CN104340990A - Method for synthesizing zeolite Y - Google Patents
Method for synthesizing zeolite Y Download PDFInfo
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- CN104340990A CN104340990A CN201310328800.1A CN201310328800A CN104340990A CN 104340990 A CN104340990 A CN 104340990A CN 201310328800 A CN201310328800 A CN 201310328800A CN 104340990 A CN104340990 A CN 104340990A
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- China
- Prior art keywords
- kaolin
- mother liquor
- acid
- zeolite
- metakaolin
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
Abstract
The invention relates to a method for synthesizing zeolite Y. According to the invention, zeolite is subjected to roasting dehydration at a temperature of 500-860 DEG C, such that zeolite is converted into metakaolin; the metakaolin is crushed, and is prepared into metakaolin powder with particle size lower than 230 micrometers; the metakaolin powder is prepared into a reaction raw material mixture with a recycled mother liquor, a directing agent, a sodium hydroxide solution, water and optionally water glass, according to a molar ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-450)H2O; the reaction raw material mixture is crystallized under stirring under a temperature of 80-100 DEG C; and filtering and drying are carried out. The method is characterized in that the recycled mother liquor is from a gel-method synthesis process of zeolite Y. In the recycled mother liquor, the concentration of SiO2 is no higher than 150g/L, the concentration of Na2O is no higher than 70g/L, and the concentration of SO4<2-> is no higher than 100g/L. According to the zeolite Y synthesizing method provided by the invention, silicon and sodium in the mother liquor of zeolite Y gel-method synthesis is effectively utilized, such that the discharge of sulfate-containing pollutants in the mother liquor is reduced. The gel-method synthesis mother liquor can be utilized without pretreatment.
Description
Technical field
The present invention relates to a kind of synthetic method of y-type zeolite, the present invention relates to the method utilizing y-type zeolite synthesis mother liquid to synthesize y-type zeolite furtherly.
Background technology
Y-type zeolite is the maximum molecular sieve of petrochemical complex application quantity, and the yearly capacity of China's y-type zeolite has reached more than 50,000 tons, and the gesture in growth.At present, the producing and manufacturing technique of y-type zeolite has gel directing agent method (Grace company of the U.S., USP3,639,099 and USP4,166,099), kaolin microsphere in-situ crystallization method (BASF AG, USP4,493,902) and kaolin former powder in-situ crystallization method (China Petrochemical Industry, CN15333982A).Gel method adopts NaOH, sodium aluminate, Starso (water glass), Tai-Ace S 150 etc. to be raw material, adds the directed agents of 5-10% in addition, and hydrothermal crystallization method synthesis obtains molecular sieve.Kaolin microsphere in-situ crystallization method first kaolin is spray dried to microballoon, and kaolin microsphere mixes with water glass, liquid caustic soda, directed agents, and hydrothermal crystallizing synthesis obtains molecular sieve.Kaolin former powder in-situ crystallization method directly adopts kaolin powder to mix with water glass, liquid caustic soda, directed agents, and hydrothermal crystallizing synthesis obtains molecular sieve.In three kinds of above-mentioned synthetic methods, in order to improve the silica alumina ratio of product, its silica alumina ratio that feeds intake is all higher, the highlyest even reach more than 9, and the silica alumina ratio of product is generally about 5 usually, therefore, the silicon of nearly about 40% is not utilized, these silicon enter in synthesis mother liquid after filtration, and in mother liquor, the amount of silicon is comparatively large, and the concentration of silicon is not high, be generally less than 100g/L, modulus is also lower, is generally less than 3.0, particularly also contains a large amount of sulfate radicals in gel method.
For the recycling of synthesis mother liquid, GRACE company discloses and is collected by mother liquor in the conventional GPC method NaY of US4164551 synthesizes, then in mother liquor, add acid aluminium salt as Tai-Ace S 150, adjust ph forms alumino silica gel, then is back to use in the synthesis of conventional GPC method NaY zeolite.The method and follow-up improving one's methods solve the Utilizing question in silicon source in mother liquor, but the waste water of a large amount of contains sodium sulfate still needs outer row, and alumino silica gel cannot ensure whole utilization, and superfluous alumino silica gel also needs further process.
