CN109133086A - A method of preparing molecular sieve - Google Patents
A method of preparing molecular sieve Download PDFInfo
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- CN109133086A CN109133086A CN201710500840.8A CN201710500840A CN109133086A CN 109133086 A CN109133086 A CN 109133086A CN 201710500840 A CN201710500840 A CN 201710500840A CN 109133086 A CN109133086 A CN 109133086A
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- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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- 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
- C01B39/26—Mordenite type
- C01B39/265—Mordenite type using at least one organic template directing agent
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- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- 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
- C01B39/44—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
- C01B39/445—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38 using at least one organic template directing agent
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/87—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by chromatography data, e.g. HPLC, gas chromatography
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Abstract
The present invention relates to a kind of methods for preparing molecular sieve.Then this method is added acidulous material in remaining mother liquor, by acid-base property neutralization reaction, eliminates template volatilization bring pollution during the separation process, while realizing the recycling and reusing of template by the way that template is recycled in Crystallization of Zeolite liquid pressure release.The content of template in mother liquor there can be through the invention tens of thousands of a ppm be reduced to several hundred a ppm, effective solution template generates toxic, unpleasant gas in subsequent separation of solid and liquid, realizes clean manufacturing.
Description
Technical field
The invention belongs to technical field of molecular sieve preparation, are related to a kind of method for preparing molecular sieve, and in particular to a kind of green
The method that color environment-friendly type prepares molecular sieve.
Background technique
Zeolite molecular sieve is a kind of crystalline material with uniform cellular structure, mainly there is following spy compared with other materials
Point: (1) high specific surface area and adsorption capacity (2) adsorption capacity can control, can be from hydrophobic to hydrophilic changes in material (3)
Duct and orifice diameter about existBetween, it is suitble to diameter range (4) unique cellular structure of most of molecules to show
Selectivity of different shapes, by product, reactant and transition state it is shape-selective and improve the yield of specific product, avoid by-product
The generation (6) of object has very high heat and hydrothermal stability.These features determine that zeolite molecular sieve has extensively in Industrial Catalysis
General application prospect is widely used in fields such as PETROLEUM PROCESSING, petrochemical industry, fine chemistry industry and daily-use chemical industries.
The preparation method of existing molecular sieve generallys use hydro-thermal synthetic method, and the basic step of preparation is as follows: will be certain
The silicon source of amount, silicon source, template, alkali source and water mixing, plastic, then crystallization certain time at a certain temperature, after crystallization
Mother liquor is then separated by solid-liquid separation, washs acquisition sieve sample.It prepares to usually require to be added in raw material and there is structure directing
That uses in template, such as ZSM-35 molecular sieve preparation process mainly has pyridine, cyclohexylamine, ethylenediamine, piperazine buttocks, pyrrolidines；
Template needed for prepared by ZSM-5 molecular sieve is mainly n-butylamine, four propylamine, ethylenediamine etc.；Template needed for prepared by modenite
Mainly there are hexamethylene imine, triethylamine, diisopropylamine etc.；Template needed for prepared by Beta zeolite is mainly tetraethylammonium bromide
Deng.These templates are mainly nitrogenous organic compound, would generally be greatly excessive in synthetic ratio.In crystallization mother liquor by
In containing excessive template, causes to generate a large amount of toxic, niff in mother liquor separation process, both polluted environment,
It causes operator's body to come to harm simultaneously, causes to be difficult to large-scale production.
Therefore, it needs to research and develop a kind of method that environmental type prepares molecular sieve at present.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of method for preparing molecular sieve in view of the deficiencies of the prior art.
Then this method is added acidulous material in remaining mother liquor, passes through by the way that template is recycled in Crystallization of Zeolite liquid pressure release
Acid-base property neutralization reaction eliminates template volatilization bring pollution during the separation process, while realizing the recycling of template again
It utilizes.
For this purpose, the present invention provides a kind of methods for preparing molecular sieve, comprising:
Step A, the colloid admixture solution that will be mixed to prepare by silicon source, silicon source, alkali source, template and water in reaction kettle
Crystallization is carried out, generates the mixed gas containing template, and obtain molecular sieve mother solution；
Step B, after crystallization, under the temperature and pressure of crystallization, the drain for opening reaction kettle carries out pressure release, obtains
Molecular sieve mother solution after pressure release；Meanwhile the template and water vapour of gas phase are liquefied and being recycled；
Acidulous material is added into reaction kettle, is neutralized after the molecular sieve mother solution cooling after pressure release by step C
Template reaction, the molecular sieve mother solution after being neutralized；
Step D filters the molecular sieve mother solution after neutralization, is washed, is dried, and molecular screen primary powder is made.
