CN108217676A - The method that alkali free metal ion system synthesizes BETA molecular sieve - Google Patents
The method that alkali free metal ion system synthesizes BETA molecular sieve Download PDFInfo
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- CN108217676A CN108217676A CN201810323572.1A CN201810323572A CN108217676A CN 108217676 A CN108217676 A CN 108217676A CN 201810323572 A CN201810323572 A CN 201810323572A CN 108217676 A CN108217676 A CN 108217676A
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- molecular sieve
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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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a kind of method of alkali free metal ion system BETA molecular sieve, step is：1) by the organic formwork agent tetraethyl ammonium hydroxide of silicon source and high concentration in 80 120 DEG C of rotary drum aging 10 24 hours；2) water and silicon source are added in the gel synthetic system of above-mentioned retrogradation in synthesis ratio, hydrothermal crystallizing is carried out at 110 180 DEG C 46 days；3) it filters, is washed to neutrality；In 120 DEG C of 10 12h of air drying, BETA molecular sieve is obtained；4) filtrate of step 3) is concentrated to give first time mother liquor, adds the tetraethyl ammonium hydroxide used in step 1), repeated step 2), step 3), obtain BETA molecular sieve product；Mother liquor is repeatedly circulated with zeolite-water washing lotion as moisture content is added；The molecular sieve that the BETA molecular sieve of the present invention produces in synthesizing does not need to carry out sour exchange processing, reduces the nano molecular sieve loss in exchanging and reduces the processing of waste water after exchange.The recycling of mother liquor can improve the utilization rate of Molecular Sieves as Template simultaneously, alleviate the pollution of molecular sieve waste water.
Description
Technical field
The present invention relates to a kind of methods of alkali free metal ion system BETA molecular sieve.Using tetraethyl ammonium hydroxide as only
One alkali source has prevented the NH that conventional BETA molecular sieve generates in exchange process3- N pollutes.Due to using tetraethyl ammonium hydroxide
As a large amount of tetraethyl ammonium hydroxide is contained in mother liquor, cost has been saved, has reduced mother liquor pollution.Divide after BETA molecular sieve crystallization
It need to repeatedly be utilized from obtained mother liquor.The water lotion of molecular sieve can be concentrated by film and be reused, while also may be used since impurity is few
As other molecular sieve industrial waters, a whole set of green synthesis method is formed.
Background technology
BETA molecular sieve is a kind of with three-dimensional structure, the molecular sieve of twelve-ring chi structure, since it has big ratio
Surface and unique mechanism and good hydrothermal stability and be widely used in alkane isomerization, NH3Oxidative degradation, VOC
It is a kind of important industrial molecular sieve catalyst in the petroleum refinings such as oxidation, alkylating aromatic hydrocarbon and fine chemistry industry catalysis reaction.Often
Rule synthesis BETA molecular sieve molecular formula can be expressed asX·Al2O3·（1-X）·SiO2, wherein Al2O3It can be by titanium oxide, oxygen
Change the substitutions such as boron, gallium oxide.Mainly using silicon source in synthesis, such as smoke silica gel, Ludox, ethyl orthosilicate and a kind of aluminium
Thin water aluminium including inorganic silicon source, is such as intended in source（AlOOH·H2O）, sodium metaaluminate, aluminum sulfate or organic silicon source, such as n-butylaluminum.
In inorganic base（Can be NaOH or KOH）With organic formwork agent tetraethyl ammonium hydroxide, hydro-thermal is closed under certain temperature and pressure
Into.
Due to BETA molecular sieve have relatively large cation exchange capacity (CEC), this customary preparation methods, mainly
Generate sodium form BETA molecular sieve.In commercial Application, need to use NH4Cl is swapped, therefore can generate the ammonium chloride of high concentration
Waste water, the synthesis cost of molecular sieve can be greatly increased by handling these waste water, while cause environmental pollution.Further, since BETA points
Son sieve crystal grain is thinner, and the loss of about 5%-10% is had in exchange process, causes to waste.
Method recycles BETA molecular sieve synthesis mother liquid disclosed in Chinese patent CN102795639, but
In actual production, using alkali metal synthesis of molecular sieve, mother liquor is usually containing a large amount of salinity, and reuse is often due to introduce a large amount of
Salt composition, and final zeolite product is made to contain stray crystal.
Method disclosed in US5683673 uses silica gel and metallic aluminium powder to be free of in system for Material synthesis BETA molecular sieve
Alkali metal ion, but ethyl alcohol is added in crystallization system, system pressure can be made to increase severely, bring greatly safety hidden for industrial production
Suffer from.
