CN101555021A - Method for preparing SAPO-34 molecular sieve by using crystallized residual liquid of SAPO-34 molecular sieve - Google Patents
Method for preparing SAPO-34 molecular sieve by using crystallized residual liquid of SAPO-34 molecular sieve Download PDFInfo
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- CN101555021A CN101555021A CNA2009100829150A CN200910082915A CN101555021A CN 101555021 A CN101555021 A CN 101555021A CN A2009100829150 A CNA2009100829150 A CN A2009100829150A CN 200910082915 A CN200910082915 A CN 200910082915A CN 101555021 A CN101555021 A CN 101555021A
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Abstract
The invention discloses a method for preparing an SAPO-34 molecular sieve by using crystallized residual liquid generated in the process of synthesizing the SAPO-34 molecular sieve. Namely, aluminum source, phosphorus source, silicon source, a template agent and other materials are added in the crystallized residual liquid generated in the process of synthesizing the SAPO-34 molecular sieve for preparing gel mixture and consequently obtaining the SAPO-34 molecular sieve through the processes of ageing, hydrothermal crystallization, washing, drying, roasting and the like. The method realizes the reuse of the crystallized residual liquid.
Description
Technical field
The crystallized residual liquid that the present invention relates to produce in a kind of SAPO-34 of utilization sieve synthesis procedure prepares the method for SAPO-34 molecular sieve.
Background technology
Novel silicon aluminium phosphate series molecular sieve (US 4440871, US 4499327)-SAPO-n molecular sieve that U.S. combinating carbide company (UCC) researched and developed out in 1984, be be template with the organic amine, be aluminium source, phosphorus source and silicon source with hydrated aluminum oxide, phosphoric acid, silicon sol respectively, at first obtain having the organic amine/aluminum phosphate/silicon complex body of micropore phase, remove by roasting then that template (organic amine) obtains by hydrothermal crystallization method.The SAPO-34 molecular sieve is wherein a kind of, and its similar chabazite has the three dimensional intersection duct, and the aperture is about 0.38nm, belongs to isometric system.Because it has suitable proton acidity, suitable pore passage structure, bigger specific surface area, absorption property and thermostability and hydrothermal stability etc. preferably preferably, makes it present catalytic activity and selectivity preferably in as the methanol to olefins reaction catalyzer.
Yet, in preparation SAPO-34 process, can produce a large amount of crystallized residual liquids, except containing big water gaging, also contain components such as residual template (organic ammonium), silicon source, aluminium source, phosphorus source in the crystallized residual liquid.Usually the treatment process to crystallized residual liquid is that crystallized residual liquid is carried out sewage disposal, or carries out appropriate separation and handle to extract the useful component in the crystallized residual liquid and then to carry out blowdown and handle.
How can fully effectively utilize crystallized residual liquid is a problem of current research.
Summary of the invention
At above problem, the invention provides a kind of method of utilizing the crystallized residual liquid that produces in the synthetic SAPO-34 molecular sieve process to prepare the SAPO-34 molecular sieve, promptly in the crystallized residual liquid that the SAPO-34 molecular sieve produces, add materials such as an amount of aluminium source, phosphorus source, silicon source, template and be prepared into gel mixture, through overaging, hydrothermal crystallizing, washing, drying and roasting etc., promptly obtain the SAPO-34 molecular sieve, realized utilizing effectively again of crystallized residual liquid.
The method that the present invention utilizes the crystallized residual liquid of SAPO-34 molecular sieve to prepare the SAPO-34 molecular sieve comprises the steps:
A) in the crystallized residual liquid that synthetic SAPO-34 molecular sieve produces, add an amount of aluminium source, phosphorus source, silicon source and template respectively, stirred 1-10 hour down, mix, make the template in the final blending solution: SiO at 25-80 ℃
2: Al
2O
3: P
2O
5: H
2The mol ratio of O is (0.5～10): (0.05～10): (0.2～3): (0.2～3): (20～200); Wherein, SiO
2, Al
2O
3, P
2O
5Mol ratio be respectively that corresponding silicon source, aluminium source, the conversion of phosphorus source are SiO
2, Al
2O
3, P
2O
5Mol ratio.
B) mixing solutions was worn out under 25-80 ℃ 1-24 hour.
