CN108910911A - A kind of recoverying and utilizing method using programmed temperature method synthesis total silicon Beta molecular sieve mother liquor - Google Patents
A kind of recoverying and utilizing method using programmed temperature method synthesis total silicon Beta molecular sieve mother liquor Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 77
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000012452 mother liquor Substances 0.000 title claims abstract description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 39
- 239000010703 silicon Substances 0.000 title claims abstract description 39
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 37
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 34
- 238000002425 crystallisation Methods 0.000 claims abstract description 34
- 230000008025 crystallization Effects 0.000 claims abstract description 34
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 16
- 239000010457 zeolite Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000000499 gel Substances 0.000 claims description 25
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 19
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 5
- 238000010899 nucleation Methods 0.000 abstract description 4
- 230000006911 nucleation Effects 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000013019 agitation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 11
- 239000012855 volatile organic compound Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 210000000987 immune system Anatomy 0.000 description 2
- -1 nitrogen hydrocarbon Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of synthetic methods of total silicon Beta molecular sieve, the component that reaction is had neither part nor lot in Beta molecular sieve synthesis mother liquid is carried out cycling and reutilization by the method for the present invention, both discharge synthesis waste liquid is avoided, it reduces environmental pollution, mother liquor is recycled again, raw material has been saved, the synthesis cost of molecular sieve is reduced；On the other hand, due to the presence of crystallite in reaction post mother liquor, greatly improve the nucleation rate and quantity of crystallization process induction period nucleus, it reduces molecular sieve and is nucleated activation energy, crystallization time can be shortened, it reduces zeolite crystal size and makes the higher of crystallinity of the molecular sieve of synthesis while reducing the particle size of sample, accelerate the crystallization process of molecular sieve, shorten the crystallization period.
Description
Technical field
The present invention relates to Zeolite synthesis method and technology fields, and in particular to a kind of to synthesize total silicon using programmed temperature method
The recoverying and utilizing method of Beta molecular sieve mother liquor.
Background technique
1967, mobil company disclosed invention containing using tetraethyl ammonium hydroxide as template in USP3308069
Synthesize Beta molecular sieve in sodium ion silica-alumina gel for the first time, it has unique three-dimensional staggered macroporous structure.With Y type
Molecular sieve is compared, the sial the mass ratio of the material of Beta molecular sieve can in tens to several hundred ranges modulation, Beta molecule
Sifter device have good structure selectivity, acid catalysis characteristic and hydrothermal stability and it absorption, in terms of show
Excellent performance, be widely used in VOCs adsorb, be hydrocracked, burn group-transfer react, acetify, isomerization, alkene hydration etc. it is more
In kind petrochemical process.
Volatile organic contaminant, i.e. VOCs are fusing points lower than the volatility of room temperature, boiling point between 50-260 DEG C
The general name of organic matter mainly includes hydro carbons, halogenated hydrocarbons, nitrogen hydrocarbon and low-boiling multiring aromatic hydrocarbon etc..VOCs is widely present in sky
Gas, soil, water body etc., and its is many kinds of, and harm is serious, and insulting breathing and immune system cause exhaling for human body
Road infection, immune system decline etc. are inhaled, furthermore, it is also possible to cause three cause effects (carcinogenic, teratogenesis, mutagenesis).Moreover,
Most of VOCs will lead to the generation of photochemical fog, forms secondary pollution and causes bigger threat and danger to human body and environment
Evil.There are many kinds of the administering methods of VOCs, and main method has absorption process, Production by Catalytic Combustion Process, photocatalytic degradation method, absorption method
Deng.Compared with the method for other processing VOCs, absorption method has the advantages that its uniqueness, and VOCs. can be effectively removed and inhale first
Attached method is easy to operate；Secondly, it is at low cost, and the pollutant of low concentration can be effectively removed.Therefore absorption method processing
VOCs is preferably to select, and apply a kind of wider method at present.The key of absorption method processing is the choosing of adsorbent
It selects, selects a kind of adsorbent that environmentally friendly and performance is good particularly important.And total silicon Beta molecular sieve has thermal stability
Feature high, hydrophobicity is good is the Ideal adsorption agent for adsorbing VOCs.
The problem of application for total silicon Beta molecular sieve, most critical is the preparation of total silicon Beta molecular sieve.Hydrothermal synthesis
Method is the classical synthetic method of total silicon Beta molecular sieve, this process needs expensive organic formwork agent participation to play structure directing
Effect；In general, hydro-thermal method synthesis of molecular sieve yield is generally in 50-80%, so meeting in the crystallization mother liquor after Zeolite synthesis
Contain a large amount of unreacting material components and molecular sieve crystallite.Template is in addition to a part is by molecular sieve absorption and a small amount of decomposition
Outside, still some is present in mother liquor, is not utilized efficiently, and template accounts for about raw material in Zeolite synthesis cost
The 50-70% of cost.Currently, such template mainly has tetrapropylammonium hydroxide, n-butylamine, ethylenediamine, tetraethyl hydroxide
Ammonium etc., but the use of this kind of template but cause molecular sieve synthesis mother liquid waste water become alkalinity it is strong, easily at the high ammonia nitrogen of colloid
Waste water becomes one of the primary pollution source of Zeolite synthesis industry.Under alkaline condition, some silicon can remain in mother liquor
In without being fully used, reduce the utilization rate of silicon.Since the big and free silica of silicon content in mother liquor is not easy
Sedimentation, easily causes the suspended matter of externally discharged waste water exceeded, to increase the processing difficulty of sewage；And the Na in crystallization mother liquor2O
Height increases filter residue processing cost.
Under the sustainable development overall situation of energy-saving and emission-reduction, a kind of system of efficient, environmental-friendly total silicon Beta molecular sieve
Preparation Method for total silicon Beta in VOCs using most important.The conjunction of molecular sieve is carried out as raw material using molecular sieve mother liquor
It has been effectively applied at method in the synthesis of a variety of molecular sieves.Chinese patent CN103787355A discloses one kind
The synthetic method of Beta molecular sieve, CN104418345A disclose a kind of preparation method for preparing multi-stage pore channel beta molecular screen.
Patent CN107311200A and patent CN102795639A discloses the method for recycling Beta mother liquor, their common spy
Sign is some or all from same type crystallization of molecular sieves mother liquor of template, carries out to mother liquor some or all of
It utilizes, can not only significantly reduce production cost in this way, but also pollution of the mother liquor to environment can be reduced, while mother liquor
In a large amount of molecular sieve crystallites be added in the Zeolite synthesis gel mixture of preparation as crystal seed, substantially reduce molecular sieve
Crystallization time, improve the crystallinity of synthesis of molecular sieve.But the Beta molecular sieve of above method synthesis is limited to low silica-alumina ratio,
Rather than total silicon Beta molecular sieve, this is also the maximum difference place of this patent and above-mentioned patent.
Summary of the invention
The purpose of the invention is to make up the deficiencies in the prior art, a kind of utilization programmed temperature method synthesis total silicon is provided
The recoverying and utilizing method of Beta molecular sieve mother liquor, is reducing environmental pollution, and saves raw material, reduces the synthesis cost of molecular sieve, drops
Low molecule sieve nucleation activation energy, improves nucleation rate, while reducing the particle size of sample, accelerates the crystallization mistake of molecular sieve
Journey shortens the crystallization period.
In order to reach the purpose of the present invention, technical solution is as follows：
A kind of recoverying and utilizing method using programmed temperature method synthesis total silicon Beta molecular sieve mother liquor, it is characterised in that：By Beta
Mother liquor after Crystallization of Zeolite is recycled, then is continued to use mother liquor as Beta Zeolite synthesis raw material, including step：
（1）By first time, the molecular sieve solid product of synthesis is separated, the mother liquor after recycling first time Zeolite synthesis；
（2）Analytical procedure（1）In SiO in the mother liquor that is recovered to2、Na2O、OH-, template content；
（3）According to the content of each component in mother liquor, silicon source, template, sodium hydroxide, He Shui are added in proportion, are configured to synthesize
Beta molecular sieve gel mixture；
（4）By step（3）Obtained in Beta molecular sieve gel mixture be fitted into the reaction kettle of polytetrafluoroethyllining lining, use
Programmed temperature method crystallization obtains corresponding Beta Crystallization of Zeolite liquid for a period of time；
（5）By step（4）Obtained in Beta Crystallization of Zeolite liquid through row separate, obtain Beta molecular sieve solid and mother liquor, will
Beta molecular sieve solid obtains total silicon Beta molecular screen primary powder through drying, roasting；
（6）To step（5）Obtained in Beta molecular sieve mother liquor repeat step（2）Extremely（5）Operation, reach to Beta molecular sieve
Mother liquor recycles.
Further, the step（3）In the silicon source added be selected from silica solution, waterglass, tetraethyl orthosilicate or silica gel
One of or it is a variety of.
Further, the step（3）Each material mol ratio is in the Beta molecular sieve gel mixture of middle synthesis：
SiO2：Na2O：H2O =1：0.01~0.3：10~150.
Further, the step（3）In the template added be selected from tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide,
N-butylamine, 4-propyl bromide or triethanolamine it is one or more；And the step（3）In the template added with add
SiO in silicon source2Mass ratio be 1：0.02~0.45.
Further, without adding silicon source.
Further, described program temperature-raising method is to be warming up to 120~180 DEG C from room temperature with 2~20 DEG C/h of rate,
Crystallization time is 24~120 hours, obtains Beta Crystallization of Zeolite liquid.
The device have the advantages that：
The method of the invention on the one hand can effectively shorten synthesis favorable dispersibility total silicon Beta molecular sieve generated time；
Due to using programmed temperature method, it is nucleated activation energy reducing molecular sieve, nucleation rate is improved, reduces the same of the particle size of sample
When, the crystallization process of molecular sieve is accelerated, the crystallization period is shortened, and keeps the crystallinity of the molecular sieve of synthesis higher；It is another
Aspect is recycled mother liquor, can significantly reduce production cost, also reduces the pollution to environment.
Detailed description of the invention
Fig. 1 is the XRD spectrum of comparative example 1；
Fig. 2 is the electromicroscopic photograph of comparative example 1；
Fig. 3 is the XRD spectrum of embodiment 1；
Fig. 4 is the electromicroscopic photograph of embodiment 1；
Fig. 5 is the XRD spectrum of comparative example 2；
Fig. 6 is the electromicroscopic photograph of comparative example 2；
Fig. 7 is the XRD spectrum of embodiment 2；
Fig. 8 is the electromicroscopic photograph of embodiment 2；
Fig. 9 is the XRD spectrum of comparative example 3；
Figure 10 is the electromicroscopic photograph of comparative example 3；
Figure 11 is the XRD spectrum of embodiment 3；
Figure 12 is the electromicroscopic photograph of embodiment 3.
Specific embodiment
The present invention will be further described below with reference to examples, but protection scope of the present invention is not limited solely to implement
Example.（Template selects tetraethyl ammonium hydroxide in example）
Comparative example 1
4.3gNaOH is added in 180.2g distilled water, solution is stirred to clarify.The silica solution of 200g is delayed under magnetic agitation
Slowly it is added drop-wise to formation silicate gel A in above-mentioned mixed solution；A certain amount of tetraethyl ammonium hydroxide is weighed, wherein be added four
The mass ratio of SiO2 is 0.25 in ethyl ammonium hydroxide and silicate gel, and above-mentioned tetraethyl ammonium hydroxide is dissolved in 30.8g's
It is stirred in deionized water to being completely dissolved, obtains mixed solution B, be slowly added to make to mix in A gel by solution B under agitation
It closes uniformly, finally mixture is transferred in the stainless steel crystallization kettle of teflon lined, from room temperature with 5 DEG C/h
130 DEG C are warming up to, then crystallization 120 hours under the conditions of 130 DEG C；Product is separated, and Beta molecular sieve solid and mother liquor are obtained,
Beta molecular sieve solid is washed, obtain total silicon Beta molecular screen primary powder after dry 14h, 550 DEG C of roasting 10h at 85 DEG C；
Embodiment 1
By the crystallization mother liquor 114.2g (SiO in comparative example 12：17.7g/L；Na2O：It 23.3g/L) mixes, is added with 16g water
3.7gNaOH stirs to clarify solution.The silica solution of 120g is slowly dropped in above-mentioned mixed solution under magnetic agitation and is formed
Silicate gel A；A certain amount of tetraethyl ammonium hydroxide is weighed, wherein in the tetraethyl ammonium hydroxide and silicate gel that are added