Sodium in conventional GPC method NaY mother liquor has two kinds of forms, sodium hydroxide and sodium sulfate, in treatment process by mother liquor acid neutralization to pH value 9.5, again solution is cooled to 5-25 DEG C, now, sodium sulfate saturated crystallization is separated out, separating sodium sulfate crystal and filtrate, product sodium sulfate is Na
2sO
410H
2o, can be used as the raw material of other techniques.A filtrate part containing gel is directly used in the synthesis of NaY, can reduce the consumption of feed intake middle water glass and liquid caustic soda; Another part can be used for Kaolinite Preparation of Catalyst, utilizes silicon concentrated in filtrate as the binding agent of catalyzer.But these processing modes only part solve the emission problem of contains sodium sulfate waste liquid, and energy consumption is high.
Adopt in US4493902 and kaolin is carried out high and low temperature roasting respectively prepare microballoon, utilize microballoon in-situ crystallization to synthesize y-type zeolite, and realize the reuse of mother liquor.The mother liquor Treatment for Reuse of this technique passes through evaporation concentration.But because the concentration of silicon is lower in mother liquor, the output of mother liquor is comparatively large, so the workload of concentration is comparatively large, energy consumption is high.
CN1709794A adopts kaolin to be raw material, synthesizes y-type zeolite matrix material and realizes this technique synthesize the direct reuse of rear filtrated stock to replace liquid caustic soda and part water glass by in-situ crystallization technology.
Summary of the invention
The present inventor is surprised to find that by great many of experiments, the synthesis mother liquid that gel method obtains can not treated, directly be used in the method for kaolin former powder in-situ crystallization method synthesis y-type zeolite, reduce gel method synthesis mother liquid and discharge the pollution caused, and change and will add acid aluminium salt and to manufacture after alumino silica gel ability cyclically utilizing to the conventional processing mode of the building-up process of gel method y-type zeolite.Based on this, form the present invention.
The synthetic method of y-type zeolite provided by the invention, that kaolin is changed into metakaolin 500-860 DEG C of roasting dehydration, pulverize, make the metakaolin powder that particle diameter is less than 230 microns again, by metakaolin powder and recovery mother liquor, directed agents, sodium hydroxide solution, water and optional water glass, make mol ratio for (1-2.5) Na
2o:Al
2o
3: (4-9) SiO
2: (40-450) H
2the reacting material mixture of O, crystallization under being stirred at 80-100 DEG C by said reacting material mixture, then filter and drying, it is characterized in that the building-up process of said recovery mother liquor from gel method y-type zeolite, its concentration is SiO
2≤ 150g/L, Na
2o≤70g/L, SO
4 2-≤ 100g/L.
The synthetic method of y-type zeolite provided by the invention, can obtain the y-type zeolite of conventional kaolin former powder in-situ crystallization method synthesis, the advantage of the method is:
1, effectively make use of the silicon in the mother liquor of gel method synthesis y-type zeolite and sodium.
2, the discharge of the pollutent of containing sulfate radicals in the mother liquor of gel method synthesis y-type zeolite is decreased.
3, the mother liquor of gel method synthesis y-type zeolite need not anticipate, can be directly used in kaolin former powder in-situ crystallization method synthesis y-type zeolite, simplifies mother liquid disposal and synthesis step.
Embodiment
The synthetic method of y-type zeolite provided by the invention, that kaolin is changed into metakaolin 500-860 DEG C of roasting dehydration, pulverize, make the metakaolin powder that particle diameter is less than 230 microns again, by metakaolin powder and recovery mother liquor, directed agents, sodium hydroxide solution, water and optional water glass, make mol ratio for (1-2.5) Na
2o:Al
2o
3: (4-9) SiO
2: (40-450) H
2the reacting material mixture of O, crystallization under being stirred at 80-100 DEG C by said reacting material mixture, then filter and drying, it is characterized in that the building-up process of said recovery mother liquor from gel method y-type zeolite, its concentration is SiO
2≤ 150g/L, Na
2o≤70g/L, SO
4 2-≤ 100g/L.
In method provided by the invention, said kaolin is selected from hard kaolin or soft kaolin; Its crystalline content should be greater than 75 heavy %, and be preferably greater than 85 heavy %, its median size is less than 4 microns, so be the original soil without forming processes.