CN131324A proposes a kind of method of alkali free metal ion system synthesis BETA molecular sieve, reaction system tool
It is made of following molar ratio：SiO2/Al2O3=15- ∞, TEAOH/SiO2=0.14-0.4, H2O/SiO2=3.0-10.Crystallization condition
It is 120-160 DEG C, 6-14 days.This patent adds in a large amount of template due to synthesis so that synthesis cost is excessively high, simultaneously because closing
It is longer into the time, therefore it is unfavorable for industrial use.
CN1923689 also proposed a kind of method of alkali free metal ion synthesis BETA molecular sieve, using two step alternating temperatures crystalline substance
BETA molecular sieve is combined to, synthesis BETA type molecular sieves reach industrial application requirement, but the tetraethyl ammonium hydroxide consumed is more,
The ratio between tetraethyl ammonium hydroxide dosage and product still reach 25 weight % at high proportion.
CN104760971, the patent of announcement is by organic formwork agent/SiO2Ratio be reduced to 0.06-0.2, but in patent
The performance parameter of product, such as specific surface are not provided.And the BETA molecular sieve specific surface that industrially uses need 600 with
On.
In addition, EP187522, which uses to soak liquid reactants on a solid surface to reach, reduces organic amine template dosage
Purpose, but due to the limitation of convey and stir etc., scale cannot be amplified by being simply possible to use in the synthesis of laboratory very little volume
Using.But similar patent also has CN1108213A, CN1108214A, CN1041616C etc..
In conclusion existing synthesize the BETA for reaching industrial requirements using alkali metal-free synthesis BETA molecular sieve in the art
Type molecular sieve, the consumption of tetraethyl ammonium hydroxide are still larger, it is difficult to industry's enlarging production.Improved synthetic method and
The reuse method of synthesis mother liquid is from having not been reported.
Invention content
The object of the present invention is to provide a kind of method of alkali free metal ion system synthesis BETA molecular sieve, with tetraethyl hydrogen
Amine-oxides have prevented the NH that conventional BETA molecular sieve generates in exchange process as unique alkali source3- N pollutes.Simultaneously because it adopts
Containing a large amount of tetraethyl ammonium hydroxide in by the use of tetraethyl ammonium hydroxide as mother liquor, mother liquor pollution is reduced, BETA molecular sieve is brilliant
Isolated mother liquor need to be utilized repeatedly after change.The water lotion of molecular sieve can be concentrated by film and be reused, together since impurity is few
When also can be used as other molecular sieve industrial waters, form a whole set of green synthesis method.The outstanding feature of the present invention is by mother liquor
Abundant reuse achievees the purpose that reduce the dosage of organic formwork agent.
The present invention provides the step of a kind of method of alkali free metal ion system synthesis BETA molecular sieve includes：
1) by the organic formwork agent tetraethyl ammonium hydroxide of silicon source and high concentration, aging 10-24 is small in 80-120 DEG C of rotary drum
When.
2) water and silicon source are added in the synthetic system of above-mentioned retrogradation in synthesis ratio, hydro-thermal is carried out at 110-180 DEG C
Crystallization 4-6 days；
3) it filters, is washed to neutrality；In 120 DEG C of air drying 10-12h, BETA molecular sieve is obtained, not needing to exchange can be straight
Connect use；
In step 1), organic formwork agent and SiO2Molar ratio in 0.15-0.4：1, preferably in 0.15-0.30：1；Final water
Silicon ratio is 8-20：1, preferably 8-15:1.
In the XRD spectrum of the Beta molecular sieves, 2 θ for 7.615,21.630,22.702,25.631,27.160,
29.061st, there is diffraction maximum at 29.921,33.739,34.550.
4) filtrate of step 3) is concentrated to give first time mother liquor, analyzes the SiO in the concentration Mother liquor2、Al2O3And
The content of TEAOH adds the tetraethyl ammonium hydroxide used in step 1), repeats step 2), step 3), obtains BETA molecules
Sieve product；Mother liquor is repeatedly circulated with zeolite-water washing lotion as moisture content is added.
Silicon source described in step 1) is silica gel, and Na contents are less than 0.05% wherein in silica gel；The tetraethyl hydroxide of high concentration
The mass percentage concentration 35% of ammonium salt solution.
The silicon source is intends thin water aluminium.
