CN102285667A - Method for efficiently synthesizing beta molecular sieve without using organic template - Google Patents
Method for efficiently synthesizing beta molecular sieve without using organic template Download PDFInfo
- Publication number
- CN102285667A CN102285667A CN 201110154662 CN201110154662A CN102285667A CN 102285667 A CN102285667 A CN 102285667A CN 201110154662 CN201110154662 CN 201110154662 CN 201110154662 A CN201110154662 A CN 201110154662A CN 102285667 A CN102285667 A CN 102285667A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- beta molecular
- source
- beta
- sio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to the synthesis of a beta molecular sieve without using an organic template and aims to provide a method for efficiently synthesizing a beta molecular sieve without using an organic template. The method comprises: dissolving an alkali metal oxide source and an alumina source in water, adding a silicon dioxide source, and stirring and mixing at room temperature to form aluminosilicate solution; adding beta molecular sieve into aluminosilicate solution as a crystal seed and crystallizing and synthesizing the beta molecular sieve in a hydrothermal manner; and cooling at room temperature after the reaction is finished, washing the solid crystals till the pH value is 7.0, and drying to obtain beta molecular sieve powder. In the invention, the finally obtained beta molecular sieve is used as a crystal seed, and the mother solution obtained after crystallization is fully used and is reused in a new beta molecular sieve synthesis process. The method disclosed by the invention well meet the requirements on use of zeolite molecular sieve in industry. When the method is used, the unit yield is increased, the production efficiency is increased, the effective utilization of the raw material is increased, and the cost is reduced; and the method for synthesizing beta molecular sieve without using the organic template can better meet the requirements for industrial use.
Description
Technical field
The invention belongs to inorganic chemistry, physical chemistry, materials chemistry, catalytic chemistry and field of chemical engineering, specially refer to employing silica gel and do the silicon source and do not have the method that organic formwork does not have the synthetic Beta zeolite molecular sieve of template.
Background technology
Traditional B eta molecular sieve is at TEA
+Prepare under the condition Deng the organic formwork existence, have very significant disadvantages: the price of organic formwork agent is relatively very high; Remove organic formwork agent in the molecular sieve and use the method for high temperature sintering usually, will produce a large amount of obnoxious flavoures, contaminate environment like this.
People such as Xiao Fengshou successfully synthesize Beta zeolite molecular sieve (CN Patent No101249968A) under the organic-free template condition, denomination of invention is " no organic formwork does not have the method for the synthetic Beta molecular sieve of template ".The feed molar proportioning of the initial silicon alumina gel of the synthetic Beta molecular sieve of this patent disclosure is: SiO
2/ Al
2O
3=31.4～40.3, Na
2O/SiO
2=0.260～0.342, H
2O/SiO
2=13～50; The mol ratio of Beta zeolite seed crystal is SiO
2/ Al
2O
3=22～25, the amount of adding is 5%～20% of a silica source by quality.Though this method has been avoided the use of organic formwork, has reduced production cost, exist the drawback of no organic formwork synthesis of molecular sieve inevitably, it is low etc. for example to be easy to generate stray crystal, raw material availability.The present utilization ratio lower (25-35%) in the silicon source of this method particularly, crystal seed can not reuse, and the higher single-autoclave yield rate that causes simultaneously of the consumption of water reduces restriction production efficiency.
Therefore, improve the unit output of synthetic Beta molecular sieve under the no organic formwork condition, greatly reduce production costs and energy consumption; The various components that make full use of mother liquor simultaneously synthesize the measured Beta molecular sieve of matter; And product can continue to utilize in synthetic as crystal seed again, and these all are the problems that the Beta heavy industrialization must solve.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of and utilizes silica gel to do the silicon source not have template, the method for efficient synthetic Beta molecular sieve under no organic formwork condition.