SiO2Mass ratio be 1：0.25, above-mentioned tetraethyl ammonium hydroxide is dissolved in the deionized water of 30.8g and is stirred to being completely dissolved,
Mixed solution B is obtained, is slowly added to make to be uniformly mixed in A gel by solution B under agitation, is finally transferred to mixture poly-
In the stainless steel crystallizing kettle of tetrafluoroethene lining, 130 DEG C are warming up to from room temperature with 5 DEG C/h, then under the conditions of 130 DEG C
Crystallization 120 hours；Product is separated, and Beta molecular sieve solid and mother liquor are obtained, Beta molecular sieve solid is washed, at 85 DEG C
Total silicon Beta molecular screen primary powder is obtained after dry 14h, 550 DEG C of roasting 10h；
Comparative example 2
7.04gNaOH is added in 130.2g distilled water, solution is stirred to clarify.The silica solution of 150g is delayed under magnetic agitation
Slowly it is added drop-wise to formation silicate gel A in above-mentioned mixed solution；A certain amount of tetraethyl ammonium hydroxide is weighed, wherein be added four
The mass ratio of SiO2 is 0.25 in ethyl ammonium hydroxide and silicate gel, and above-mentioned tetraethyl ammonium hydroxide is dissolved in 30.8g's
It is stirred in deionized water to being completely dissolved, obtains mixed solution B, be slowly added to make to mix in A gel by solution B under agitation
It closes uniformly, finally mixture is transferred in the stainless steel crystallizing kettle of teflon lined, heat up from room temperature with 10 DEG C/h
To 120 DEG C, then crystallization 72 hours under the conditions of 130 DEG C；Product is separated, and Beta molecular sieve solid and mother liquor are obtained, will
Beta molecular sieve solid is washed, obtains total silicon Beta molecular screen primary powder after dry 14h, 550 DEG C of roasting 10h at 85 DEG C；
Embodiment 2
By the crystallization mother liquor 110.2g (SiO in comparative example 22：17.7g/L；Na2O：It 23.3g/L) mixes, adds with 20g water
Enter 3.9gNaOH, stirs to clarify solution.The silica solution of 125g is slowly dropped to shape in above-mentioned mixed solution under magnetic agitation
At aluminosilicate gels A；A certain amount of tetraethyl ammonium hydroxide is weighed, wherein the tetraethyl ammonium hydroxide being added and silicate are solidifying
SiO in glue2Mass ratio be 1：0.25, above-mentioned tetraethyl ammonium hydroxide is dissolved in the deionized water of 30.8g and is stirred to complete
Dissolution, obtains mixed solution B, is slowly added to make to be uniformly mixed in A gel by solution B under agitation, finally by mixture
It is transferred in the stainless steel crystallizing kettle of teflon lined, 130 DEG C is warming up to from room temperature with 10 DEG C/h, then at 130 DEG C
Under the conditions of crystallization 72 hours；Product is separated, and Beta molecular sieve solid and mother liquor are obtained, Beta molecular sieve solid is washed,
Total silicon Beta molecular screen primary powder is obtained after dry 14h, 550 DEG C of roasting 10h at 85 DEG C；
Comparative example 3
7.04gNaOH is added in 130.2g distilled water, solution is stirred to clarify.The silica solution of 150g is delayed under magnetic agitation
Slowly it is added drop-wise to formation silicate gel A in above-mentioned mixed solution；A certain amount of tetraethyl ammonium hydroxide is weighed, wherein be added four
SiO in ethyl ammonium hydroxide and silicate gel2Mass ratio be 1：0.25, above-mentioned tetraethyl ammonium hydroxide is dissolved in 30.8g
Deionized water in stir to being completely dissolved, obtain mixed solution B, be slowly added to make in A gel by solution B under agitation
It is uniformly mixed, finally mixture is transferred in the stainless steel crystallizing kettle of teflon lined, heat up from room temperature with 5 DEG C/h
To 150 DEG C, then crystallization 24 hours under the conditions of 150 DEG C；Product is separated, and Beta molecular sieve solid and mother liquor are obtained, will
Beta molecular sieve solid is washed, obtains total silicon Beta molecular screen primary powder after dry 14h, 550 DEG C of roasting 10h at 85 DEG C；
Embodiment 3
By the crystallization mother liquor 113.4g (SiO in comparative example 32：65g/L；Na2O：It 25.6g/L) mixes, adds with 16.8g water
Enter 4.1gNaOH, stirs to clarify solution.The silica solution of 120g is slowly dropped to shape in above-mentioned mixed solution under magnetic agitation
At silicate gel A；A certain amount of tetraethyl ammonium hydroxide is weighed, wherein the tetraethyl ammonium hydroxide and silicate gel that are added
Middle SiO2Mass ratio be 1：0.25, above-mentioned tetraethyl ammonium hydroxide is dissolved in the deionized water of 30.8g and is stirred to completely molten
Solution, obtains mixed solution B, is slowly added to make to be uniformly mixed in A gel by solution B under agitation, finally turns mixture
Enter in the stainless steel crystallizing kettle of teflon lined, 150 DEG C is warming up to from room temperature with 5 DEG C/h, then in 150 DEG C of conditions
Lower crystallization 24 hours；Product is separated, and Beta molecular sieve solid and mother liquor are obtained, Beta molecular sieve solid is washed, 85 DEG C
Total silicon Beta molecular screen primary powder is obtained after lower dry 14h, 550 DEG C of roasting 10h.
From Fig. 1 compared with Fig. 3 result, it is apparent that in the reaction kettle unit volume obtained using the method for the present invention
The grain crystalline of ZSM-5 molecular sieve improves；From Fig. 2 compared with Fig. 4 result, it is apparent that being obtained using the method for the present invention
Reaction kettle unit volume in the particle size of ZSM-5 molecular sieve be substantially reduced；From Fig. 6, result can be obviously compared with Fig. 8
Out, the particle size of ZSM-5 molecular sieve is substantially reduced in the reaction kettle unit volume obtained using the method for the present invention；From Fig. 9 with
Figure 11 compare result, it is apparent that using the method for the present invention obtain reaction kettle unit volume in ZSM-5 molecular sieve knot
Crystalline substance significantly improves.
Finally it should be noted that：Above embodiments are only to illustrate the present invention and not limit technology described in the invention
Scheme, therefore, although this specification is referring to above-mentioned each embodiment, the present invention has been described in detail, this
Field it is to be appreciated by one skilled in the art that still can modify to the present invention or equivalent replacement, and all do not depart from this
The technical solution and its improvement of the spirit and scope of invention, should all cover within the scope of the claims of the present invention.
Claims (6)
1. a kind of recoverying and utilizing method using programmed temperature method synthesis total silicon Beta molecular sieve mother liquor, it is characterised in that：It will
Mother liquor after Beta Crystallization of Zeolite is recycled, then is continued to use mother liquor as Beta Zeolite synthesis raw material, including step
Suddenly：
（1）By first time, the molecular sieve solid product of synthesis is separated, the mother liquor after recycling first time Zeolite synthesis；
（2）Analytical procedure（1）In SiO in the mother liquor that is recovered to2、Na2O、OH-, template content；
（3）According to the content of each component in mother liquor, silicon source, template, sodium hydroxide, He Shui are added in proportion, are configured to synthesize
Beta molecular sieve gel mixture；
（4）By step（3）Obtained in Beta molecular sieve gel mixture be fitted into the reaction kettle of polytetrafluoroethyllining lining, use
Programmed temperature method crystallization obtains corresponding Beta Crystallization of Zeolite liquid for a period of time；
（5）By step（4）Obtained in Beta Crystallization of Zeolite liquid through row separate, obtain Beta molecular sieve solid and mother liquor, will
Beta molecular sieve solid obtains total silicon Beta molecular screen primary powder through drying, roasting；
（6）To step（5）Obtained in Beta molecular sieve mother liquor repeat step（2）Extremely（5）Operation, reach to Beta molecular sieve
Mother liquor recycles.
2. the recoverying and utilizing method according to claim 1 using programmed temperature method synthesis total silicon Beta molecular sieve mother liquor,
It is characterized in that：The step（3）In the silicon source added in silica solution, waterglass, tetraethyl orthosilicate or silica gel one
Kind is a variety of.
3. the recoverying and utilizing method according to claim 1 using programmed temperature method synthesis total silicon Beta molecular sieve mother liquor,
It is characterized in that：The step（3）Each material mol ratio is in the Beta molecular sieve gel mixture of middle synthesis：SiO2：Na2O：
H2O =1：0.01~0.3：10~150.
4. the recoverying and utilizing method according to claim 1 using programmed temperature method synthesis total silicon Beta molecular sieve mother liquor,
It is characterized in that：The step（3）In the template added be selected from tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, n-butylamine,
4-propyl bromide or triethanolamine it is one or more；And the step（3）In the template added in the silicon source added
SiO2Mass ratio be 1：0.02~0.45.
5. the recoverying and utilizing method according to claim 1 using programmed temperature method synthesis total silicon Beta molecular sieve mother liquor,
It is characterized in that：Without adding silicon source.
6. the recoverying and utilizing method according to claim 1 using programmed temperature method synthesis total silicon Beta molecular sieve mother liquor,
It is characterized in that：Described program temperature-raising method is to be warming up to 120~180 DEG C from room temperature with 2~20 DEG C/h of rate, when crystallization
Between be 24~120 hours, obtain Beta Crystallization of Zeolite liquid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482565A (en) * | 2019-09-11 | 2019-11-22 | 江苏国瓷天诺新材料科技股份有限公司 | A method of utilizing total silicon Beta crystallization mother liquor synthesizing low silicon aluminium ratio Beta molecular sieve |
| CN113636566A (en) * | 2021-08-05 | 2021-11-12 | 肯特催化材料股份有限公司 | All-silicon Beta molecular sieve synthesis process and all-silicon Beta molecular sieve prepared by same |
| CN113753910A (en) * | 2020-06-03 | 2021-12-07 | 中国石油化工股份有限公司 | Method for treating crystallization mother liquor of mordenite molecular sieve |
| CN118724008A (en) * | 2024-08-30 | 2024-10-01 | 吉林大学 | A method for preparing silicalite-1 molecular sieve by circulating crystallization mother solution |
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2018
- 2018-08-31 CN CN201811006954.8A patent/CN108910911A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482565A (en) * | 2019-09-11 | 2019-11-22 | 江苏国瓷天诺新材料科技股份有限公司 | A method of utilizing total silicon Beta crystallization mother liquor synthesizing low silicon aluminium ratio Beta molecular sieve |
| CN113753910A (en) * | 2020-06-03 | 2021-12-07 | 中国石油化工股份有限公司 | Method for treating crystallization mother liquor of mordenite molecular sieve |
| CN113753910B (en) * | 2020-06-03 | 2023-03-28 | 中国石油化工股份有限公司 | Method for treating crystallization mother liquor of mordenite molecular sieve |
| CN113636566A (en) * | 2021-08-05 | 2021-11-12 | 肯特催化材料股份有限公司 | All-silicon Beta molecular sieve synthesis process and all-silicon Beta molecular sieve prepared by same |
| CN113636566B (en) * | 2021-08-05 | 2023-03-21 | 肯特催化材料股份有限公司 | All-silicon Beta molecular sieve synthesis process and all-silicon Beta molecular sieve prepared by same |
| CN118724008A (en) * | 2024-08-30 | 2024-10-01 | 吉林大学 | A method for preparing silicalite-1 molecular sieve by circulating crystallization mother solution |
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