C) crystallizing kettle of packing into of the mixing solutions after will wearing out airtightly is heated to crystallization temperature 150-250 ℃, carries out under the constant crystallization temperature then crystallization 10-120 hour; Described crystallizing kettle is that this area liner commonly used is the stainless steel crystallizing kettle of PPL.
D) mixture after the crystallization is carried out centrifugation, filtration, washing after, solid sample just obtains the former powder of SAPO-34 by heat drying after the drying.
E) be 450-650 ℃ of roasting temperature 4-8 hour with the former powder of SAPO-34 in temperature, obtain the SAPO-34 molecular sieve.
In the inventive method, in the crystallized residual liquid that the SAPO-34 molecular sieve produces, add aluminium source, phosphorus source, silicon source, template material to form gel mixture.
Wherein, described template can be preferably organic amine for this area template commonly used, the present invention includes but is not limited to tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine, aniline, Isopropylamine, di-n-propylamine or they mixture arbitrarily.
Described silicon source can be the silicon source of this area routine, and wherein the present invention preferably includes but is not limited to silicon sol, silicic acid, silicon-dioxide, white carbon black, water glass or the tetraethoxy of silica comprises 40 weight %, perhaps their mixtures arbitrarily.
Described phosphorus source can be the phosphorus source of this area routine, includes but not limited to phosphoric acid, phosphoric acid salt or phosphite or they mixture arbitrarily, and the present invention is preferably phosphoric acid, and described phosphoric acid to contain weight percent be 85% ortho-phosphoric acid.
Described aluminium source can include but not limited to pseudo-boehmite, aluminum isopropylate, aluminum oxide or aluminium hydroxide for the aluminium source of this area routine.
The present invention utilizes the crystallized residual liquid of SAPO-34 molecular sieve to prepare in the method for SAPO-34 molecular sieve, and described step a preferably adopts following operating method:
At first, the crystallized residual liquid of the preparation SAPO-34 molecular sieve gained collected is analyzed the amount of its silicon source of containing, aluminium source, phosphorus source and template.Then according to the amount of remaining silicon source, aluminium source, phosphorus source and template in the crystallized residual liquid of measuring, according to template: SiO
2: Al
2O
3: P
2O
5: H
2The mol ratio of O is (0.5～10): (0.05～10): (0.2～3): (0.2～3): the proportion relation of (20～200) calculates the amount of the silicon source, aluminium source, phosphorus source, template and the deionized water that need adding.
Wherein, analyzing the method that is adopted is the method for this area routine, can adopt direct method of analysis, also can adopt difference to subtract analytical procedure, deduct with the amount of making for the first time silicon source, aluminium source, phosphorus source and template that the SAPO-34 molecular sieve added promptly that to form the amount that the SAPO-34 framework of molecular sieve consumes definite.
It is even then described crystallized residual liquid to be inserted container for stirring.And, described aluminium source joined in the uniform crystallized residual liquid and continue stir according to the amount in the aluminium source that calculates; According to the phosphorus source amount of calculating, join in the above-mentioned solution described phosphorus source and lasting the stirring afterwards; And then, join in the above-mentioned solution silicon source and lasting the stirring according to the silicon source amount of calculating; According to the template dosage that calculates, join in the above-mentioned solution described template and lasting the stirring at last.
Compare with traditional raffinate treatment process, the present invention its advantage has been to realize that active principles such as aluminium source remaining in the crystallized residual liquid, phosphorus source, silicon source, template utilize again, is fit to large-scale industrial production; Save water resources, can realize the sewage near zero release of catalyst plant; The operation of appropriate separation and then the corresponding Catalyst Production cost that reduced are handled or carried out to the industrial sewage that has reduced traditional crystallized residual liquid; The prepared indexs such as catalyst activity, selectivity, thermostability and hydrothermal stability that go out all satisfy industrial service requirements.
Description of drawings
Fig. 1 is the process flow sheet of embodiment 1;
Fig. 2 is the process flow sheet of embodiment 2-4;
Fig. 3 is X-ray diffraction (XRD) figure of the SAPO-34 molecular sieve of embodiment 1-4 preparation.
Embodiment
Further specify the method for utilizing the crystallized residual liquid that produces in the synthetic SAPO-34 molecular sieve process to prepare the SAPO-34 molecular sieve below by embodiment, but therefore the present invention is not subjected to any restriction.