In method provided by the invention, said kaolin also can be through the kaolin that acid or alkali or Ficus caricaL obtain, said acid can be mineral acid and the organic acids such as hydrochloric acid, nitric acid, acetic acid, oxalic acid, oxalic acid, sulfuric acid, phosphoric acid, wherein preferred hydrochloric acid and nitric acid; Said alkali can be sodium hydroxide, potassium hydroxide, ammoniacal liquor etc., wherein preferred sodium hydroxide; Said salt is selected from sodium carbonate or sodium bicarbonate.
Described kaolinic maturing temperature is 500 ~ 900 DEG C, preferably 500 ~ 700 DEG C, and more preferably 640 ~ 680 DEG C, general roasting time is 1 ~ 10 hour.
Said directed agents can conventionally be synthesized, as the preparation method according to USP3574538, USP3639099, USP3671191, USP4166099 and EUP0435625 synthesizes.The composition of directed agents is preferably: (10-17) SiO
2: (0.7-1.3) Al
2o
3: (1-18) Na
2o:(200-450) H
2o.Said directed agents is preferably aging at 4 ~ 20 DEG C to be obtained.
The said recovery mother liquor of the present invention is from the building-up process of gel method y-type zeolite, and being filter the first-time filtrate obtained, also can be the mixing solutions of first-time filtrate and follow-up scavenging solution.Said filter type can be centrifugation, band filter etc.Said gel method reclaims mother liquor, and its concentration is SiO
2≤ 150g/L, Na
2o≤70g/L, SO
4 2-≤ 100g/L; In the preferred case, said gel method reclaims mother liquor, and its concentration is SiO
220 ~ 100g/L, Na
2o 15 ~ 70g/L, SO
4 2-5 ~ 100g/L; In further preferred situation, said gel method reclaims mother liquor, and its concentration is SiO
220 ~ 50g/L, Na
2o 18 ~ 30g/L, SO
4 2-5 ~ 60g/L.Such as, in a concrete embodiment of the present invention, its concentration can be SiO
228.5g/L, Na
2o 22.6g/L, SO
4 2-25g/L; In another concrete embodiment of the present invention, its concentration can be SiO
220.2g/L, Na
2o 18.6g/L, SO
4 2-40g/L; In another concrete embodiment of the present invention, its concentration can be SiO
238.5g/L, Na
2o 28.6g/L, SO
4 2-60g/L.
Said water glass determines whether it adds in reacting material mixture according to the needs of reacting material mixture proportioning.
Said crystallization all can be carried out in stirring or under leaving standstill.If crystallization under agitation, stirring velocity is 100-1000 rev/min, preferred 400-600 rev/min, and the time is 16-48 hour, preferred 24-32 hour.After crystallization, the drying temperature of zeolite is 100-120 DEG C.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
The relative crystallinity that the NaY content of embodiment mesolite measures according to RIPP146-90 standard method and drawing; Lattice constant a
0measure according to RIPP145-90 standard method.
Zeolite data calculate according to following formula:
SiO
2/ Al
2o
3(mol ratio)=2 × (2.5858-a
0)/(a
0-2.4191), wherein, lattice constant a
0unit is nm.
Embodiment 1
The preparation of directed agents: get 250 grams of sodium silicate solutions (containing the SiO of 20.05 heavy %
2, 6.41 heavy % Na
2o), 120 grams of sodium aluminate solutions are slowly added under 30 DEG C of rapid stirrings (containing the Al of 3.15 heavy %
2o
3, the Na of 21.1 heavy %
2o), constant temperature 30 DEG C stirs 1 hour, at 20 DEG C static aging 24 hours, obtains directed agents.Directed agents consists of 16Na
2o:Al
2o
3: 15SiO
2: 320H
2o.
Be the kaolin (China Kaolin Co., Ltd, crystalline content is 80 heavy % for Suzhou, Yangshan board) of 4 μm by median size, 660 DEG C of roastings 3 hours, obtain metakaolin powder, pulverize the metakaolin powder made particle diameter and be less than 230 μm.
Get 80 grams of metakaolin powder, add 2600 grams of regular industrial gel method NaY synthesis mother liquids under stirring (containing SiO
228.5g/L, Na
2o 22.6g/L, SO
4 2-25g/L), 60 grams of directed agents, 80 grams of concentration are the sodium hydroxide solution of 5 heavy %.Be warming up to 90 DEG C of constant temperature and stir crystallization 28 hours, reinforced is 400 revs/min with mixing speed during crystallization.After crystallization terminates, crystallization tank is cooled, filter, be washed to washing lotion pH value and be less than 10.120 DEG C of dryings 2 hours, obtain zeolite Y-1.
