CN102745718B - Synthesis method of sub-micron ZSM-5 molecular sieve - Google Patents
Synthesis method of sub-micron ZSM-5 molecular sieve Download PDFInfo
- Publication number
- CN102745718B CN102745718B CN201210251128.6A CN201210251128A CN102745718B CN 102745718 B CN102745718 B CN 102745718B CN 201210251128 A CN201210251128 A CN 201210251128A CN 102745718 B CN102745718 B CN 102745718B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- zsm
- synthesis
- crystallization
- crystal seed
- 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.)
- Active
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a synthesis method of a sub-micron ZSM-5 molecular sieve, belonging to the field of synthesis of molecular sieves. The method is characterized in that silica gel and water glass are used as a mixed silicon source, aluminum salt is used as an aluminum source, and crystallization is carried out in the presence of an organic template agent to obtain the ZSM-5 molecular sieve. The method is simple to operate, simplifies the synthesis steps of the ZSM-5 molecular sieve, and has the advantage of high synthesis efficiency; and the product has the advantages of high relative degree of crystallization, and complete crystal form, and the grain size ranges from 300nm to 500nm.
Description
Technical field
The present invention relates to a kind of synthetic method of submicron order ZSM-5 molecular sieve, belong to Zeolite synthesis field.
Background technology
There is the ZSM-5 molecular sieve of MFI crystal structure, since open by Mobil oil company of the U.S. from 1972, almost become except Y zeolite, at the field such as petrochemical industry and fine chemistry industry purposes molecular sieve catalytic material the most widely.ZSM-5 molecular sieve may be used for petroleum cracking catalyst and octane enhancing additive, for voluminous liquefied gas and propylene additive, for selecting shape aromatisation, isomerization, alkylation catalyst, for novel environment friendly catalyst, etc.
The synthesis of ZSM-5 molecular sieve, with regard to its synthetic route, can be divided into and have amine method and the large class of non-amine method two.
Non-amine method synthesis ZSM-5 molecular sieve, its maximum advantage is that synthesis cost is lower, and non-environmental-pollution, therefore its scope of application is wider.But its pulp furnish and product silica alumina ratio scope have certain limitation, and its crystal structure or grain size still can not meet various instructions for use completely.
Use template to have amine method to synthesize ZSM-5 molecular sieve, the product silica alumina ratio that substantially can meet in a big way requires and crystal grain requirement.
The feature of little crystal grain or sub-micron ZSM-5 molecular sieve is that zeolite crystal is little, and specific area is large, and number of active center is many, is more conducive to the catalysis efficiency improving molecular sieve catalyst.
But existing template has amine method synthesis ZSM-5 molecular sieve, and combined coefficient is low, and products obtained therefrom relative crystallinity is low, and crystal formation is imperfect.
Summary of the invention
According to the deficiencies in the prior art, the technical problem to be solved in the present invention is: the synthetic method providing a kind of submicron order ZSM-5 molecular sieve, simplifies the synthesis step of ZSM-5 molecular sieve, and improve combined coefficient, products obtained therefrom relative crystallinity is high, and crystal formation is complete.
The technical solution adopted for the present invention to solve the technical problems is: the synthetic method providing a kind of submicron order ZSM-5 molecular sieve, it is characterized in that: with silica gel and waterglass for mixing silicon source, with aluminium salt for aluminium source, crystallization synthesis ZSM-5 molecular sieve under organic formwork agent existence condition.
Described silica gel is powder silica series products.
Add molecular sieve crystal seed in described mixing silicon source, the addition of molecular sieve crystal seed is the 0-10% of total quality of material.
Described aluminium salt is one or more the mixture in aluminum sulfate, aluminium chloride or aluminum nitrate, is wherein preferably aluminum sulfate.
Silica alumina ratio 20-100 in described mixing silicon source and aluminium source.
Described organic formwork agent is organic amine, and wherein organic amine is ethamine, propylamine or n-butylamine.
Described molecular sieve crystal seed joins in water glass solution and fully pulls an oar at 50-100 DEG C.
Described silica gel adds in the mixed serum of waterglass and molecular sieve crystal seed pulls an oar, and then adds aluminium salt, forms the mixed serum of synthesis of molecular sieve, finally adds organic formwork agent and continues making beating.
Described crystallization temperature is 100-200 DEG C, and crystallization time is 10-100h.
Described silica gel and waterglass mixed serum, wherein the pH value of the addition hierarchy of control of waterglass is 11-13.