Embodiment 1:
Respectively 85% phosphoric acid of 41g, the pseudo-boehmite of 30g, the triethylamine of 55g, the deionized water of 167g, 40% silicon sol of 16g are prepared according to operation shown in Figure 1, wherein aging temperature is 25 ℃, and digestion time is 6 hours; Crystallization temperature is 200 ℃, and crystallization time is 48 hours; Maturing temperature is 550 ℃, and roasting time is 7 hours, gets product A.
Embodiment 2:
Get crystallized residual liquid 85g among the embodiment 1, analyze the amount of its silicon source of containing, aluminium source, phosphorus source, template and deionized water, it is even that crystallized residual liquid is inserted container for stirring.With the pseudo-boehmite of 4g, 85% phosphoric acid of 2g, 40% silicon sol of 5g, the triethylamine of 10g, be prepared according to operation shown in Figure 2 respectively, wherein aging temperature is 25 ℃, and digestion time is 6 hours; Crystallization temperature is 200 ℃, and crystallization time is 48 hours; Maturing temperature is 550 ℃, and roasting time is 7 hours, gets product B.
Embodiment 3:
Get crystallized residual liquid 85g among the embodiment 1, it is even that crystallized residual liquid is inserted container for stirring.With the pseudo-boehmite of 2.5g, 85% phosphoric acid of 1.0g, 40% silicon sol of 5.0g, the triethylamine of 7.5g, be prepared according to operation shown in Figure 2 respectively, wherein aging temperature is 25 ℃, and digestion time is 4 hours; Crystallization temperature is 210 ℃, and crystallization time is 44 hours; Maturing temperature is 550 ℃, and roasting time is 6 hours, gets products C.
Embodiment 4:
Get crystallized residual liquid 85g among the embodiment 1, it is even that crystallized residual liquid is inserted container for stirring.With the pseudo-boehmite of 6g, 85% phosphoric acid of 3g, 40% silicon sol of 5g, the tetraethyl ammonium hydroxide of 7.5g, be prepared according to operation shown in Figure 2 respectively, wherein aging temperature is 25 ℃, and digestion time is 6 hours; Crystallization temperature is 200 ℃, and crystallization time is 72 hours; Maturing temperature is 500 ℃, and roasting time is 7 hours, gets product D.
Claims (6)
1, a kind of crystallized residual liquid of the SAPO-34 of utilization molecular sieve prepares the method for SAPO-34 molecular sieve, it is characterized in that, described method comprises the steps:
A) in the crystallized residual liquid that synthetic SAPO-34 molecular sieve produces, add aluminium source, phosphorus source, silicon source and template respectively, stirred 1-10 hour down, mix, make the template in the final blending solution: SiO at 25-80 ℃
2: Al
2O
3: P
2O
5: H
2The mol ratio of O is (0.5～10): (0.05～10): (0.2～3): (0.2～3): (20～200);
B) mixing solutions was worn out under 25-80 ℃ 1-24 hour;
C) crystallizing kettle of packing into of the mixing solutions after will wearing out airtightly is heated to crystallization temperature 150-250 ℃, carries out under the constant crystallization temperature then crystallization 10-120 hour;
D) mixture after the crystallization is carried out centrifugation, filtration, washing after, solid sample just obtains the former powder of SAPO-34 by heat drying after the drying;
E) be 450-650 ℃ of roasting temperature 4-8 hour with the former powder of SAPO-34 in temperature, obtain the SAPO-34 molecular sieve.
2, method according to claim 1 is characterized in that, adds aluminium source, phosphorus source, silicon source and template in the described step a) to form gel mixture in the crystallized residual liquid of SAPO-34 molecular sieve.
3, method according to claim 2 is characterized in that, described template is tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine, aniline, Isopropylamine, di-n-propylamine or they mixture arbitrarily.
4, method according to claim 2 is characterized in that, described silicon source is the silicon sol, silicic acid, silicon-dioxide, white carbon black, water glass, tetraethoxy of 40 weight % or they mixture arbitrarily.
5, method according to claim 2 is characterized in that, described phosphorus source is phosphoric acid, phosphoric acid salt or phosphite or they mixture arbitrarily; Be preferably phosphoric acid, and described phosphoric acid to contain weight percent be 85% ortho-phosphoric acid.
6, method according to claim 2 is characterized in that, described aluminium source is pseudo-boehmite, aluminum isopropylate, aluminum oxide or aluminium hydroxide.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898768A (en) * | 2010-06-24 | 2010-12-01 | 神华集团有限责任公司 | Titanium modified SAPO-34 molecular sieve and preparation method and application thereof |
| CN101993095A (en) * | 2010-10-28 | 2011-03-30 | 神华集团有限责任公司 | Method for preparing SAPO-5 molecular sieve and product obtained through same |
| CN105126903A (en) * | 2015-07-29 | 2015-12-09 | 太原大成环能化工技术有限公司 | Recycle method of catalyst fine powder obtained by preparation of olefin from waste and old methanol |
| CN105417555A (en) * | 2016-01-12 | 2016-03-23 | 神华集团有限责任公司 | SAPO-34 molecular sieve raw powder and synthetic method thereof |
| CN105668587A (en) * | 2016-02-23 | 2016-06-15 | 山东齐鲁华信高科有限公司 | Recycling method for SAPO-34 molecular-sieve synthesized mother liquid |
| CN108557838A (en) * | 2018-06-25 | 2018-09-21 | 陕西延长石油（集团）有限责任公司 | A kind of preparation method of aluminium silicophosphate molecular sieve |
| CN109225318A (en) * | 2018-07-30 | 2019-01-18 | 中国华能集团有限公司 | A kind of multiple stage circulation of methanol-to-olefin catalyst synthetic wastewater utilizes method |
| CN109305690A (en) * | 2018-10-17 | 2019-02-05 | 山东齐鲁华信高科有限公司 | Utilize the green synthesis method of recycling template and crystallization mother liquor synthesizing P-Al si molecular sieves |
| CN112010327A (en) * | 2020-09-11 | 2020-12-01 | 上海第二工业大学 | Method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material |
-
2009
- 2009-04-22 CN CNA2009100829150A patent/CN101555021A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898768A (en) * | 2010-06-24 | 2010-12-01 | 神华集团有限责任公司 | Titanium modified SAPO-34 molecular sieve and preparation method and application thereof |
| CN101898768B (en) * | 2010-06-24 | 2012-02-22 | 神华集团有限责任公司 | Titanium modified SAPO-34 molecular sieve and preparation method and application thereof |
| CN101993095A (en) * | 2010-10-28 | 2011-03-30 | 神华集团有限责任公司 | Method for preparing SAPO-5 molecular sieve and product obtained through same |
| CN101993095B (en) * | 2010-10-28 | 2012-06-27 | 神华集团有限责任公司 | Method for preparing SAPO-5 molecular sieve and product obtained through same |
| CN105126903A (en) * | 2015-07-29 | 2015-12-09 | 太原大成环能化工技术有限公司 | Recycle method of catalyst fine powder obtained by preparation of olefin from waste and old methanol |
| CN105417555A (en) * | 2016-01-12 | 2016-03-23 | 神华集团有限责任公司 | SAPO-34 molecular sieve raw powder and synthetic method thereof |
| CN105668587A (en) * | 2016-02-23 | 2016-06-15 | 山东齐鲁华信高科有限公司 | Recycling method for SAPO-34 molecular-sieve synthesized mother liquid |
| CN105668587B (en) * | 2016-02-23 | 2018-06-22 | 山东齐鲁华信高科有限公司 | The circulation utilization method of SAPO-34 molecular sieve synthesis mother liquids |
| CN108557838A (en) * | 2018-06-25 | 2018-09-21 | 陕西延长石油（集团）有限责任公司 | A kind of preparation method of aluminium silicophosphate molecular sieve |
| CN108557838B (en) * | 2018-06-25 | 2021-05-07 | 陕西延长石油（集团）有限责任公司 | Preparation method of silicon-phosphorus-aluminum molecular sieve |
| CN109225318A (en) * | 2018-07-30 | 2019-01-18 | 中国华能集团有限公司 | A kind of multiple stage circulation of methanol-to-olefin catalyst synthetic wastewater utilizes method |
| CN109225318B (en) * | 2018-07-30 | 2022-01-18 | 中国华能集团有限公司 | Multistage recycling method for methanol-to-olefin catalyst synthesis wastewater |
| CN109305690A (en) * | 2018-10-17 | 2019-02-05 | 山东齐鲁华信高科有限公司 | Utilize the green synthesis method of recycling template and crystallization mother liquor synthesizing P-Al si molecular sieves |
| CN112010327A (en) * | 2020-09-11 | 2020-12-01 | 上海第二工业大学 | Method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material |
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Application publication date: 20091014 |