The solution that the present invention proposes is:
The method of efficient synthetic Beta molecular sieve under no organic formwork condition comprises step:
(1) alkalimetal oxide source, alumina source are dissolved in the water, add silica source again, stirring at room is mixed 1～4 hour formation sial solution; Control the add-on of each reactant, make to possess following molar ratio relation: Na in the sial solution
2O/SiO
2=0.188～0.376, SiO
2/ Al
2O
3=20.0～40.0, H
2O/SiO
2=8～12;
(2) add-on by silicon-dioxide source quality 1.0～20.0% adds SiO in sial solution
2/ Al
2O
3=20～28 Beta molecular sieve is as crystal seed, and crystallization is 0.5～8 day under 100～180 ℃ of conditions, and hydro-thermal is synthesized the Beta molecular sieve; The room temperature cooling separated solid crystallized product after reaction was finished with mother liquor, and to neutrality, drying obtains the Beta molecular sieve powder with deionized water wash.
The present invention can use the industrial Beta zeolite that is provided by molecular sieve factory of Nankai as the Beta molecular sieve of crystal seed, also can use other Beta molecular sieve baked or not roasting to do crystal seed, the SiO of crystal seed
2/ Al
2O
3=20～28.The amount of the Beta zeolite seed crystal that adds is 1～20% of a silica source by quality optimization.Select SiO
2/ Al
2O
3Different Beta zeolites are done crystal seed, and are little to silica alumina ratio, the degree of crystallinity influence of the finished product.
Crystallization temperature of the present invention can be the crystallization temperature of common synthesis of molecular sieve, as 130～150 ℃ of background technology; Preferred crystallization temperature is at 100～180 ℃, and preferred crystallization time is at 0.5～8d.
Among the present invention, as the application method of expansion, the Beta molecular sieve that is finally acquisition continues to use in the process of the synthetic Beta molecular sieve of a new round as crystal seed.
Among the present invention, be that the mother liquor after the crystallization is made full use of as the application of expanding: after solid crystallized product and mother liquor static layering, get the Beta sieve synthesis procedure that supernatant liquor is used for a new round.
By the application mode of above-mentioned expansion, can be among the present invention with the silicon source (with SiO
2Meter) utilization ratio is brought up to more than 85%.
Among the present invention, described alkalimetal oxide source is a sodium hydroxide.
Among the present invention, described alumina source is sodium aluminate or Tai-Ace S 150.
Among the present invention, described silica source is silica solid or the white carbon black that contains 1～3% water.Silica source can be silica gel (Qingdao silica gel factory), also can be white carbon black (chemical plant, Shenyang)
The invention has the beneficial effects as follows:
Because the molecular sieve industrial applications cost problem that must consider to produce molecular sieve, in addition, the synthetic organic formwork agent that all needs of most of molecular sieves can damage and environment is polluted during the burn off organic formwork agent simultaneously framework of molecular sieve.Method disclosed by the invention by optimizing synthesis condition, has well adapted to the requirement of industrial application zeolite molecular sieve.Improved the unit productive rate, improved the efficient of producing, improved raw-material effective rate of utilization simultaneously, lowered cost, the method that makes no organic formwork synthesize the Beta molecular sieve more meets the requirement of industrial applications.
Description of drawings
Fig. 1 is the XRD spectra of the embodiment of the invention 1 synthetic Beta molecular sieve.
Fig. 2 is the XRD spectra of the embodiment of the invention 2 synthetic Beta molecular sieves.
Fig. 3 is the XRD spectra of the embodiment of the invention 3 synthetic Beta molecular sieves.
Fig. 4 is the XRD spectra of the embodiment of the invention 3 synthetic Beta molecular sieves.
Fig. 5 is the XRD spectra that the embodiment of the invention 3 mother liquors reuse synthetic Beta molecular sieve after 1 time.
Fig. 6 is the XRD spectra that the embodiment of the invention 3 mother liquors reuse synthetic Beta molecular sieve after 2 times.
Fig. 7 is the XRD spectra that the embodiment of the invention 3 mother liquors reuse synthetic Beta molecular sieve after 3 times.
Fig. 8 is the XRD spectra of the embodiment of the invention 4 synthetic Beta molecular sieves.
Fig. 9 is the XRD spectra that the embodiment of the invention 4 crystal seeds reuse synthetic Beta molecular sieve after 1 time.