The invention belongs to a kind of method of synthesizing submicron ZSM-5 molecular sieve under template existence condition.Its zeolite crystal size is in 300-500 nanometer range.
The method of synthesis ZSM-5 molecular sieve provided by the invention, its main feature is using solid silicone and the liquid soluble glass mixture silicon source as synthesis ZSM-5 molecular sieve, thus reach raising synthetic pulp fluid solid content, there is amine to synthesize the object of ZSM-5 molecular sieve under realizing high concentration.
The present invention utilizes the basicity of water glass solution self, meets the basicity requirement of synthetic system, simplifies the synthesis step of ZSM-5 molecular sieve.Other alkaline matters or acidic materials regulation system acid-base value is no longer added in synthetic system.
This synthetic method, simple to operate, combined coefficient is high, and products obtained therefrom relative crystallinity is high, and crystal formation is complete, and grain colony is in 300-500 nanometer.
Synthetic system no longer adds the acid-base value of alkaline matter or acidic materials regulation system, only utilizes the basicity of water glass solution self, meets the basicity requirement of synthetic system, and raw material drops into the adjustment of ratio, must meet the pH value requirement of synthetic system.The additional proportion of the water glass solution in system is the major components of regulation system basicity.Require that synthesis slurry pH value is in 11 ~ 13 scopes.
Adding of mixed serum Middle molecule sieve crystal seed, crystallization rate can be improved.Crystal seed need dissolve in water glass solution 50-100 DEG C of heating condition lower part, forms translucent emulsion.This emulsion play the guiding role to Crystallization of Zeolite.
The synthesis condition of ZSM-5 molecular sieve provided by the present invention, its crystallization temperature General Requirements 100 ~ 200 DEG C of scopes, crystallization time 10 ~ 100 hours.
ZSM-5 molecular sieve provided by the present invention, its BET specific surface area is greater than 350m
2/ g.
The invention has the beneficial effects as follows: this method is simple to operate, simplify the synthesis step of ZSM-5 molecular sieve, combined coefficient is high, and products obtained therefrom relative crystallinity is high, and crystal formation is complete, and grain colony is in 300-500 nanometer.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further:
In an embodiment, said relative crystallinity is the ratio of the peak area sum of 5 characteristic peaks of 2 θ angles between 22.5 ~ 25.0 in respective X-ray diffracting spectrum with product and standard specimen.Molecular sieve specific area adopts nitrogen adsorption BET method to measure.
Embodiment 1
235.3 grams of water glass solutions are added (containing SiO in 25.2 grams of deionized waters
219.9%, containing Na
2o 6.3%), add 3.8 grams of crystal seeds, after making beating evenly, be warming up to 90 DEG C, stir 5 hours continuously, then add solid silicone 8.2 grams (containing SiO
289.3%), after making beating evenly, aluminum sulfate solution 43.5 grams is added (containing Al
2o
37.2%), finally add n-butylamine 10.6 grams, after mixing making beating, in 180 DEG C of crystallization, terminate crystallization after 20 hours, material exchanges after washing through 0.5N hydrochloric acid, and 550 DEG C of Muffle furnace roastings, obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 89%, silica alumina ratio 25, specific area 350m
2/ g, crystallite dimension 400 nanometer.
Embodiment 2
217.5 grams of water glass solutions are added (containing SiO in 56.5 grams of deionized waters
220.5%, containing Na
2o 6.8%), add 3.0 grams of crystal seeds, after making beating evenly, be warming up to 80 DEG C, stir 6 hours continuously, then add solid silicone 18.8 grams (containing SiO
290.7%), after making beating evenly, aluminum sulfate solution 36.2 grams is added (containing Al
2o
37.5%), finally add n-butylamine 11.6 grams, after mixing making beating, in 170 DEG C of crystallization, terminate crystallization after 24 hours, material exchanges after washing through 0.5N hydrochloric acid, and 550 DEG C of Muffle furnace roastings, obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 88%, silica alumina ratio 33, specific area 340m
2/ g, crystallite dimension 300 nanometer.
Embodiment 3
276.4 grams of water glass solutions are added (containing SiO in 97.3 grams of deionized waters
218.5%, containing Na
2o 5.8%), add 4.5 grams of crystal seeds, after making beating evenly, be warming up to 100 DEG C, stir 4 hours continuously, then add solid silicone 23.2 grams (containing SiO
289.3%), after making beating evenly, aluminum sulfate solution 40.6 grams is added (containing Al
2o
37.7%), finally add n-butylamine 15.6 grams, after mixing making beating, in 180 DEG C of crystallization, terminate crystallization after 22 hours, material exchanges after washing through 0.5N hydrochloric acid, and 550 DEG C of Muffle furnace roastings, obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 86, silica alumina ratio 41, specific area 342m
2/ g, crystallite dimension 400 nanometer.