Concentration Mother liquor described in step 4) is the 40%-50% of original mother liquor volume.Since raw material is relatively simple in the present invention
It is single, therefore mother liquor analysis is also very simple, is suitble to contact the needs to feed intake in industrial production.But the addition of mother liquor, it is necessary to consider
Industry proportioning needs, main to consider according to circumstances using all or part of.
The BETA molecular sieve product that preparation method described above is prepared.The BETA molecular sieve is carried as catalyst
Body.
The present invention provides a kind of method of alkali free metal ion system synthesis BETA molecular sieve, with tetraethyl ammonium hydroxide
As unique alkali source, the NH that conventional BETA molecular sieve generates in exchange process is prevented3- N pollutes.Simultaneously because using tetrem
Base ammonium hydroxide reduces mother liquor pollution, divides after BETA molecular sieve crystallization as a large amount of tetraethyl ammonium hydroxide is contained in mother liquor
It need to repeatedly be utilized from obtained mother liquor, the dosage of tetraethyl ammonium hydroxide reduced by the method for reuse after mother liquor concentrations.Finally
The usage amount of tetraethyl ammonium hydroxide is in 0.15-0.25 or so.Due to reducing NH4Salt exchanges, and without waste water pollution problem and
Loss is exchanged, industrial production can receive.The water lotion of the molecular sieve can be concentrated by film and be reused, together since impurity is few
When also can be used as other molecular sieve industrial waters, form a whole set of green synthesis method.The outstanding feature of the present invention is to synthesize
Completely without using alkali metal ion in Beta molecular sieves, the silicon source used is low sodium silica gel or Ludox；Silicon source is intended thin for low sodium
Water aluminium；Template is tetraethyl ammonium hydroxide.By the abundant reuse of mother liquor, achieve the purpose that reduce the dosage of organic formwork agent, close
Into BETA molecular sieve have specific surface it is big（>600m2/g）, the characteristics of crystal form is complete, and quality is high.
Description of the drawings
Fig. 1 is the XRD diagram of BETA-40A that the present invention obtains.
Specific embodiment
With reference to specific embodiment, the present invention will be further described, and the experiment side of actual conditions is not specified in embodiment
Method, condition usually according to normal condition and described in handbook or according to the normal condition proposed by manufacturer；Used sets
Standby, material, reagent etc., are commercially available unless otherwise specified.
Embodiment 1.
According to mol ratio 12TEAOH：40SiO2：Al2O3：600H2O calculates material quantity, by low sodium silica gel and 35% tetraethyl
Ammonium hydroxide mixing adds a small amount of water mixing, be put into rotary drum 100 DEG C of agings 24 hours, generate gel, at this time gel
It matches as 12TEAOH：40SiO2：320H2O, gel are mixed with intending thin water aluminium and remaining water, transfer system synthesis crystallizing kettle
In, 160 DEG C of constant temperature crystallization 4 days.Product is washed to neutrality by separation, disposing mother liquor, solid product, is done in 120 DEG C of air
Dry 12h obtains beta molecular screen primary powders labeled as Beta-40A.Analyze SiO in mother liquor2Content is 0.6-0.7g/L, Al2O3Contain
It measures as 3-4mg/L, tetraethyl ammonium hydroxide 12%.Mother liquor amount is about that every liter of crystallization liquid goes out 50-60L.Concentrated mother liquor measures
Tetraethyl ammonium hydroxide a concentration of 26%.
Beta-40A original powders carry out XRD analysis and are determined as Beta molecular sieves, and it is 633 that specific surface is measured after product is fired
m2·g-1。
Embodiment 2.
By concentrated mother liquor, the tetraethyl ammonium hydroxide with 35% shares, and raw material silica gel is added in, by mol ratio 12TEAOH：
40SiO2：320H2O, 100 DEG C of agings 24 hours are then mixed with intending thin water aluminium and remaining water.The water of supplement, using point
Son sieve water lotion substitutes.The slurry of formation is transferred in synthesis crystallizing kettle, 160 DEG C of constant temperature crystallization 4 days.Product passes through separation,
Disposing mother liquor, solid product are washed to neutrality, in 120 DEG C of air drying 12h, obtain beta molecular screen primary powders and are labeled as
Beta-40B.Mother liquor concentrations are simultaneously analyzed.
Embodiment 3.
By concentrated mother liquor, zeolite-water washing lotion is repeatedly used with fresh feed, prepares beta molecular screen primary powders Beta-
40C --- Beta-40H, the specific surface of product, crystallinity are listed in the table below.
The crystallinity and specific surface of 1. molecular sieve of table
| Sample ID | Crystallinity % | Specific surface m2·g-1 |
| Beta-40A | 110 | 633 |
| Beta-40B | 108 | 648 |
| Beta-40C | 105 | 635 |
| Beta-40D | 113 | 630 |
| Beta-40E | 105 | 643 |
| Beta-40F | 107 | 650 |
| Beta-40G | 99 | 613 |
| Beta-40H | 103 | 628 |
Claims (8)
1. a kind of method of alkali free metal ion system synthesis BETA molecular sieve, it is characterised in that including the step of：
1) by the organic formwork agent tetraethyl ammonium hydroxide of silicon source and high concentration, aging 10-24 is small in 80-120 DEG C of rotary drum
When；
2) water and silicon source are added in the gel synthetic system of above-mentioned retrogradation in synthesis ratio, hydro-thermal is carried out at 110-180 DEG C
Crystallization 4-6 days；
3) it filters, is washed to neutrality；In 120 DEG C of air drying 10-12h, BETA molecular sieve is obtained；
4) filtrate of step 3) is concentrated to give first time mother liquor, analyzes the SiO in the concentration Mother liquor2、Al2O3And TEAOH
Content, add the tetraethyl ammonium hydroxide used in step 1), repeat step 2), step 3), obtain BETA molecular sieve production
Product；Mother liquor is repeatedly circulated with zeolite-water washing lotion as moisture content is added；
In step 1), organic formwork agent and SiO2Molar ratio be 0.15-0.4：1；Final water silicon ratio is 8-20：1；
In the XRD spectrum of the Beta molecular sieves, 2 θ for 7.615,21.630,22.702,25.631,27.160,29.061,
29.921st, there is diffraction maximum at 33.739,34.550.
2. the method for synthesis BETA molecular sieve according to claim 1, it is characterised in that the silicon source described in step 1) is silicon
Na contents are less than 0.05% in colloidal sol or silica gel, wherein silica gel；The mass percentage concentration of the tetraethyl ammonium hydroxide solution of high concentration
35%。
3. the method for synthesis BETA molecular sieve according to claim 1, it is characterised in that the organic formwork described in step 1)
Agent and SiO2Molar ratio be 0.15-0.30：1.
4. the method for synthesis BETA molecular sieve according to claim 1, it is characterised in that the final water silicon ratio of step 1) is 8-
15：1.
5. the method for synthesis BETA molecular sieve according to claim 1, it is characterised in that the silicon source described in step 2) is intends
Thin water aluminium.
6. the method for synthesis BETA molecular sieve according to claim 1, it is characterised in that the concentration stepmother described in step 4)
Liquid is the 40%-50% of original mother liquor volume.
7. the BETA molecular sieve that the preparation method in claim 1-6 described in any one is prepared.
8. a kind of carrier, which is characterized in that the carrier includes the BETA molecular sieve described in claim 7.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920260A (en) * | 2022-05-26 | 2022-08-19 | 盐城工学院 | A kind of preparation method of nanometer H-Beta molecular sieve |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313244A (en) * | 2001-03-12 | 2001-09-19 | 复旦大学 | Process for synthesizing beta-zeolite from non-alkali-metal ion system |
| CN102795639A (en) * | 2012-07-27 | 2012-11-28 | 大连理工大学 | Utilization method of beta molecular sieve synthetic mother liquid |
| CN104760971A (en) * | 2014-01-07 | 2015-07-08 | 中国石油化工股份有限公司 | Beta molecular sieve alkali-free metal ion synthesis method |
| CN106268965A (en) * | 2015-05-18 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst containing Beta molecular sieve and application thereof |
-
2018
- 2018-04-12 CN CN201810323572.1A patent/CN108217676A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313244A (en) * | 2001-03-12 | 2001-09-19 | 复旦大学 | Process for synthesizing beta-zeolite from non-alkali-metal ion system |
| CN102795639A (en) * | 2012-07-27 | 2012-11-28 | 大连理工大学 | Utilization method of beta molecular sieve synthetic mother liquid |
| CN104760971A (en) * | 2014-01-07 | 2015-07-08 | 中国石油化工股份有限公司 | Beta molecular sieve alkali-free metal ion synthesis method |
| CN106268965A (en) * | 2015-05-18 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst containing Beta molecular sieve and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920260A (en) * | 2022-05-26 | 2022-08-19 | 盐城工学院 | A kind of preparation method of nanometer H-Beta molecular sieve |
| CN114920260B (en) * | 2022-05-26 | 2023-09-01 | 盐城工学院 | A kind of preparation method of nano H-Beta molecular sieve |
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