CN1051334A - The method of synthesis of zeolite by vapor phase - Google Patents
The method of synthesis of zeolite by vapor phase Download PDFInfo
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- CN1051334A CN1051334A CN 89108240 CN89108240A CN1051334A CN 1051334 A CN1051334 A CN 1051334A CN 89108240 CN89108240 CN 89108240 CN 89108240 A CN89108240 A CN 89108240A CN 1051334 A CN1051334 A CN 1051334A
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Abstract
The method of synthesis of zeolite by vapor phase.It is a kind of novel method that is mixed into zeolite at water vapor or organism and water.It opens up the new way of a synthetic zeolite, its process is simple, need not carry out liquid-solid separation, only directed synthetic gel is placed on the upper screen of reactor, put at the bottom of the still an amount of a certain proportion of liquid phase, sealing, crystallization quenching then, oven dry get final product various types of zeolites, its liquid phase also can repeatedly recycle, so raw material consumption is few, the single-autoclave yield rate height has to be produced and researching value widely.
Description
The method of synthesis of zeolite by vapor phase of the present invention be a kind of in steam the method for synthetic zeolite.Specifically be exactly the method for synthetic zeolite in the steam that the blended liquid phase of water vapor or organism and water forms.
Now the method for disclosed synthetic zeolite is generally hydrothermal synthesis method, is to be template with the itrogenous organic substance, and entire synthesis process is all carried out in water medium, organic amine, Na
2O, Sio
2, Al
2O
3Dissolve in water Deng active principle, caused the product silica alumina ratio wayward, active principle loses with the mother liquor discharging, cause raw material consumption big, single still yield is low, the defective of mother liquor exhaust emission environment, for addressing the above problem, we have successively invented " mordenite is synthetic in the non-aqueous system ", " supersiliceous zeolite is synthetic in two kinds of organic-compound systems ", " the ZSM-35 zeolite is synthetic in the non-aqueous system ", the novel method of " high silicon crystalline aluminosilicate and derivative thereof is synthetic in the non-aqueous system " a series of zeolite synthesis, all apply for a patent in Patent Office of the People's Republic of China, number of patent application is respectively: 88100228,88104266,88106196,89101174, but still there is liquid-solid isolating problem, with adhere to organic amine on the product zeolite and be difficult for to handle, bring the loss raw material and be difficult for problem as sorbent material and catalyzer.
In order further to cut down the consumption of raw materials, improve single-autoclave yield rate, simplify building-up process, we have proposed a kind of not only silica alumina ratio again and have easily controlled, single-autoclave yield rate height, raw material consumption are low, and building-up process simple, need not carry out liquid-solid separation, its product can be used as zeolite synthesis new departure of sorbent material or catalyzer.
The method of synthesis of zeolite by vapor phase of the present invention be a kind of in steam the method for synthetic zeolite, whole syntheticly all in the steam of the blended liquid phase formation of water vapor or organism and water, carry out.The product zeolite that can synthesize series of different according to the liquid phase and the directed synthetic gel of different components.Its building-up process is: the solid phase gel that silica alumina ratio requires that meets that will be synthesized by the solution orientation of silicon sol (or water glass), sodium hydroxide (or sodium salt) and aluminium salt places on the ventilation property screen cloth on reactor top through suction filtration, washing, the liquid phase of certain component places at the bottom of the still, (as shown in Figure 1) reactor sealing, stood in 120～250 ℃ the baking oven crystallization 1～20 day, quenching then, washing, oven dry can obtain can be as the product zeolite of sorbent material and catalyzer, and its liquid phase also can repeatedly recycle.
Realize that chemical composition of the present invention (is mol ratio) as shown in Table 1
Skeleton component of the present invention also has diversity, promptly can all be silicon and aluminium, also can be to be similar to other element of aluminium and silicon such as Be, Co, the Ni of divalent state in nature; The B of three valence states, V, Ga, In, Cr, AS, Fe; The Ti of tetravalence attitude, Zr, Sn; The V of pentavalent attitude, p etc. can partly or entirely replace aluminium and silicon.
Metallic cation coordination mode of the present invention and introducing mode also are various, can be that other metallic cation of basic metal or alkaline-earth metal class such as K, Li, Rb, CS, Mg, Ca, Sr, Ba etc. can partly or entirely replace sodium; It can be oxyhydroxide that the coordination metallic cation is introduced the source, also can be halogenide, and nitrate, vitriol, carbonate can partly or entirely replace oxyhydroxide.
Realize that most preferred embodiment of the present invention is as follows:
Example 1: get MSio
2=4.9 silicon sol 60.8ml adds in the container and adds NaO solution (MOH successively
-=3.1) 24.4ml and MAl
2O
3=1.4 alum liquor 15ml becomes glue under high degree of agitation, and continues to stir 15 minutes, and suction filtration, washing then makes gel component be: 1.2Na
2O: Al
2O
3: 13.8Sio
2: 30HO, place on the upper screen of still, put into 50mlH at the bottom of the still
2O
3Reactor sealing, stand in 200 ℃ of baking ovens crystallization 5 days, can obtain being similar to the product zeolite of mordenite.(as shown in Figure 2)
Example 2: get Msio
2=4.9 silicon sol 80ml under violent stirring, adds MOH in turn in container
-=3.1 sodium hydroxide solution 6.3ml and MAl
2O
3=1.2 alum liquor 10ml continues to stir 15 minutes, gel suction filtration, washing, and making its chemical ingredients is 0.7Na
2O: Al
2O
3: 31.3Sio: 160H
2O places on the still upper screen, puts into 50ml liquid at the bottom of the still, and its mole consists of: 0.4EDA: 1.5Et
3N: 1.0H
2O sealing back crystallization 4 days in 200 ℃ of baking ovens can obtain being similar to ZSM-35 type zeolite.(seeing accompanying drawing 3)
Example 3: the silicon sol 90ml that gets M=2.67 adds Mcl under violent stirring in container
-=1.5 NaCl solution 35ml and MAl
2O
3=0.50 alum liquor 17ml, the colloid of formation is through suction filtration, washing, and it consists of 4.0Na
2O: Al
2O
3: 24.95Sio
2: 140H
2O places on the screen cloth on still top, and (mole consists of 0.8EDA: 2.0Et, N: 1.0HO), after the sealing, crystallization is 6 days in 180 ℃ baking oven, can obtain being similar to ZSM-35 type product zeolite to put into 50ml liquid at the bottom of the still.
Example 4: get 150ml water glass (Msio
2=2.72, MOH
-=1.59) with 18ml Tai-Ace S 150 (MAl
2O
3=0.50) under agitation become glue, through suction filtration, washing, its Chemical Composition is 163Na
2O: Al
2O
3: 44.8sio: 230H
2O places on the still upper screen, and putting into chemical constitution at the bottom of the still is 0.18 triethylamine: the liquid 50ml of 0.07 quadrol: 1.0HO, sealing back crystallization in 200 ℃ of baking ovens can obtain being similar to ZSM-5 type product zeolite in 6 days.(seeing accompanying drawing 4)
Example 5: get 100ml water glass (Msio
2=2.72, MOH
-=1.59) add that alum liquor 22.6ml Tai-Ace S 150 becomes glue in the container under high degree of agitation, through suction filtration, wash its Chemical Composition and be: 1.0Na
2O: Al
2O
3: 24.0sio
2: 120H
2O places on the screen cloth on still top, and putting into chemical composition at the bottom of the still is 1.0H
2O: 0.4 tetramethyleneimine: the liquid 40ml of 15 triethylamines, sealing back crystallization 8 days in 200 ℃ baking oven can obtain being similar to the product zeolite of ZSM-21 type.(seeing accompanying drawing 5)
The present invention without washing, directly measures example 3 products its thermal analysis curve (seeing accompanying drawing 6) result with RigakuDTA-TG10A and shows the product zeolite, and amine consumption is very little, and the rate of weight loss of its amine is 9%.
With the present invention, synthetic ZSM-5 product zeolite is used 1N NH respectively
4Cl and 1NHCl exchange at normal temperatures, and washing is to not having chlorion, 120 ℃ of oven dry, 300 ℃ of roastings 3 hours, 550 ℃ of roastings 6 hours make modified ZSM-5, compressing tablet, obtain 40～60 order samples, utilize the pulse micro-inverse technical research, the o-xylene isomerization reaction, loaded catalyst is 0.1g, the pulse sample size is 0.35ml, and its catalytic performance is shown in following table two:
O-xylene isomerization on the ZSM-5 (temperature of reaction is 500 ℃)
| Exchange solution | Transformation efficiency | Selection rate | Dimethylbenzene is formed (%) | ||
| P-X | m-x | O-X | |||
| NHCl | 70.93 | 19.84 | 19.84 | 48.82 | 31.34 |
| HCl | 72.89 | 19.34 | 19.34 | 50.16 | 30.48 |
The method of synthesis of zeolite by vapor phase of the present invention, be that a kind of product zeolite is easy to control, raw material consumption is few, the single-autoclave yield rate height, three-waste free discharge, building-up process are simple, the not treated novel method that can be used as sorbent material and catalyzer of its product zeolite opens up a new way to the production and the research of zeolite molecular sieve.
Description of drawings:
Fig. 1: reactor synoptic diagram; 1. 2. 3. 4. 5. liquid phase of support of ventilation property screen cloth of solid phase of container wherein
Fig. 2: the X-ray powder diffraction pattern of mordenite;
Fig. 3: the X-ray powder diffraction pattern of ZSM-35 zeolite;
Fig. 4: the X-ray powder diffraction pattern of ZSM-5 zeolite;
Fig. 5: the X-ray powder diffraction pattern of ZSM-21 zeolite;
Fig. 6: the TG-DTA curve of ZSM-35 zeolite.
Reference:
①u、s、p3，702，886（1972）
②u、s、p4，046，859（1977）
③u、s、p4，016，245（1977）
4. 1989:179 catalysis journal 10(2),
Claims (7)
1, the method of synthesis of zeolite by vapor phase be a kind of in steam the method for synthetic zeolite, the process that it is characterized in that zeolite synthesis is all carried out in the steam that the blended liquid phase of water vapor or organism and water forms, the product zeolite that can synthesize series of different according to the liquid phase and the directed synthetic gel of different components, its building-up process is: will be by silicon sol (or water glass), the solution orientation of sodium hydroxide (or sodium salt) and aluminium salt synthesizes meets the solid phase gel that silica alumina ratio requires, through suction filtration, washing places on the ventilation property screen cloth on reactor top, the liquid phase of certain component places at the bottom of the still, the reactor sealing, stand on crystallization in the baking oven, quenching then, washing, oven dry, can obtain can be as the product zeolite of sorbent material and catalyzer, and its liquid phase also can repeatedly recycle mutually.
2, according to the method for the described synthesis of zeolite by vapor phase of claim 1, it is characterized in that being: (0.8～3.0) M according to gel component
2O: (10～40) Sio
2: Al
2O
3: (0～80) H
2The O liquid phase is a distilled water, and its volume can synthesize the product zeolite that is similar to mordenite for (10～100) ml.
3, the method according to the described synthesis of zeolite by vapor phase of claim 1 is characterized in that, according to gel component is: (0～2.5) M
2O: (40～) Sio
2: AL
2O
3: (0～250) H
2O, liquid phase component is: (0～10.0) R
1N: (0～10.0) R
2N: H
2O, wherein R
1N+R
2N＞0.2, R
1N=Et
3N, n-pr
3N; R
2N=EDA, Et
2NH, EtNH
2, n-prNH
2, n-ButNH
2Can synthesize the product zeolite that is similar to the ZSM-5 type.
4,, it is characterized in that being according to gel component according to the method for the described synthesis of zeolite by vapor phase of claim 1:
(0～3.0) M
2O: (8.0～40) sio
2: Al
2O
3: (0～200) H
2O, liquid phase component are (0.3～10.0) R
1N: (0.1～10.0) R
2N: H
2O is R wherein
1N=Et
3N or n-pr
3N, R
2The N=tetramethyleneimine can synthesize the product zeolite that is similar to the ZSM-21 type.
5, according to the method for the described synthesis of zeolite by vapor phase of claim 1, it is characterized in that, be: (0～5.0) M according to gel component
2O: (8～40) sio
2: Al
2O
3: (0～200) H
2O, liquid phase component is: (0.2～10) R
1N: (0～10.0) R
2N: H
2O, wherein R
1N=Et
3N, n-pr
3N, ButNH
2, R
2N=EDA, Et
2NH, tetramethyleneimine can synthesize and is similar to ZSM-35 type product zeolite.
6, the method according to the described synthesis of zeolite by vapor phase of claim 1 is characterized in that crystallization time was generally 1～20 day.
7, the method according to the described synthesis of zeolite by vapor phase of claim 1 is characterized in that crystallization temperature is 120～250 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108240 CN1023554C (en) | 1989-10-28 | 1989-10-28 | Synthesis of zeolite by vapor phase method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108240 CN1023554C (en) | 1989-10-28 | 1989-10-28 | Synthesis of zeolite by vapor phase method |
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| Publication Number | Publication Date |
|---|---|
| CN1051334A true CN1051334A (en) | 1991-05-15 |
| CN1023554C CN1023554C (en) | 1994-01-19 |
Family
ID=4857496
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89108240 Expired - Fee Related CN1023554C (en) | 1989-10-28 | 1989-10-28 | Synthesis of zeolite by vapor phase method |
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| Country | Link |
|---|---|
| CN (1) | CN1023554C (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101338C (en) * | 1997-02-05 | 2003-02-12 | 张雪成 | Production process of zeolite powder |
| CN101439296B (en) * | 2007-11-23 | 2010-08-25 | 北京化工大学 | In-situ gas-phase method for preparing industrial zeolite catalyst |
| CN102674388A (en) * | 2012-06-06 | 2012-09-19 | 北京化工大学 | Method for preparing zeolite molecular sieve catalyst through circulating gas phase method |
| CN103121690A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for synthetizing mordenite by utilizing vapor phase process |
| CN103183356A (en) * | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Method for modifying titanium silicalite molecular sieve by precious metal source |
| CN103183355A (en) * | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Precious metal modification method of titanium silicalite molecular sieve |
| CN104445255A (en) * | 2014-12-04 | 2015-03-25 | 南京工业大学 | Preparation method of heteroatom MCM-49 zeolite molecular sieve |
| CN105417518A (en) * | 2014-09-05 | 2016-03-23 | 中国科学院金属研究所 | Gas-phase post-treatment modification apparatus and gas-phase post-treatment modification method of solid carbon material |
| CN105523565A (en) * | 2016-02-05 | 2016-04-27 | 福建师范大学 | Method for preparing W molecular sieve by adopting steam assisted solid phase transformation |
| CN107399743A (en) * | 2016-05-20 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of preparation method of NaY molecular sieve |
| CN109928404A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of synthetic method of zeolite molecular sieve |
| CN110614121A (en) * | 2018-06-20 | 2019-12-27 | 中国科学院大连化学物理研究所 | ZSM-35 molecular sieve, preparation method and application thereof |
| CN110759357B (en) * | 2018-07-25 | 2021-08-27 | 中国石油天然气股份有限公司 | Synthesis method of zsm-35/zsm-5 eutectic molecular sieve |
| WO2022033192A1 (en) * | 2020-08-10 | 2022-02-17 | 中国民航大学 | Method for preparing metal surface chemical conversion film |
-
1989
- 1989-10-28 CN CN 89108240 patent/CN1023554C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101338C (en) * | 1997-02-05 | 2003-02-12 | 张雪成 | Production process of zeolite powder |
| CN101439296B (en) * | 2007-11-23 | 2010-08-25 | 北京化工大学 | In-situ gas-phase method for preparing industrial zeolite catalyst |
| CN103121690B (en) * | 2011-11-18 | 2015-01-07 | 中国石油化工股份有限公司 | Method for synthetizing mordenite by utilizing vapor phase process |
| CN103121690A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for synthetizing mordenite by utilizing vapor phase process |
| CN103183355B (en) * | 2011-12-30 | 2015-05-20 | 中国石油化工股份有限公司 | Precious metal modification method of titanium silicalite molecular sieve |
| CN103183356A (en) * | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Method for modifying titanium silicalite molecular sieve by precious metal source |
| CN103183356B (en) * | 2011-12-30 | 2015-03-18 | 中国石油化工股份有限公司 | Method for modifying titanium silicalite molecular sieve by precious metal source |
| CN103183355A (en) * | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Precious metal modification method of titanium silicalite molecular sieve |
| CN102674388B (en) * | 2012-06-06 | 2013-10-16 | 北京化工大学 | Method for preparing zeolite molecular sieve catalyst through circulating gas phase method |
| CN102674388A (en) * | 2012-06-06 | 2012-09-19 | 北京化工大学 | Method for preparing zeolite molecular sieve catalyst through circulating gas phase method |
| CN105417518B (en) * | 2014-09-05 | 2017-07-07 | 中国科学院金属研究所 | Gas phase post processing reforming apparatus and the method for a kind of solid carbonaceous material |
| CN105417518A (en) * | 2014-09-05 | 2016-03-23 | 中国科学院金属研究所 | Gas-phase post-treatment modification apparatus and gas-phase post-treatment modification method of solid carbon material |
| CN104445255A (en) * | 2014-12-04 | 2015-03-25 | 南京工业大学 | Preparation method of heteroatom MCM-49 zeolite molecular sieve |
| CN105523565A (en) * | 2016-02-05 | 2016-04-27 | 福建师范大学 | Method for preparing W molecular sieve by adopting steam assisted solid phase transformation |
| CN105523565B (en) * | 2016-02-05 | 2018-10-09 | 福建师范大学 | Vapor assisted Solid-state converts the method for preparing W molecular sieves |
| CN107399743A (en) * | 2016-05-20 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of preparation method of NaY molecular sieve |
| CN109928404A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of synthetic method of zeolite molecular sieve |
| CN110614121A (en) * | 2018-06-20 | 2019-12-27 | 中国科学院大连化学物理研究所 | ZSM-35 molecular sieve, preparation method and application thereof |
| CN110614121B (en) * | 2018-06-20 | 2021-03-02 | 中国科学院大连化学物理研究所 | ZSM-35 molecular sieve, preparation method and application thereof |
| CN110759357B (en) * | 2018-07-25 | 2021-08-27 | 中国石油天然气股份有限公司 | Synthesis method of zsm-35/zsm-5 eutectic molecular sieve |
| WO2022033192A1 (en) * | 2020-08-10 | 2022-02-17 | 中国民航大学 | Method for preparing metal surface chemical conversion film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1023554C (en) | 1994-01-19 |
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