Embodiment 4
261.3 grams of water glass solutions are added (containing SiO in 157.4 grams of deionized waters
219.9%, containing Na
2o 6.3%), add 5.6 grams of crystal seeds, after making beating evenly, be warming up to 80 DEG C, stir 6 hours continuously, then add solid silicone 32.6 grams (containing SiO
289.3%), after making beating evenly, aluminum nitrate solution 39.1 grams is added (containing Al
2o
37.2%), finally add n-butylamine 18.9 grams, after mixing making beating, in 175 DEG C of crystallization, terminate crystallization after 24 hours, material exchanges after washing through 0.5N hydrochloric acid, and 550 DEG C of Muffle furnace roastings, obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 89%, silica alumina ratio 45, specific area 345m
2/ g, crystallite dimension 300 nanometer.
Embodiment 5
285.3 grams of water glass solutions are added (containing SiO in 134.5 grams of deionized waters
218.5%, containing Na
2o 5.8%), add 5.5 grams of crystal seeds, after making beating evenly, be warming up to 90 DEG C, stir 6 hours continuously, then add solid silicone 24.8 grams (containing SiO
289.3%), after making beating evenly, aluminium chloride and aluminum sulfate solution 34.7 grams is added (containing Al
2o
37.7%), finally add n-butylamine 19.5 grams, after mixing making beating, in 180 DEG C of crystallization, terminate crystallization after 20 hours, material exchanges after washing through 0.5N hydrochloric acid, and 550 DEG C of Muffle furnace roastings, obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 85%, silica alumina ratio 45, specific area 335m
2/ g, crystallite dimension 400 nanometer.
Embodiment 6
331.2 grams of water glass solutions are added (containing SiO in 167.3 grams of deionized waters
219.9%, containing Na
2o 6.3%), after making beating evenly, be warming up to 100 DEG C, stir 5 hours continuously, then add solid silicone 31.2 grams (containing SiO
289.3%), after making beating evenly, aluminum sulfate solution 37.7 grams is added (containing Al
2o
37.2%), finally add n-butylamine 23.1 grams, after mixing making beating, in 160 DEG C of crystallization, terminate crystallization after 100 hours, material exchanges after washing through 0.5N hydrochloric acid, and 550 DEG C of Muffle furnace roastings, obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 82%, silica alumina ratio 48, specific area 335m
2/ g, crystallite dimension 500 nanometer.
Claims (5)
1. a synthetic method for submicron order ZSM-5 molecular sieve, is characterized in that: with silica gel and waterglass for mixing silicon source, with aluminium salt for aluminium source, take ZSM-5 molecular sieve as crystal seed, crystallization synthesis ZSM-5 molecular sieve under organic formwork agent existence condition;
Described silica gel is powder silica series products;
Add molecular sieve crystal seed in described mixing silicon source, the addition of molecular sieve crystal seed be total quality of material be greater than 0%-10%;
Described molecular sieve crystal seed joins in water glass solution and fully pulls an oar at 50-100 DEG C;
Described silica gel adds in the mixed serum of waterglass and molecular sieve crystal seed pulls an oar, and then adds aluminium salt, forms the mixed serum of synthesis of molecular sieve, finally adds organic formwork agent and continues making beating;
The pH value of the addition hierarchy of control of described waterglass is 11-13.
2. the synthetic method of submicron order ZSM-5 molecular sieve according to claim 1, is characterized in that described aluminium salt is one or more the mixture in aluminum sulfate, aluminium chloride or aluminum nitrate.
3. the synthetic method of submicron order ZSM-5 molecular sieve according to claim 1, is characterized in that in described mixing silicon source and aluminium source, silica alumina ratio is 20-100.
4. the synthetic method of submicron order ZSM-5 molecular sieve according to claim 1, it is characterized in that described organic formwork agent is organic amine, wherein organic amine is ethamine, propylamine or n-butylamine.