It is 72.4 heavy % that X-ray diffraction measures NaY content in Y-1, and lattice constant is 2.472nm.Zeolite is 4.30.
Embodiment 2
Get 80 grams of metakaolin powder, add 2900 grams of regular industrial gel method NaY synthesis mother liquids under stirring (containing SiO
220.2g/L, Na
2o 18.6g/L, SO
4 2-40g/L), directed agents prepared by 60 grams of embodiments 1,76 grams of concentration are the sodium hydroxide solution of 5 heavy %.Be warming up to 90 DEG C of constant temperature and stir crystallization 28 hours, reinforced is 400 revs/min with mixing speed during crystallization.After crystallization terminates, crystallization tank is cooled, filters,
Be washed to washing lotion pH value and be less than 10.120 DEG C of dryings 2 hours, obtain zeolite Y-2.
It is 75.4 heavy % that X-ray diffraction measures NaY content in Y-2, and lattice constant is 2.469nm.Zeolite is 4.67.
Embodiment 3
Get 80 grams of metakaolin powder, add 1800 grams of regular industrial gel method NaY synthesis mother liquids under stirring (containing SiO
238.5g/L, Na
2o 28.6g/L, SO
4 2-60g/L), directed agents prepared by 60 grams of embodiments 1,75 grams of industrial waterglass are (containing SiO
2258.5g/L, Na
2o 80.6g/L), 75 grams of concentration are the sodium hydroxide solution of 5 heavy %.Be warming up to 90 DEG C of constant temperature and stir crystallization 26 hours, reinforced is 400 revs/min with mixing speed during crystallization.After crystallization terminates, crystallization tank is cooled, filter, be washed to washing lotion pH value and be less than 10.120 DEG C of dryings 2 hours, obtain zeolite Y-3.
It is 72.9 heavy % that X-ray diffraction measures NaY content in Y-3, and lattice constant is 2.471nm.Zeolite is 4.42.
Embodiment 4
Get 80 grams of metakaolin powder, add 1400 grams of regular industrial gel method NaY synthesis mother liquids under stirring (containing SiO
238.5g/L, Na
2o 28.6g/L, SO
4 2-60g/L), directed agents prepared by 60 grams of embodiments 1,81 grams of industrial waterglass are (containing SiO
2258.5g/L, Na
2o 80.6g/L), 78 grams of concentration are the sodium hydroxide solution of 5 heavy %.Be warming up to 90 DEG C of constant temperature and stir crystallization 26 hours, reinforced is 400 revs/min with mixing speed during crystallization.After crystallization terminates, crystallization tank is cooled, filter, be washed to washing lotion pH value and be less than 10.120 DEG C of dryings 2 hours, obtain zeolite Y-4.
It is 75.9 heavy % that X-ray diffraction measures NaY content in Y-4, and lattice constant is 2.468nm.Zeolite is 4.82.
Embodiment 5
Get 80 grams of metakaolin powder, add 1000 grams of regular industrial gel method NaY synthesis mother liquids under stirring (containing SiO
238.5g/L, Na
2o 28.6g/L, SO
4 2-60g/L), directed agents prepared by 60 grams of embodiments 1,170 grams of industrial waterglass are (containing SiO
2258.5g/L, Na
2o 80.6g/L), 94 grams of concentration are the sodium hydroxide solution of 5 heavy %.Be warming up to 90 DEG C of constant temperature and stir crystallization 26 hours, reinforced mixing speed is 400 revs/min, leaves standstill crystallization.After crystallization terminates, crystallization tank is cooled, filter, be washed to washing lotion pH value and be less than 10.120 DEG C of dryings 2 hours, obtain zeolite Y-5.
It is 71.9 heavy % that X-ray diffraction measures NaY content in Y-5, and lattice constant is 2.468nm.Zeolite sial is 4.82.