Figure 10 is the XRD spectra that the embodiment of the invention 4 crystal seeds reuse synthetic Beta molecular sieve after 2 times.
Embodiment
Embodiment 1
Material molar ratio is as follows: 20.08SiO
2/ 1.00Al
2O
3/ 7.56Na
2O/160H
2O, H here
2O/SiO
2Be 8.Concrete building-up process is as follows: 0.41gNaAlO
2: and 0.87gNaOH is dissolved in the H of 5.06ml
2Among the O, after waiting to dissolve, 2.11g silica gel is joined in the above-mentioned solution.After stirring about 1～3h, 0.1gBeta molecular sieve crystal seed is joined in the above-mentioned solution, continue stirring at room 10～15 minutes.Afterwards, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 100 ℃ of conditions, crystallization 8d.After the cooling, filter in room temperature, 100 ℃ of dried overnight can obtain product.Process x-ray diffractometer is obtained and is known that product is the very high Beta molecular sieve of degree of crystallinity, as Fig. 1.Obtain product 0.91g, silicon source effective rate of utilization 43%.
Embodiment 2
Material molar ratio is as follows: 40.08SiO
2/ 1.00Al
2O
3/ 7.56Na
2O/480H
2O, H here
2O/SiO
2Be 12.Concrete building-up process is as follows: 0.34gAl
2(SO
4)
3Be dissolved in the H of 8.6ml with 0.60gNaOH
2Among the O, after waiting to dissolve, the white carbon black of 2.39g is joined in the above-mentioned solution.After stirring about 1～3h, 0.086gBeta molecular sieve crystal seed is joined in the above-mentioned solution, continue stirring at room 10～15 minutes.Afterwards, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 180 ℃ of conditions, crystallization 0.5d.After the cooling, filter in room temperature, 100 ℃ of dried overnight can obtain product.Process x-ray diffractometer is obtained and is known that product is the Beta molecular sieve, as Fig. 2.Obtain product 0.78g, silicon source effective rate of utilization 33%.
Embodiment 3
Material molar ratio is as follows: 30.08SiO
2/ 1.00Al
2O
3/ 7.56Na
2O/300H
2O, H here
2O/SiO
2Be 10.Concrete building-up process is as follows: 0.90gAl
2(SO
4)
3: and 1.06gNaOH is dissolved in the H of 9.49ml
2Among the O, after waiting to dissolve, 2.11g silica gel is joined in the above-mentioned solution.After stirring about 1～3h, 0.1gBeta molecular sieve crystal seed is joined in the above-mentioned solution, continue stirring at room 10～15 minutes.Afterwards, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 ℃ of conditions, crystallization 5d.After the cooling, filter, obtain mother liquor and product separately in room temperature.100 ℃ of dried overnight of product can obtain product.Process x-ray diffractometer is obtained and is known that product is the Beta molecular sieve, as Fig. 3.Obtain product 1.32g, silicon source effective rate of utilization 42%.In mother liquor, replenish certain silicon source, aluminium source and alkali source and make composition and initial gel phase seemingly.Add 0.1gBeta molecular sieve crystal seed, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 ℃ of conditions, crystallization 5d.After the cooling, filter, obtain mother liquor and product separately in room temperature.100 ℃ of dried overnight of product can obtain product.Process x-ray diffractometer is obtained and is known that product is the Beta molecular sieve, as Fig. 4.Obtain product 1.2g, the total effective rate of utilization 61% in silicon source is replenished certain silicon source, aluminium source and alkali source and is made composition and initial gel phase seemingly in mother liquor.Add 0.1gBeta molecular sieve crystal seed, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 ℃ of conditions, crystallization 5d.After the cooling, filter, obtain mother liquor and product separately in room temperature.100 ℃ of dried overnight of product can obtain product.Process x-ray diffractometer is obtained and is known that product is the Beta molecular sieve, as Fig. 5.Obtain product 1.18g, the total effective rate of utilization 72% in silicon source.In mother liquor, replenish certain silicon source, aluminium source and alkali source and make composition and initial gel phase seemingly.Add 0.1gBeta molecular sieve crystal seed, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 ℃ of conditions, crystallization 5d.After the cooling, filter, obtain mother liquor and product separately in room temperature.100 ℃ of dried overnight of product can obtain product.Process x-ray diffractometer is obtained and is known that product is the Beta molecular sieve, as Fig. 6.Obtain product 1.16g, the total effective rate of utilization 80% in silicon source.In mother liquor, replenish certain silicon source, aluminium source and alkali source and make composition and initial gel phase seemingly.Add 0.1gBeta molecular sieve crystal seed, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 ℃ of conditions, crystallization 5d.After the cooling, filter, obtain mother liquor and product separately in room temperature.100 ℃ of dried overnight of product can obtain product.Process x-ray diffractometer is obtained and is known that product is the Beta molecular sieve, as Fig. 7.Obtain product 1.12g, the total effective rate of utilization in silicon source reaches 85%.