According to certain embodiments of the present invention, step C is after molecular sieve mother solution pressure release and template recycling
It carries out.
The present inventor is cooled to too low temperature and is unfavorable for subsequent filter, there is certain temperature the study found that in step C
It is more advantageous to filters pressing；But temperature is too high, causes template a small amount of in crystallization liquid that can also volatilize, and smell is generated, after being unfavorable for
Continuous processing.For example, needing to be cooled down with cooling water, water loss and time, while too low when being cooled to temperature lower than 30 DEG C
Temperature be unfavorable for subsequent filter, there is certain temperature to be more advantageous to filters pressing；And when being cooled to temperature higher than 80 DEG C, then cause crystallization
A small amount of template can also volatilize in liquid, generate smell, be unfavorable for subsequent processing.Therefore, in some preferred implementations of the invention
In example, in step C, it is cooled to 30-80 DEG C, is preferably cooled to 40-50 DEG C, and carries out neutralizing the anti-of template at such a temperature
It answers.
According to certain embodiments of the present invention, in step C, the acidulous material is that solid or liquid are organic weak
Acid, the preferably described acidulous material include one or more of citric acid, oxalic acid, carbonic acid and acetic acid, further preferably described
Acidulous material includes one or more of citric acid, oxalic acid and acetic acid.
According to certain embodiments of the present invention, in step C, the pH value of the crystallization molecular sieve mother liquor after neutralization is 5.5-
7.4, preferably 6.0-7.2.
In some embodiments of the invention, in step C, the dosage of acidulous material is the throwing of colloid admixture solution
Expect the 0.5wt%-20wt%, preferably 2wt%-15wt% of total weight.
In some embodiments of the invention, in step C, the content of template in the molecular sieve mother solution after neutralization
< 1000ppm, preferably≤500ppm, further preferably≤300ppm, or even it is more highly preferred to≤250ppm.
In some currently preferred embodiments of the present invention, in stepb, the temperature of pressure release is the temperature of crystallization.
In other preferred embodiments of the invention, in stepb, the initial pressure of pressure release is the pressure of crystallization.
In other preferred embodiment of the invention, in stepb, the pressure in pressure release to reaction kettle is normal pressure, i.e.,
Gauge pressure is zero.
According to certain embodiments of the present invention, in stepb, the amount of the template of recycling is by being added in step A
The 50wt%-85wt% of the total weight of template, preferably 60wt%-85wt%, further preferably 70wt%-85wt%.
In the present invention for gas phase template and the water vapour mode that liquefies and recycle be not particularly limited,
The template and water vapour of gas phase can be liquefied and be recycled using method and apparatus conventional in the art, for example, can
The template and water vapour of gas phase are liquefied and be recycled using heat exchanger and/or condenser.
In some embodiments of the invention, source of aluminium includes one of aluminum sulfate, boehmite and sodium aluminate
Or it is several.
In other embodiments of the invention, the silicon source includes silica solution, silicic acid, white carbon black, sodium metasilicate and positive silicon
One or more of acetoacetic ester.
In other embodiment of the invention, the template includes pyridine, ethylenediamine, ring amine, pyrrolidines, positive fourth
One or more of amine, four propylamine, ethylenediamine, triethylamine, diisopropylamine, tetraethylammonium bromide and piperazine buttocks.
According to certain embodiments of the present invention, in step, the temperature of the crystallization is 160-210 DEG C, preferably
165-200℃。
Other embodiments according to the present invention, in step, the time of the crystallization are 10-48h, preferably 15-
36h。
Molecular sieve of the present invention be Si-Al molecular sieve, preferably ZSM-35, ZSM-5, modenite, beta-molecular sieve, further
It is preferred that the molecular sieve is ZSM-35.
In some specific preferred embodiments of the invention, the molecular sieve be ZSM-35, in step, silicon source and
Silicon source molar ratio is with SiO2/Al2O3Be calculated as (5-100): the molar ratio of 1 template and silicon source is with R/SiO2It is calculated as (0.1-
2.0): 1, wherein R represents template；The molar ratio of the alkali source and silicon source is with OH-/SiO2It is calculated as (0.1-1.0): 1, the water
Molar ratio with silicon source is with H2O/SiO2It is calculated as (10-100): 1.
In the actual operation process, during the hydrothermal synthesis of step A, as the temperature rises, in reaction kettle body just
The saturated vapor pressure of water can be generated, this is equivalent to the pressure (i.e. self-generated pressure) that reaction system itself generates, and is not outer to pressure.
Therefore, crystallization process is the temperature in crystallization, is carried out under self-generated pressure, and during this, the pressure of crystallization is self-generated pressure,
For 0.5-1.7MPa.
Heretofore described one word of water, be not particularly illustrated or it is specified in the case where refer to deionized water or distilled water or
Ultrapure water.
The method for preparing molecular sieve provided by according to the present invention, makes Crystallization of Zeolite liquid in subsequent separation process,
Both the recycling of template had been realized, while having also eliminated harm of the smell of organic amine generation in separation process to human body, had been realized
Cleanly production.
Specific embodiment
To be readily appreciated that the present invention, below in conjunction with embodiment, the present invention will be described in detail, these embodiments only rise
Bright property effect, it is not limited to application range of the invention.If raw material used in the present invention or component are equal without specified otherwise
It can be made by commercial sources or conventional method.
Template agent content in the molecular sieve mother solution of following embodiments uses gas chromatography, utilizes
Agilent6890 gas chromatograph (Agilent) is detected.
Embodiment
Embodiment 1: ZSM-35 molecular sieve is prepared using cyclohexylamine amine as template
Step 1: be stirred at room temperature under state by 50 grams of aluminum sulfate (analysis it is pure, content be greater than 99.5%) is added to
In the deionized water of 785.7ml, stir 40 minutes.After being completely dissolved to aluminum sulfate, it is slowly added to 720 grams of silica solution (SiO2
The silica solution that content is 25%), it stirs 1 hour, is then slowly added into the sodium hydroxide of 72g, stir 1h, 148g cyclohexylamine is added
Obtained reaction mixture is stirred evenly as template.The mixture has following mole of composition: OH-:Al2O3:SiO2:R:H2O
=0.6:0.025:1:0.5:25.Reaction mixture is transferred in autoclave, crystallization 15 hours under 200 DEG C and self-generated pressure
Afterwards, crystallization terminates, and ZSM-35 molecular sieve crystallization mother liquor is made.
Step 2: after crystallization, the gas phase portion in reaction system is the mixture of cyclohexylamine and vapor, is beaten
The drain for opening reaction kettle carries out pressure release, draws gas gas-phase objects using the self-generated pressure of reaction system, recycles heat through heat exchanger
Afterwards, condenser condensation is introduced by pipeline, is directly recovered to fluid reservoir, the ZSM-35 molecular sieve crystallization mother liquor after recycling pressure release.
Step 3: the ZSM-35 molecular sieve crystallization mother liquor after the pressure release of recycling being cooled to 40 DEG C, 62.8g citric acid is added
(analyzing pure, solid), is stirred 1h, pH value 6.8 in the ZSM-35 molecular sieve crystallization mother liquor after neutralization, hexamethylene amine content is down to
1000ppm (gas-chromatography, Agilent6890, Agilent).
Step 4: the ZSM-35 molecular sieve crystallization mother liquor after neutralization being filtered, wash, is dried, ZSM-35 molecule is made
Sieve original powder.
Embodiment 2:
Steps 1 and 2,4 are the same as embodiment 1.
Step 3: mother liquor after the recovery being cooled to 40 DEG C, 125.6g citric acid is added, 1h is stirred, after neutralization
PH value 5.6 in ZSM-35 molecular sieve crystallization mother liquor, hexamethylene amine content are down to 300ppm.
Embodiment 3:
Steps 1 and 2,4 are the same as embodiment 1.
Step 3: mother liquor after the recovery being cooled to 60 DEG C, 53.8g oxalic acid is added, is stirred 1h, the ZSM- after neutralization
PH value 6.0 in 35 molecular sieve mother solutions, hexamethylene amine content are down to 500ppm.
Embodiment 4:
148g cyclohexylamine becomes 118g pyridine, the other the same as in Example 1 in step 1.
Step 2,4 are the same as embodiment 1.
Step 3: mother liquor after the recovery being cooled to 40 DEG C, 150g citric acid is added, is stirred 1h, the ZSM- after neutralization
PH5.5 in 35 molecular sieve mother solutions, pyridine content are down to 200ppm.
Embodiment 5:
Steps 1 and 2,3 are the same as embodiment 4.
Step 3: mother liquor after the recovery being cooled to 50 DEG C, 67g oxalic acid is added, is stirred 1h, the ZSM-35 after neutralization
PH value 5.8 in molecular sieve mother solution, pyridine content are down to 250ppm.
Embodiment 6:
Steps 1 and 2,3 are the same as embodiment 4.
Step 3: mother liquor after the recovery being cooled to 40 DEG C, 45g acetic acid is added, is stirred 1h, the ZSM-35 after neutralization
PH value 7.0 in molecular sieve mother solution, pyridine content are down to 280ppm.
Embodiment 7: ZSM-5 molecular sieve is prepared by template of n-butylamine
Step 1: at room temperature, the sulfuric acid of 9.9g being taken to be added in 160g water, add 4g aluminum sulfate, stirring is allowed to complete
Dissolution.23.5g n-butylamine solution is added slowly in above-mentioned solution, stirs evenly and A liquid is made.121g waterglass is taken, water is added
224g is stirred evenly and B liquid is made.Under rapid stirring, A drop is added in B liquid, Primogel is made, by reaction mixture
It is transferred in autoclave, under 180 DEG C and self-generated pressure after crystallization 48 hours, crystallization terminates, and it is female that ZSM-5 molecular sieve crystallization is made
Liquid.
Step 2,4 are the same as embodiment 1.
Step 3: mother liquor after the recovery being cooled to 40 DEG C, 21.7g citric acid is added, 1h is stirred, after neutralization
PH value 6.3 in ZSM-5 molecular sieve crystallization mother liquor, n-butylamine content are down to 220ppm.
Embodiment 8: modenite is prepared by template of hexamethylene imine
Step 1: at room temperature, by 2.9g sodium aluminate solution in 286g water, sodium hydroxide 7.24g is added, in stirring state
Under, hexamethylene imine 20.8g, uniformly rear addition silica solution 90.14g to be mixed, then under agitation by chlorination is added
Mixture is added in sodium 5.6g and remaining water 200g, stirs the mixture for aging 30min, reaction mixture is then transferred to high pressure
In kettle, crystallization 50 hours under 170 DEG C and self-generated pressure, crystallization terminates, and mordenite molecular sieve crystallization mother liquor is made.
Step 2,4 are the same as embodiment 1.
Step 3: mother liquor after the recovery being cooled to 40 DEG C, 18.4g oxalic acid is added, is stirred 1h, the mercerising after neutralization
PH value 6.8 in zeolite molecular sieve crystallization mother liquor, triethylamine content are down to 320ppm.
Comparative example 1: ZSM-35 molecular sieve is prepared by template of cyclohexylamine
Step 1: be stirred at room temperature under state by 50 grams of aluminum sulfate (analysis it is pure, content be greater than 99.5%) is added to
In the deionized water of 785.7ml, stir 40 minutes.After being completely dissolved to aluminum sulfate, it is slowly added to 720 grams of silica solution (SiO2
The silica solution that content is 25%), it stirs 1 hour, is then slowly added into 72 sodium hydroxide, stir 1h, 148g cyclohexylamine is added
Obtained reaction mixture is stirred evenly as template.The mixture has following mole of composition: OH-:Al2O3:SiO2:R:H2O
=0.6:0.025:1:0.5:25.Reaction mixture is transferred in autoclave under 200 DEG C and self-generated pressure after crystallization 15 hours,
Crystallization terminates, and ZSM-35 molecular sieve crystallization mother liquor is made.
Step 2: after crystallization, the gas phase portion in reaction system is the mixture of cyclohexylamine and vapor, benefit
Gas gas-phase objects are drawn with the self-generated pressure of reaction system, after heat exchanger recycles heat, condenser condensation are introduced by pipeline, directly
It takes back and receives fluid reservoir.
Cyclohexylamine concentration is 1.2% in ZSM-35 molecular sieve crystallization mother liquor.
Comparative example 2: ZSM-35 molecular sieve is prepared by template of cyclohexylamine
Be stirred at room temperature under state by 50 grams of aluminum sulfate (analysis it is pure, content be greater than 99.5%) is added to going for 785.7ml
In ionized water, stir 40 minutes.After being completely dissolved to aluminum sulfate, it is slowly added to 720 grams of silica solution (SiO2Content is 25%
Silica solution), it stirs 1 hour, is then slowly added into 72 sodium hydroxide, stir 1h, 148ml cyclohexylamine is added and is stirred as template
Mix uniformly obtained reaction mixture.The mixture has following mole of composition: OH-:Al2O3:SiO2:R:H2O=0.6:0.025:
1:0.5:25.Reaction mixture is transferred in autoclave under 200 DEG C and self-generated pressure after crystallization 15 hours, crystallization terminates, system
Obtain ZSM-35 molecular sieve crystallization mother liquor.
Cyclohexylamine concentration is 8-10% or more in ZSM-35 molecular sieve crystallization mother liquor.