Claims (13)
1. the synthetic method of a y-type zeolite, that kaolin is changed into metakaolin 500-860 DEG C of roasting dehydration, pulverize, make the metakaolin powder that particle diameter is less than 230 microns again, by metakaolin powder with reclaim mother liquor, directed agents, sodium hydroxide solution, water and and optional water glass, make mol ratio for (1-2.5) Na
2o:Al
2o
3: (4-9) SiO
2: (40-450) H
2the reacting material mixture of O, crystallization under being stirred at 80-100 DEG C by said reacting material mixture, then filter and drying, it is characterized in that the building-up process of said recovery mother liquor from gel method y-type zeolite, its concentration is SiO
2≤ 150g/L, Na
2o≤70g/L, SO
4 2-≤ 100g/L.
2., according to the process of claim 1 wherein, said kaolin is selected from hard kaolin, soft kaolin or coal gangue.
3. according to the method for claim 2, wherein, in said kaolin, crystalline content is greater than 75 heavy %.
4. according to the method for claim 3, wherein, in said kaolin, crystalline content is greater than 85 heavy %.
5. according to method arbitrary in Claims 1 to 4, wherein, said kaolin is the kaolin obtained through peracid or alkali or Ficus caricaL, said acid is selected from one in hydrochloric acid, nitric acid, acetic acid, oxalic acid, oxalic acid, sulfuric acid, phosphoric acid or its mixture, said alkali is selected from one in sodium hydroxide, potassium hydroxide, ammoniacal liquor or its mixture, and said salt is selected from sodium carbonate or sodium bicarbonate.
6. according to the method for claim 5, wherein, said acid is hydrochloric acid or nitric acid.
7. according to the method for claim 5, wherein, said alkali is sodium hydroxide.
8., according to the process of claim 1 wherein, said kaolin changes into metakaolin 500 ~ 700 DEG C of roasting dehydrations.
9. according to the method for claim 8, wherein, said kaolin changes into metakaolin 640 ~ 680 DEG C of roasting dehydrations.
10. according to the process of claim 1 wherein, said directed agents, consists of: (10-17) SiO
2: (0.7-1.3) Al
2o
3: (1-18) Na
2o:(200-450) H
2o.
11. according to the method for claim 1 or 10, and wherein, said directed agents is aging at 4 ~ 20 DEG C obtaining.
12. according to the process of claim 1 wherein, the recovery mother liquor of the said building-up process from gel method y-type zeolite, its concentration is SiO
220 ~ 150g/L, Na
2o 15 ~ 70g/L, SO
4 2-5 ~ 100g/L.
13. according to the process of claim 1 wherein, the recovery mother liquor of the said building-up process from gel method y-type zeolite, its concentration is SiO
220 ~ 50g/L, Na
2o 18 ~ 30g/L, SO
4 2-5 ~ 60g/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108624326A (en) * | 2018-06-04 | 2018-10-09 | 陕西师范大学 | The preparation method and method of modifying of a kind of soil passivator and application |
| CN111320184A (en) * | 2018-12-13 | 2020-06-23 | 湖北赛因化工有限公司 | Method for preparing NaY molecular sieve by recycling NaY mother liquor |
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| JP2003277046A (en) * | 2002-03-19 | 2003-10-02 | Nippon Oil Corp | Y type zeolite and method for manufacturing the same |
| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | Method for synthesizing Y-zeolite composite material |
| CN101537368A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Method for preparing in situ crystallization type catalytic cracking catalyst |
| CN101993092A (en) * | 2009-08-27 | 2011-03-30 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5 zeolite |
-
2013
- 2013-07-31 CN CN201310328800.1A patent/CN104340990B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042523A (en) * | 1989-06-15 | 1990-05-30 | 中国石油化工总公司兰州炼油化工总厂 | A kind of method for preparing high-silicon Y-Zeolite |
| JP2003277046A (en) * | 2002-03-19 | 2003-10-02 | Nippon Oil Corp | Y type zeolite and method for manufacturing the same |
| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | Method for synthesizing Y-zeolite composite material |
| CN101537368A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Method for preparing in situ crystallization type catalytic cracking catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108624326A (en) * | 2018-06-04 | 2018-10-09 | 陕西师范大学 | The preparation method and method of modifying of a kind of soil passivator and application |
| CN111320184A (en) * | 2018-12-13 | 2020-06-23 | 湖北赛因化工有限公司 | Method for preparing NaY molecular sieve by recycling NaY mother liquor |
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