Embodiment 4
Material molar ratio is as follows: 20.08SiO
2/ 1.00Al
2O
3/ 7.56Na
2O/160H
2O, H here
2O/SiO
2Be 8.Concrete building-up process is as follows: 0.60gAl2 (SO4) 3: and 1.06gNaOH is dissolved in the H of 5.06ml
2Among the O, after waiting to dissolve, 2.11g silica gel is joined in the above-mentioned solution.After stirring about 1～3h, 0.1gBeta molecular sieve crystal seed is joined in the above-mentioned solution, continue stirring at room 10～15 minutes.Afterwards, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 ℃ of conditions, crystallization 5d.After the cooling, filter, obtain mother liquor and product separately in room temperature.100 ℃ of dried overnight of product can obtain product.Process x-ray diffractometer is obtained and is known that product is the Beta molecular sieve, as Fig. 8.Obtain product 0.88g, silicon source effective rate of utilization 42%.The product that obtains is used as crystal seed.After joining in the above-mentioned similar gel, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 ℃ of conditions, crystallization 5d.After the cooling, filter, obtain mother liquor and product separately in room temperature.100 ℃ of dried overnight of product can obtain product.Process x-ray diffractometer is obtained and is known that product is the Beta molecular sieve, as Fig. 9.Obtain product 0.86g, silicon source effective rate of utilization 41%.The product that obtains is reused as crystal seed.After joining in the above-mentioned similar gel, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 ℃ of conditions, crystallization 5d.After the cooling, filter, obtain mother liquor and product separately in room temperature.100 ℃ of dried overnight of product can obtain product.Process x-ray diffractometer is obtained and is known that product is the Beta molecular sieve, as Figure 10.Obtain product 0.83g, silicon source effective rate of utilization 40%.
Claims (6)
1. under no organic formwork condition, efficiently synthesize the method for Beta molecular sieve, comprise step:
(1) alkalimetal oxide source, alumina source are dissolved in the water, add silica source again, stirring at room is mixed 1～4 hour formation sial solution; Control the add-on of each reactant, make to possess following molar ratio relation: Na in the sial solution
2O/SiO
2=0.188～0.376, SiO
2/ Al
2O
3=20.0～40.0, H
2O/SiO
2=8～12;
(2) add-on by silicon-dioxide source quality 1.0～20.0% adds SiO in sial solution
2/ Al
2O
3=20～28 Beta molecular sieve is as crystal seed, and crystallization is 0.5～8 day under 100～180 ℃ of conditions, and hydro-thermal is synthesized the Beta molecular sieve; The room temperature cooling separated solid crystallized product after reaction was finished with mother liquor, and to neutrality, drying obtains the Beta molecular sieve powder with deionized water wash.
2. method according to claim 1 is characterized in that, the Beta molecular sieve that finally obtains as crystal seed, is continued to use in the process of the synthetic Beta molecular sieve of a new round.
3. method according to claim 1 is characterized in that, the mother liquor after the crystallization is made full use of: after solid crystallized product and mother liquor static layering, get the Beta sieve synthesis procedure that supernatant liquor is used for a new round.
4. according to the method described in any one of the claim 1 to 3, it is characterized in that described alkalimetal oxide source is a sodium hydroxide.
5. according to the method described in any one of the claim 1 to 3, it is characterized in that described alumina source is sodium aluminate or Tai-Ace S 150.
6. according to the method described in any one of the claim 1 to 3, it is characterized in that described silica source is silica solid or the white carbon black that contains 1～3% water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110154662 CN102285667A (en) | 2011-06-09 | 2011-06-09 | Method for efficiently synthesizing beta molecular sieve without using organic template |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110154662 CN102285667A (en) | 2011-06-09 | 2011-06-09 | Method for efficiently synthesizing beta molecular sieve without using organic template |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102285667A true CN102285667A (en) | 2011-12-21 |
Family
ID=45332456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110154662 Pending CN102285667A (en) | 2011-06-09 | 2011-06-09 | Method for efficiently synthesizing beta molecular sieve without using organic template |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102285667A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992343A (en) * | 2012-12-09 | 2013-03-27 | 浙江大学 | Method for synthesizing zeolite molecular sieve via solid phase method without organic template |
| CN103204517A (en) * | 2012-01-16 | 2013-07-17 | 湖北大学 | Method for synthesizing microporous molecular sieve with methylene doped in skeleton without template |
| CN104649290A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Organic-template-free [beta]-molecular sieve synthesizing method |
| CN104649296A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | H[beta] molecular sieve preparing method capable of increasing silicon-aluminum ratio |
| CN105271287A (en) * | 2015-10-10 | 2016-01-27 | 吉林大学 | Method for preparation of Beta molecular sieve from modified diatomite without organic template |
| CN105540605A (en) * | 2014-10-30 | 2016-05-04 | 中国石油化工股份有限公司 | Aluminum-rich Beta Zeolite synthesis method |
| CN106000454A (en) * | 2016-05-20 | 2016-10-12 | 浙江大学 | Method for preparing metal@ zeolite single crystal capsule catalytic material without organic template |
| CN107416859A (en) * | 2017-04-24 | 2017-12-01 | 福州大学 | A kind of preparation method and application of step hole Beta molecular sieves |
| US10899971B2 (en) | 2019-02-13 | 2021-01-26 | Exxonmobil Research And Engineering Company | Stabilization of zeolite beta for FCC processes |
| CN112441598A (en) * | 2020-12-15 | 2021-03-05 | 山东齐鲁华信高科有限公司 | Preparation method of mesoporous Beta molecular sieve |
| CN115245838A (en) * | 2022-06-16 | 2022-10-28 | 天津大学 | T molecular sieve rapid synthesis method, catalyst and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154342A (en) * | 1996-01-11 | 1997-07-16 | 中国石油化工总公司 | Method for synthesis of beta-zeolite |
| CN101249968A (en) * | 2008-03-10 | 2008-08-27 | 吉林大学 | Method for synthesizing Beta molecular sieve by organic-free template |
-
2011
- 2011-06-09 CN CN 201110154662 patent/CN102285667A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154342A (en) * | 1996-01-11 | 1997-07-16 | 中国石油化工总公司 | Method for synthesis of beta-zeolite |
| CN101249968A (en) * | 2008-03-10 | 2008-08-27 | 吉林大学 | Method for synthesizing Beta molecular sieve by organic-free template |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204517A (en) * | 2012-01-16 | 2013-07-17 | 湖北大学 | Method for synthesizing microporous molecular sieve with methylene doped in skeleton without template |
| WO2014086300A1 (en) * | 2012-12-09 | 2014-06-12 | Basf Se | Organotemplate-free solid-state synthetic method for zeolite molecular sieves |
| US10160656B2 (en) | 2012-12-09 | 2018-12-25 | Basf Se | Organotemplate-free solid-state synthetic method for zeolite molecular sieves |
| CN102992343A (en) * | 2012-12-09 | 2013-03-27 | 浙江大学 | Method for synthesizing zeolite molecular sieve via solid phase method without organic template |
| CN104649290B (en) * | 2013-11-19 | 2017-02-15 | 中国石油天然气股份有限公司 | Organic-template-free [beta]-molecular sieve synthesizing method |
| CN104649290A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Organic-template-free [beta]-molecular sieve synthesizing method |
| CN104649296A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | H[beta] molecular sieve preparing method capable of increasing silicon-aluminum ratio |
| CN105540605A (en) * | 2014-10-30 | 2016-05-04 | 中国石油化工股份有限公司 | Aluminum-rich Beta Zeolite synthesis method |
| CN105540605B (en) * | 2014-10-30 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of method of synthesizing aluminum-enriched Beta zeolites |
| CN105271287A (en) * | 2015-10-10 | 2016-01-27 | 吉林大学 | Method for preparation of Beta molecular sieve from modified diatomite without organic template |
| CN106000454A (en) * | 2016-05-20 | 2016-10-12 | 浙江大学 | Method for preparing metal@ zeolite single crystal capsule catalytic material without organic template |
| CN107416859A (en) * | 2017-04-24 | 2017-12-01 | 福州大学 | A kind of preparation method and application of step hole Beta molecular sieves |
| US10899971B2 (en) | 2019-02-13 | 2021-01-26 | Exxonmobil Research And Engineering Company | Stabilization of zeolite beta for FCC processes |
| CN112441598A (en) * | 2020-12-15 | 2021-03-05 | 山东齐鲁华信高科有限公司 | Preparation method of mesoporous Beta molecular sieve |
| CN115245838A (en) * | 2022-06-16 | 2022-10-28 | 天津大学 | T molecular sieve rapid synthesis method, catalyst and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102285667A (en) | Method for efficiently synthesizing beta molecular sieve without using organic template | |
| CN106185977B (en) | A kind of method of green syt ZSM-5 molecular sieve | |
| CN103848439B (en) | Synthetic method of ZSM-5 type molecular sieve | |
| CN101249968B (en) | Method for synthesizing Beta molecular sieve by organic-free template | |
| CN1911800A (en) | Method for preparing white carbon black and pure zeolite molecular sieve using flyash | |
| CN102992343A (en) | Method for synthesizing zeolite molecular sieve via solid phase method without organic template | |
| CN103121695B (en) | Synthetic method of molecular sieve ZSM-5 (zeolite socony mobil-5) with heteroatom-containing frame | |
| CN104724720B (en) | A kind of synthetic method of the molecular sieves of HZSM 5 | |
| CN101962193B (en) | Method for preparing ZSM-34 and heteroatom substituted molecular sieve thereof by using crystal seed synthesis method | |
| CN104291349A (en) | Method for preparing P type molecular sieve by using coal ash as raw material | |
| CN103204516B (en) | Preparation method of FER (Ferritin) zeolite molecular sieve with high silica-alumina ratio | |
| WO2015000254A1 (en) | Method for preparation of mordenite | |
| CN104085899A (en) | Template-free hydrothermal synthesis method of small crystal ZSM-5 molecular sieve | |
| CN103232044A (en) | Synthesis method of nanoscale MCM-49 (Multi Chip Module) molecular sieve | |
| CN109336129A (en) | A kind of method of the illite without templated synthesis multi-stage porous ZSM-5 zeolite molecular sieve | |
| CN110482564B (en) | Method for synthesizing zeolite molecular sieve by treating illite through microwave heating solid-phase acid steam conversion method | |
| CN107601520B (en) | Preparation method of ETS-10 molecular sieve | |
| CN102180478A (en) | Method for synthesizing Beta molecular sieve by using silica gel under the condition without organic template | |
| CN109592696A (en) | A kind of preparation method of nano-sheet clinoptilolite molecular sieve | |
| CN105271287B (en) | A kind of method for preparing Beta molecular sieves under the conditions of without organic formwork by modification infusorial earth | |
| CN101279746A (en) | Method for fast synthesizing ZSM-5 molecular sieve by variable temperature crystallization method | |
| CN104649290B (en) | Organic-template-free [beta]-molecular sieve synthesizing method | |
| CN103539148B (en) | Potassium felspar sand is utilized to produce the method for molecular sieve | |
| CN104671252A (en) | Method for synthesizing and preparing ZSM-22 molecular sieve under conditions of no organic template and no crystal seed | |
| CN101654258A (en) | 4A zeolite molecular sieve based on kaoline synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111221 |