Comparative example 1-6 and comparative example 1 and 2 are compared, in comparative example 2 after hydro-thermal reaction, are not brought up anti-
Answering the gas phase portion in system is the mixture of cyclohexylamine and vapor, and also acid adding is not handled, in final molecular sieve mother solution
Template agent content is high, reaches 8-10% or more, smell is very big, and seriously polluted, later separation is difficult to operate；Hydro-thermal is anti-in comparative example 1
After answering, the mixture that the gas phase portion in reaction system is cyclohexylamine and vapor is drawn, but acid adding is not handled, final point
Template agent content is still higher in son sieve crystallization mother liquor, is 1.2%, smell is still larger, there is pollution, and later separation is difficult to operate；And
The method provided according to the present invention drops the content of template in the molecular sieve mother solution after recycling template from tens of thousands of a ppm
For several hundred a ppm, effective solution template generates toxic, unpleasant gas when subsequent mother liquor is separated by solid-liquid separation, real
Existing clean manufacturing.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (12)
1. a kind of method for preparing molecular sieve, comprising:
Step A carries out the colloid admixture solution being mixed to prepare by silicon source, silicon source, alkali source, template and water in reaction kettle
Crystallization generates the mixed gas containing template, and obtains molecular sieve mother solution；
Step B, under the temperature and pressure of crystallization, the drain for opening reaction kettle carries out pressure release, the molecular sieve after obtaining pressure release
Crystallization mother liquor；Meanwhile the template and water vapour of gas phase are liquefied and being recycled；
Acidulous material is added into reaction kettle, carries out neutralization template after the molecular sieve mother solution cooling after pressure release by step C
Agent reaction, the molecular sieve mother solution after being neutralized；
Step D filters the molecular sieve mother solution after neutralization, is washed, is dried, and molecular screen primary powder is made.
2. the method according to claim 1, wherein the acidulous material is solid or liquid in step C
Organic monoacid, the preferably described acidulous material include one or more of citric acid, oxalic acid, carbonic acid and acetic acid.
3. method according to claim 1 or 2, which is characterized in that the crystallization molecular sieve mother liquor in step C, after neutralization
PH value be 5.5-7.4, preferable ph 6.0-7.2.
4. method described in any one of -3 according to claim 1, which is characterized in that in step C, the use of acidulous material
Amount is the 0.5wt%-20wt%, preferably 2wt%-15wt% of the total weight that feeds intake of colloid admixture solution.
5. method described in any one of -4 according to claim 1, which is characterized in that the molecular sieve in step C, after neutralization
Content < 1000ppm, the preferably≤500ppm of template in crystallization mother liquor, further preferably≤300ppm, or even be more highly preferred to
≤250ppm。
6. method described in any one of -5 according to claim 1, which is characterized in that step C is in molecular sieve mother solution
It is carried out after pressure release and template recycling.
7. method described in any one of -6 according to claim 1, which is characterized in that in step C, it is cooled to 30-80 DEG C,
It is preferred that being cooled to 40-50 DEG C.
8. method according to any one of claims 1-7, which is characterized in that in stepb, the temperature of pressure release is crystalline substance
The temperature of change；And/or the initial pressure of pressure release is the pressure of crystallization；And/or the pressure in pressure release to reaction kettle is normal pressure.
9. method described in any one of -8 according to claim 1, which is characterized in that in stepb, the template of recycling
50wt%-90wt%, the preferably 70wt%-90wt% of the total weight of the template by being added in step A are measured, it is further excellent
It is selected as 70wt%-80wt%.
10. method described in any one of -9 according to claim 1, which is characterized in that in step, source of aluminium includes
One or more of aluminum sulfate, boehmite and sodium aluminate；And/or the silicon source include silica solution, silicic acid, white carbon black,
One or more of sodium metasilicate and ethyl orthosilicate；And/or the template includes pyridine, ethylenediamine, ring amine, pyrrolidines
One or more of with piperazine buttocks.
11. method described in any one of -10 according to claim 1, which is characterized in that in step, the temperature of the crystallization
Degree is 160-210 DEG C, preferably 165-200 DEG C；And/or the time of the crystallization is 10-48h, preferably 15-36h.
12. method described in any one of -10 according to claim 1, which is characterized in that the molecular sieve is silicoaluminophosphate molecular
Sieve, preferably Si-Al molecular sieve includes one or more of ZSM-35, ZSM-5, modenite and beta-molecular sieve.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116409792A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Method for recovering organic template agent in molecular sieve synthesis mother liquor |
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