5. the synthetic method of submicron order ZSM-5 molecular sieve according to claim 1, it is characterized in that described crystallization temperature is 100-200 DEG C, crystallization time is 10-100h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210251128.6A CN102745718B (en) | 2012-07-19 | 2012-07-19 | Synthesis method of sub-micron ZSM-5 molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210251128.6A CN102745718B (en) | 2012-07-19 | 2012-07-19 | Synthesis method of sub-micron ZSM-5 molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102745718A CN102745718A (en) | 2012-10-24 |
| CN102745718B true CN102745718B (en) | 2014-12-24 |
Family
ID=47026293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210251128.6A Active CN102745718B (en) | 2012-07-19 | 2012-07-19 | Synthesis method of sub-micron ZSM-5 molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102745718B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103495378B (en) * | 2013-09-27 | 2015-08-05 | 上海绿强新材料有限公司 | A kind of alkene purifying adsorbent and the method for alkene process for purifying thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442686A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of ZSM-5 molecular sieve |
| CN102502696A (en) * | 2011-11-16 | 2012-06-20 | 大连理工大学 | Synthetic method of ZSM-5 zeolites |
| CN102530986A (en) * | 2012-01-10 | 2012-07-04 | 复旦大学 | Method for producing MFI type zeolites |
-
2012
- 2012-07-19 CN CN201210251128.6A patent/CN102745718B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442686A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of ZSM-5 molecular sieve |
| CN102502696A (en) * | 2011-11-16 | 2012-06-20 | 大连理工大学 | Synthetic method of ZSM-5 zeolites |
| CN102530986A (en) * | 2012-01-10 | 2012-07-04 | 复旦大学 | Method for producing MFI type zeolites |
Non-Patent Citations (2)
| Title |
|---|
| 不同晶粒大小ZSM-5的合成和表征;张领辉等;《催化学报》;199411;第15卷(第6期);468-473 * |
| 高硅铝比ZSM-5分子筛的合成及催化裂化性能研究;苏建明等;《石油炼制与化工》;200404;第35卷(第4期);18-22 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102745718A (en) | 2012-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104211085B (en) | Core-shell type ZSM-5 molecular sieve and preparation and application thereof | |
| CN109126861A (en) | A kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve | |
| CN106809855A (en) | A kind of porous material and preparation method thereof | |
| CN103071523A (en) | Lanthanum-phosphorus double-heteroatom ZSM-5 molecular sieve catalyst and preparation method thereof | |
| CN106904636A (en) | It is a kind of with the molecular sieves of SSZ 13 and its synthetic method of microporous mesoporous multi-stage artery structure and application | |
| CN107487777A (en) | The synthetic method of the nanometer molecular sieve catalysts of HZSM 5 | |
| CN103803576B (en) | A kind of low silica-alumina ratio ZSM-48 molecular sieve and preparation method thereof | |
| CN106745036A (en) | With the microporous mesoporous molecular sieves of multi-stage porous SSZ 13 and its synthetic method and application | |
| CN104812703A (en) | Synthesis of zsm-5 crystals with improved morphology | |
| CN106830003A (en) | SSZ-13/SCM-9 composite molecular screens and its synthetic method | |
| CN103420391B (en) | The preparation method of fine grain SAPO-34 molecular sieve | |
| CN102233282B (en) | Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as carrier and application thereof | |
| CN101993091B (en) | Method for synthesizing ZSM-5 zeolite | |
| CN102745718B (en) | Synthesis method of sub-micron ZSM-5 molecular sieve | |
| CN115872415B (en) | Nano ZSM-5 molecular sieve and preparation method thereof | |
| CN105776245B (en) | A kind of application of the synthetic method of the molecular sieves of ZSM 5 and products thereof in propylene from methanol | |
| CN101723395B (en) | Method for preparing double-micropore composite molecular sieve | |
| CN108262061A (en) | A kind of iron is modified the preparation method of sheet-type ZSM-5 zeolite catalyst | |
| CN104229829A (en) | Preparation method of small grain SAPO-34 molecular sieve | |
| CN102757069A (en) | Method for reusing mother liquor generated in ZSM (zeolite socony mobil)-5 molecular sieve preparation | |
| CN103288098B (en) | Preparation method of nano-beta zeolite molecular sieve | |
| CN102838128A (en) | Mordenite/ZSM-5 intergrowth molecular sieve and synthesis method thereof | |
| CN103723740B (en) | Synthesis method of IM-5 molecular sieve | |
| CN105621433B (en) | A kind of preparation method for having core shell structure Y Beta composite molecular screens | |
| CN112142064B (en) | Y-type molecular sieve composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |