantages that and achieve by silicon source, aluminium source, the recycling of the valuable element of the liquid that phosphorus source and template crystallization synthesis SAPO molecular sieve produce, evaluate via fixed bed evaluating apparatus, it is good that the S powder utilizing spraying dry to make or S powder use the molecular sieve performance more directly utilizing S liquid to synthesize in aluminium phosphate molecular sieve synthesis after roasting, the olefine selective that the methanol to olefins reaction of the SAPO-34 molecular sieve of the S powder synthesis of S powder and roasting comparatively applied by the SAPO-34 molecular sieve that direct application SAPO-34 Zeolite synthesis produces the synthesis of S liquid is low, the SAPO-34 molecular sieve of the S powder synthesis of application S powder and roasting reaches productive capacity requirement substantially.The method reduces the add-on of part material in sial phosphorus molecular sieve building-up process, also save water resources simultaneously, achieve the cycling and reutilization of molecular sieve liquid and the zero release of industrial sewage, reduce the cost of sewage disposal.
Accompanying drawing explanation
The product XRD analysis figure of Fig. 1 embodiment.
Embodiment
Below by specific embodiment, the method utilizing the liquid produced by silicon source, aluminium source, phosphorus source, template and deionized water hydrothermal crystallizing synthesis SAPO molecular sieve process to prepare SAPO molecular sieve analog is further described, but the present invention is not therefore subject to any restriction.
Embodiment 1
Under agitation condition, in container, add 1500g deionized water, 500g pseudo-boehmite (Al successively 2o 3massfraction 65%), 1142g phosphoric acid (H 3pO 4massfraction 85%), then add 1500g deionized water, 207g silicon sol (SiO 2massfraction 37%), stir, finally add the mixed solution of 388g diamines and 596g triethylamine.After stirring, mixing solutions is moved on in reactor, loadings 70%, aging 7 hours at 120 DEG C, crystallization 15 hours at 200 DEG C, through filtration, washing, drying, obtaining product note SAPO-34-1, X-ray powder diffraction pattern and see SAPO-34-1 in Fig. 1, is SAPO-34 molecular sieve through MDIJade5.0 software analysis.Through fixed bed activity rating, (methyl alcohol air speed is 8h to molecular sieve for temperature of reaction 400 DEG C, reaction pressure position normal pressure -1), life-span and olefine selective are in table 1.
Embodiment 2
The S liquid produced in Example 1, measures its sial phosphorus content (SiO 2content 0.35wt%, Al 2o 3content 3.87wt%, P 2o 5content 7.77wt%), and measure its butt, the amount in the aluminium source going out to need to add according to ore mix constitution, silicon source, phosphorus source.Respectively by the S liquid in 3000g example 1,1000g water, 500g pseudo-boehmite (Al 2o 3massfraction 65%), 1200g phosphoric acid (H 3pO 4massfraction 85%), 283g silicon sol (SiO 2massfraction 37%), the diethylamine of 450g and the mixed solution of 692g triethylamine put into autoclave, loadings 70%, be uniformly mixed, 100 DEG C aging 7 hours, 200 DEG C of crystallization 18 hours, obtain product note SAPO-34-2, X-ray powder diffraction pattern is shown in SAPO-34-2 in Fig. 1, is SAPO-34 molecular sieve through MDI Jade5.0 software analysis, and molecular sieve is through fixed bed activity rating (temperature of reaction 400 DEG C, reaction pressure position normal pressure, methyl alcohol air speed is 8h -1), life-span and olefine selective are in table 1.
Embodiment 3
The S liquid (filtrate after filtration) produced in Example 1, analyzes its sial phosphorus content (SiO 2content 0.35wt%, Al 2o 3content 3.87wt%, P 2o 5content 7.77wt%).S powder is made in the drying of S liquid, and determines the butt of micro mist.According to ore mix constitution go out need add aluminium source, silicon source, phosphorus source amount.Respectively by the phosphoric acid (H of 3000g deionized water, 1950gS powder, 20g 3pO 4massfraction 85%), the silicon sol (SiO of 177g 37% 2massfraction 37%), the diethylamine of 420g and 645g triethylamine liquid puts into autoclave, stir, 80 DEG C aging 10 hours, 200 DEG C of crystallization 20 hours, obtain product S APO-34-3, X-ray powder diffraction pattern is shown in SAPO-34-3 in Fig. 1, is SAPO-34 molecular sieve through MDI Jade5.0 software analysis.Through fixed bed activity rating, (methyl alcohol air speed is 8h to molecular sieve for temperature of reaction 400 DEG C, reaction pressure position normal pressure -1), life-span and olefine selective are in table 1.
Embodiment 4
S liquid in Example in 1, measures its sial phosphorus content (SiO 2content 0.35wt%, Al 2o 3content 3.87wt%, P 2o 5content 7.77wt%), and dry S liquid becomes S powder, then after 600 DEG C of roasting 1h.According to ore mix constitution go out need add aluminium source, silicon source, phosphorus source amount.Respectively by the S powder after 3600g deionized water, 1000g roasting, 192g phosphoric acid (H 3pO 4massfraction 85%), the silicon sol (SiO of 224g 37% 2massfraction 37%), 140g pseudo-boehmite (Al 2o 3massfraction 65%) diethylamine of 430g and 610g triethylamine liquid puts into autoclave, stir, 80 DEG C aging 10 hours, 200 DEG C of crystallization 20 hours, obtain product and be designated as SAPO-34-4, X-ray powder diffraction pattern is shown in SAPO-34-4 in Fig. 1, is SAPO-34 molecular sieve through MDI Jade5.0 software analysis.Through fixed bed activity rating, (methyl alcohol air speed is 8h to molecular sieve for temperature of reaction 400 DEG C, reaction pressure position normal pressure -1), life-span and olefine selective are in table 1.
Embodiment 5
In Example 1 S liquid, measure its sial phosphorus content (SiO 2content 0.35wt%, Al 2o 3content 3.87wt%, P 2o 5content 7.77wt%), according to proportioning calculate need add aluminium source, silicon source, phosphorus source amount.By S liquid 41g and 12g phosphoric acid (H 3pO 4massfraction 85%) in 35 DEG C of water-baths, be mixed to form colloidal sol; Add the aluminum isopropylate of 22g 98% and the isopropanol mixture of 38g, stir 60min, add the positive silicic acid propyl ester of 4.5g 97%, continue to stir 60min, add the di-n-propylamine of 7.9g 99% again, then the mixture stirred is loaded 150mL with in teflon-lined stainless steel cauldron, crystallization 20 hours at 180 DEG C, obtain the molecular sieve liquid of SAPO-11, product note SAPO-11-1 is obtained after distillation, washing, drying, X-ray powder diffraction pattern is shown in SAPO-11-1 in Fig. 1, is SAPO-11 molecular sieve through MDI Jade5.0 software analysis.
Embodiment 6
S liquid in Example 1, measures its sial phosphorus content (SiO 2content 0.35wt%, Al 2o 3content 3.87wt%, P 2o 5content 7.77wt%), according to proportioning calculate need add aluminium source, silicon source, phosphorus source.Get 70gS liquid, add 25.95gAlOOH, stir, add 8.86g phosphoric acid (H 3pO 4massfraction 85%), after stirring 30min, add 10.34g tetraethoxy, 8.86g triethylamine, fully stirs into gel, move into 150mL with in teflon-lined stainless steel cauldron, crystallization 48 hours at 200 DEG C, product, after separation, washing, drying, obtains product note SAPO-5-1, X-ray powder diffraction pattern is shown in SAPO-5-1 in Fig. 1, is SAPO-5 molecular sieve through MDI Jade5.0 software analysis.
Embodiment 7
S liquid in Example 1, measures its sial phosphorus content (SiO 2content 0.35wt%, Al 2o 3content 3.87wt%, P 2o 5content 7.77wt%), according to proportioning calculate need add aluminium source, silicon source, phosphorus source.Get 70gS liquid, add 8.48g phosphoric acid (H 3pO 4massfraction 85%) stir, add 8.03g pseudo-boehmite (Al after stirring 10min 2o 3massfraction 65%), continue to stir 60min, then add 22.28g silicon sol (SiO 2massfraction 37%), continue to stir 20min, add 10.42g vulkacit H again, be moved into in teflon-lined stainless steel autoclave after being mixed into gel, crystallization 24 hours at 200 DEG C, product after filtration, washing, obtain product note SAPO-35-1, X-ray powder diffraction pattern after drying and see SAPO-35-1 in Fig. 1, be SAPO-35 molecular sieve through MDI Jade5.0 software analysis.
Embodiment 8
By 523g pseudo-boehmite (Al 2o 3massfraction 65%) join 768g phosphoric acid (H 3pO 4massfraction 85%) in, add deionized water 3000g, stir, then add 270g silicon sol (SiO 2massfraction 37%), di-n-propylamine 404g, becomes gel after stirring 60min, move in autoclave, loadings 80%, crystallization 20h at 180 DEG C, obtain SAPO-11 molecular sieve liquid, product, after separation, washing, drying, obtains SAPO-11 molecular screen primary powder.
Embodiment 9
The S liquid of Example 7, measures the content (SiO of its sial phosphorus 2content 0.25wt%, Al 2o 3content 2.50wt%, P 2o 5content 8.81wt%), according to ore mix constitution go out need add aluminium source, silicon source, phosphorus source amount.Get 75g S liquid, add 8.45g pseudo-boehmite (Al 2o 3massfraction 65%), 18.66g phosphoric acid (H 3pO 4massfraction 85%), 3.90g silicon sol (SiO 2massfraction 37%) and 13.4g triethylamine and 8.74g diethylamine mix, 100 DEG C are aging 7 hours, and crystallization 20 hours at 200 DEG C, obtains SAPO-34 molecular sieve liquid, product through being separated, washing, obtain SAPO-34 molecular screen primary powder after drying.
Embodiment 10
S liquid in Example 8, measures sial phosphorus content (SiO 2content 0.25wt%, Al 2o 3content 2.50wt%, P 2o 5content 8.81wt%), according to ratio of components, calculate need add aluminium source, silicon source, phosphorus source amount.Get S liquid 70g, add 7.98g pseudo-boehmite (Al 2o 3massfraction 65%), 8.42g phosphoric acid (H 3pO 4massfraction 85%), stir, then add 5g silicon sol (SiO 2massfraction 37%), 8.47g di-n-propylamine, becomes gel after stirring 60min, move into 150mL with in teflon-lined autoclave, crystallization 20 hours at 180 DEG C, obtains SAPO-11 molecular sieve liquid, and product obtains SAPO-11 molecular screen primary powder after separation, washing, drying.
Embodiment 11
S liquid in Example 8, measures its sial phosphorus content (SiO 2content 0.25wt%, Al 2o 3content 2.50wt%, P 2o 5content 8.81wt%), according to proportioning calculate need add aluminium source, silicon source, phosphorus source.Get 70gS liquid, add 25.09gAlOOH, stir, add 11.70g phosphoric acid (H 3pO 4massfraction 85%), after stirring 30min, add 10.05g tetraethoxy 10.34g, triethylamine 8.82g, fully stir into gel, move into 150mL with in teflon-lined stainless steel cauldron, crystallization 48 hours at 200 DEG C, product, after separation, washing, drying, obtains the former powder of SAPO-5.
Embodiment 12
S liquid in Example 8, measures its sial phosphorus content (SiO 2content 0.25wt%, Al 2o 3content 2.50wt%, P 2o 5content 8.81wt%), according to proportioning calculate need add aluminium source, silicon source, phosphorus source.Get 70gS liquid, add 7.76g phosphoric acid (H 3pO 4massfraction 85%) stir, add 7.68g hydrated aluminum oxide (Al after stirring 10min 2o 3massfraction 65%), continue to stir 60min, then add 22.00g silicon sol (SiO 2massfraction 37%), continue to stir 20min, then add 10.37g vulkacit H, be moved into in teflon-lined stainless steel autoclave after being mixed into gel, crystallization 24 hours at 200 DEG C, product after filtration, washing, obtain SAPO-35 molecular screen primary powder after drying.
Compared with prior art, the liquid containing aluminium source, silicon source, phosphorus source that the present invention produces in utilizing SAPO molecular sieve analog to synthesize is as raw material, decrease the add-on in synthesis Raw aluminium source, silicon source, phosphorus source, not only achieve molecular sieve liquid recycling, and reduce production cost, also save the expense of this liquid of environmental protection treatment simultaneously.
Table 1 embodiment 1-4 product evaluation result

Claims (9)

1. a method for sial phosphorus molecular sieve synthetic fluid comprehensive utilization, is characterized in that:
In synthesizing Si-Al phosphorus molecular sieve process, the liquid that system produces after removing zeolite product, i.e. S liquid, S liquid can be directly used in synthesis SAPO molecular sieve, or micro mist is made in the drying of S liquid, i.e. S powder, or the S powder of roasting will be obtained after the roasting of S powder, the S powder of S powder or roasting is used further to synthesis SAPO molecular sieve, and process is as follows:
1) measure the solid content of S liquid, with oxide basis, measure silicon oxide, aluminum oxide and the phosphorus pentoxide content in S liquid; Solid matter content in the S powder of S powder or roasting, with oxide basis, and calculates silicon oxide, aluminum oxide and phosphorus pentoxide content in the S powder of S powder or roasting;
With oxide basis, the feed molar proportioning of synthesis SAPO molecular sieve analog is: (0.05-2) SiO 2: (0.2-3) Al 2o 3: (0.2-3) P 2o 5: (20-100) H 2o: (0.5-10) template;
Serve as the aluminium source of 1% ~ 40% with aluminum oxide in S liquid, or serve as the aluminium source of 1% ~ 100% with aluminum oxide in the S powder of S powder or roasting, calculate need to add silicon source, aluminium source, phosphorus source, the amount of deionized water and the template of interpolation amount;
2) directly use S liquid: according to step 1) in proportioning, take S liquid, template, deionized water and the silicon source added, aluminium source, phosphorus source, by each mixing of materials, fully stir, mix;
Or, utilize the S powder of S powder or roasting: according to step 1) in proportioning, take S powder, template, deionized water and the silicon source added, aluminium source, phosphorus source, by each mixing of materials, fully stir, mix;
3) mixed solution that step 2 obtains is moved in reactor, agingly under whipped state is no less than 6 hours, crystallization 12-48 hour at 150-250 DEG C;
4) reaction terminates the cooling of rear reactor by material releasing, and molecular sieve liquid carries out washing and drying, obtains the former powder of SAPO molecular sieve analog.
2. method according to claim 1, is characterized in that: S liquid is one or more after system removes zeolite product when producing SAPO-34, SAPO-11, SAPO-35, SAPO-5 or SAPO-56 molecular sieve in the liquid that produces; S powder is prepared from by the drying of S liquid, will obtain the S powder of roasting, the temperature of roasting S powder 350 ~ 650 DEG C, roasting time 0.5 ~ 10h after the roasting of S powder;
The S powder of S liquid, S powder or roasting all can be used for producing SAPO-34, SAPO-11, SAPO-35, SAPO-5 or SAPO-56 molecular sieve.
3. method according to claim 1, is characterized in that: the phosphorus source that the S powder synthesis SAPO molecular sieve analog of S liquid, S powder and roasting is added adopts the one in phosphoric acid, aluminum phosphate, phosphite;
When using aluminum phosphate for phosphorus source, wherein aluminium serves as a part of aluminium source, according to alumina content, if need add, then adds other aluminium sources.
4. the method according to claim 1 or 3, is characterized in that: the silicon source that the S powder synthesis SAPO molecular sieve analog of S liquid, S powder and roasting is added adopts the one in silicon sol, silicic acid, tetraethoxy, positive silicic acid propyl ester, commodity active silica.
5. the method according to claim 1 or 3, is characterized in that: the aluminium source that the S powder synthesis SAPO molecular sieve analog of S liquid, S powder and roasting is added can adopt pseudo-boehmite, γ-Al 2o 3, δ-Al 2o 3, ρ-Al 2o 3, Al (OH) 3, aluminum phosphate, aluminum isopropylate, one in AlOOH;
When using aluminum phosphate for aluminium source, wherein phosphorus is phosphorus source, according to phosphorus oxide content, if need add, then adds other phosphorus sources.
6. method according to claim 1, it is characterized in that: described template can adopt mixture, the N of morphine beautiful jade, tetraethyl-aqua ammonia (TEAOH), triethylamine, diethylamine, diethylamine and triethylamine, N, N ', one in the mixture of N '-tetramethyl--1,6-hexanediamine (TMHD), vulkacit H, di-n-propylamine, di-n-propylamine and Diisopropylamine.
7. method according to claim 1 and 2, is characterized in that:
Adopt conventional prior art to use the S liquid produced during the SAPO Zeolite synthesis synthesized by silicon source, aluminium source, phosphorus source and template crystallization or the S powder be dried to, may be used for synthesizing different SAPO molecular sieve, there is versatility.
8. preparation method according to claim 2, is characterized in that:
S liquid is utilize the liquid produced in the SAPO molecular sieve process of being synthesized by silicon source, aluminium source, phosphorus source and template hydrothermal crystallizing.
9. the method according to claim 1 or 8, it is characterized in that: with oxide basis, S liquid main component is silicon oxide, aluminum oxide and Vanadium Pentoxide in FLAKES, and massfraction is 0.15% ~ 1.20%, 1% ~ 8.50%, 1.00% ~ 12.00%, and solid content is 2.25% ~ 21.7%.
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CN106082266B (en) * 2016-05-31 2018-05-15 南开大学 Two kinds of microporous crystals coordinate the method that conversion prepares SAPO-34 molecular sieves
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CN111099606B (en) * 2018-10-25 2021-11-30 中国石油化工股份有限公司 Nano-rod shaped AFI type molecular sieve and preparation method thereof
CN110152724A (en) * 2019-05-22 2019-08-23 陕西煤化工技术工程中心有限公司 A kind of reuse method of aluminium silicophosphate molecular sieve catalyst
CN112591763B (en) * 2020-12-23 2022-10-04 正大能源材料(大连)有限公司 Preparation method for directly synthesizing Y-type molecular sieve with phosphorus-containing framework by utilizing SAPO-34 molecular sieve mother liquor

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