CN104671252A - Method for synthesizing and preparing ZSM-22 molecular sieve under conditions of no organic template and no crystal seed - Google Patents
Method for synthesizing and preparing ZSM-22 molecular sieve under conditions of no organic template and no crystal seed Download PDFInfo
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- CN104671252A CN104671252A CN201510072221.4A CN201510072221A CN104671252A CN 104671252 A CN104671252 A CN 104671252A CN 201510072221 A CN201510072221 A CN 201510072221A CN 104671252 A CN104671252 A CN 104671252A
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Abstract
The invention relates to the field of preparation of molecular sieves, and aims to provide a method for synthesizing and preparing a ZSM-22 molecular sieve under the conditions of no organic template and no crystal seed. The method comprises the following steps: uniformly mixing deionized water and an alkali source, adding aluminum sulfate, adding a silicon source under stirring conditions, continuing stirring to form a silica-alumina gel, and carrying out crystallizing reaction on the obtained silica-alumina gel in a reaction kettle; after the reaction finishes, obtaining the product, carrying out vacuum filtration on the product, and drying to obtain the ZSM-22 molecular sieve raw powder. The method thoroughly avoids the use of the organic template agent, and lowers the crystallizing temperature on the premise that the crystallizing time is not obviously changed, thereby reducing the unnecessary energy consumption and environmental pollution in the production process. More importantly, the method has very high silicon raw material utilization ratio and high yield, thereby greatly saving the production cost and being beneficial to application in other industrial fields.
Description
Technical field
The invention relates to the preparation field of molecular sieve, particularly without organic formwork and the method preparing ZSM-22 molecular sieve without crystal seed synthesis.
Background technology
Zeolite molecular sieve is a kind of crystalline material with regular micropore canals, strongly-acid and large specific surface area, therefore possesses good shape selective catalysis performance.Again because it has high thermostability and hydrothermal stability, therefore the fields such as refining of petroleum, petrochemical complex and fine chemistry are widely used in.Zeolite molecular sieve, except being widely used at traditional chemical field, also slowly represents its development potentiality in other related materials fields now.Last century the eighties, the Mobil company of the U.S. investigated ZSM-22 molecular sieve, and its skeleton comprises five-ring, six-ring, ten-ring structure, is a kind of high-silica zeolite material with TON topological framework.ZSM-22 molecular sieve forms mesopore one-dimensional channels by ten-ring, and channel diameter is 0.47 × 0.55nm.Because ZSM-22 molecular sieve has suitable pore passage structure and stronger surface acidity, so it is show good selectivity in the reactions such as alkene at catalytic dewaxing, aromatic hydrocarbon alkylation and methanol conversion.
ZSM-22 molecular sieve all synthesizes under organic formwork agent existent condition in the past few decades.But the use of organic formwork agent not only adds production cost, wastes resource, also obnoxious flavour can be produced in roasting process, contaminate environment.Therefore investigators are devoted to the synthetic route of environmental protection always.Recently, Xiao Fengshou seminar utilizes crystal seed method organic-free template to successfully synthesize high-silicon ZSM-5-22 molecular sieve (CN Patent No.ZL 2,013 1 0047018.2).Although crystal seed method synthetic route decreases synthesis cost and reduce environmental pollution to a great extent, it should be noted that and employ organic formwork agent in the building-up process of ZSM-22 crystal seed.That is, crystal seed method synthesizes the use not avoiding organic formwork agent in the process of ZSM-22 molecular sieve completely.This constrains again the industrial application of ZSM-22 molecular sieve to a certain extent.
What pursue due to industrial application is low, the environmentally friendly molecular sieve of production cost, therefore, avoids the use of organic formwork agent to be worth research in the building-up process of ZSM-22 molecular sieve completely, and the promise well of industrial application.
Summary of the invention
Main purpose of the present invention is to overcome deficiency of the prior art, provides a kind of method preparing ZSM-22 molecular sieve not using organic formwork agent and crystal seed.For solving the problems of the technologies described above, solution of the present invention is:
There is provided without organic formwork and the method preparing ZSM-22 molecular sieve without crystal seed synthesis, specifically comprise the steps:
(1) remove after ionized water and alkali source mix, then get Tai-Ace S 150 and add, after then adding silicon source under agitation, continue to stir (4 ~ 6 hours) until dissolution homogeneity forms silica-alumina gel;
Described alkali source is potassium hydroxide or sodium hydroxide; Described silicon source is tetraethyl orthosilicate or white carbon black; And when ensureing reaction, Component molar proportioning meets, SiO
2: Al
2o
3: K
2o:H
2o is 1:0.004 ~ 0.035:0.03 ~ 0.25:5 ~ 100 (alkali source employing potassium hydroxide), or SiO
2: Al
2o
3: Na
2o:H
2o is 1:0.004 ~ 0.035:0.03 ~ 0.25:5 ~ 100 (alkali source employing sodium hydroxide);
(2) silica-alumina gel obtained in step (1) is placed in reactor and carries out crystallization, the temperature of reaction of crystallization is 140 ~ 180 DEG C, and the reaction times is 1 ~ 4 day; Obtain product after crystallization completes, by product suction filtration, oven dry, namely obtain ZSM-22 molecular screen primary powder.
In the present invention, described obtained ZSM-22 molecular screen primary powder is bar-shaped ZSM-22 molecular sieve, and crystal grain length is between 1 ~ 5um.
Compared with prior art, the invention has the beneficial effects as follows:
The ZSM-22 molecular sieve that the present invention utilizes organic-free template and prepares without crystal seed synthesis method, not only thoroughly avoid the use of organic formwork agent, and reduce crystallization temperature, and crystallization time does not have considerable change, which reduces energy consumption unnecessary in process of production and avoid environment; The more important thing is that the method has very high silicon raw material availability, productive rate high, this has just saved production cost greatly, contributes to its application at industrial circle.
Inorganic raw material of the present invention is all environmentally friendly, and cheap, thus significant in actual chemical production field.
The product of the present invention's synthesis not only maintains good degree of crystallinity and purity, also has good catalytic reaction activity, shows very high selectivity in isomerization reaction, have potential using value for some important catalyzed reactions.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the product that the present invention synthesizes.
Fig. 2 is the scanning electron microscope (SEM) photograph of the product that the present invention synthesizes.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail:
The following examples can make professional and technical personnel's comprehend the present invention of this specialty, but do not limit the present invention in any way.
Embodiment 1 alkali source is organic-free template and prepare ZSM-22 without crystal seed method under KOH condition
First, by 25g H
2o and 0.38g KOH mixes, then adds 0.21g Tai-Ace S 150 wherein, adds 6g tetraethyl orthosilicate (TEOS) after stirring clarification, continues to stir until solution becomes evenly form silica-alumina gel.Then added by gel in tetrafluoroethylene stainless steel cauldron, dynamic still rotating speed is 50rpm, and 150 DEG C of crystallization are complete crystallization in 2 days, and product suction filtration, obtains product after oven dry.In this reaction system, Component molar proportioning meets, SiO
2: Al
2o
3: K
2o:H
2o is 1:0.011:0.118:55.7.
The XRD spectra of ZSM-22 molecular sieve that Fig. 1 is organic-free template and prepares without crystal seed method, can see that product has typical ZSM-22 molecular sieve structure, and sample has higher degree of crystallinity and purity by spectrogram.
The stereoscan photograph (SEM) of ZSM-22 zeolite product that Fig. 2 is organic-free template and prepares without crystal seed method, from photo, we can see some products that are bar-shaped or needle-like, and size is between 1 ~ 5um.
Embodiment 2 NaOH replaces KOH as alkali source
First, by 25g H
2o and 0.30g NaOH mixes, then adds 0.21g Tai-Ace S 150 wherein, adds 6g tetraethyl orthosilicate (TEOS) after stirring clarification, continues to stir until solution becomes evenly form silica-alumina gel.Then added by gel in tetrafluoroethylene stainless steel cauldron, dynamic still rotating speed is 50rpm, and 150 DEG C of crystallization are complete crystallization in 2 days, and product suction filtration, obtains product after oven dry.In this reaction system, Component molar proportioning meets, SiO
2: Al
2o
3: Na
2o:H
2o is 1:0.011:0.125:55.7.
Embodiment 3 is organic-free template and prepare ZSM-22 without crystal seed method under high alkalinity condition relatively
First, by 25g H
2o and 0.81g KOH or 0.60g NaOH mixes, then adds 0.21g Tai-Ace S 150 wherein, adds 6g tetraethyl orthosilicate (TEOS) after stirring clarification, continues to stir until solution becomes evenly form silica-alumina gel.Then added by gel in tetrafluoroethylene stainless steel cauldron, dynamic still rotating speed is 50rpm, and 150 DEG C of crystallization 2 days, product suction filtration, obtains product after oven dry.In this reaction system, Component molar proportioning meets, SiO
2: Al
2o
3: K
2o/Na
2o:H
2o is 1:0.011:0.25:55.7.Through X-ray diffraction analysis, it consists of crystobalite and ZSM-22 molecular sieve to the product obtained.
Embodiment 4 is organic-free template and prepare ZSM-22 without crystal seed method under low alkalinity condition relatively
First, by 25g H
2o and 0.097g KOH or 0.072g NaOH mixes, then adds 0.21g Tai-Ace S 150 wherein, adds 6g tetraethyl orthosilicate (TEOS) after stirring clarification, continues to stir until solution becomes evenly form silica-alumina gel.Then added by gel in tetrafluoroethylene stainless steel cauldron, dynamic still rotating speed is 50rpm, and 150 DEG C of crystallization 2 days, product suction filtration, obtains product after oven dry.In this reaction system, Component molar proportioning meets, SiO
2: Al
2o
3: K
2o/Na
2o:H
2o is 1:0.011:0.03:55.7.Through X-ray diffraction analysis, it consists of amorphous and ZSM-22 molecular sieve to the product obtained.
Embodiment 5 white carbon black replaces tetraethyl orthosilicate as silicon source
First, by 25g H
2o and 0.38g KOH mixes, then adds 0.21g Tai-Ace S 150 wherein, adds 1.73g white carbon black after stirring clarification, continues to stir until gel becomes evenly form silica-alumina gel.Then added by gel in tetrafluoroethylene stainless steel cauldron, dynamic still rotating speed is 50rpm, 150 DEG C of crystallization 2 days, and product suction filtration is dried.Through X-ray diffraction analysis, it consists of ZSM-22 molecular sieve to the product obtained.In this reaction system, Component molar proportioning meets, SiO
2: Al
2o
3: K
2o:H
2o is 1:0.011:0.118:55.7.
ZSM-22 is synthesized under the different deionized water condition of embodiment 6
The addition of deionized water, with embodiment 1, is just changed, is made in reaction system by the preparation method of ZSM-22 molecular sieve, and Component molar proportioning meets, SiO
2: Al
2o
3: K
2o:H
2o is 1:0.011:0.118:5.Through X-ray diffraction analysis, it consists of crystobalite and ZSM-22 molecular sieve to the product obtained.
ZSM-22 is synthesized under the different deionized water condition of embodiment 7
The addition of deionized water, with embodiment 1, is just changed, is made in reaction system by the preparation method of ZSM-22 molecular sieve, and Component molar proportioning meets, SiO
2: Al
2o
3: K
2o:H
2o is 1:0.011:0.118:100.Through X-ray diffraction analysis, it consists of amorphous and ZSM-22 molecular sieve to the product obtained.
ZSM-22 is synthesized under embodiment 8 high silica alumina ratio condition
The addition of Tai-Ace S 150, with embodiment 1, is just changed, is made in reaction system by the preparation method of ZSM-22 molecular sieve, and Component molar proportioning meets, SiO
2: Al
2o
3: K
2o:H
2o is 1:0.004:0.118:55.7.Through X-ray diffraction analysis, it consists of crystobalite and ZSM-22 molecular sieve to the product obtained.
ZSM-22 is synthesized under embodiment 9 low silica-alumina ratio condition
The addition of Tai-Ace S 150, with embodiment 1, is just changed, is made in reaction system by the preparation method of ZSM-22 molecular sieve, and Component molar proportioning meets, SiO
2: Al
2o
3: K
2o:H
2o is 1:0.035:0.118:55.7.Through X-ray diffraction analysis, it consists of amorphous and ZSM-22 molecular sieve to the product obtained.
ZSM-22 is synthesized under the relative mild temperature of embodiment 10
The preparation of initial silicon alumina gel is with embodiment 1.ZSM-22 zeolite molecular sieve preparation process is as follows: after the gelling system of embodiment 1 preparation stirs, form silica-alumina gel, added by gel in tetrafluoroethylene stainless steel cauldron, dynamic still rotating speed is 50rpm, crystallization 2 days in 140 DEG C of baking ovens.Product suction filtration, dries.Through X-ray diffraction analysis, it consists of ZSM-22 molecular sieve and amorphous to the product obtained.
ZSM-22 is synthesized under embodiment 11 relatively-high temperature condition
The preparation of initial silicon alumina gel is with embodiment 1.ZSM-22 zeolite molecular sieve preparation process is as follows: after the gelling system of embodiment 1 preparation stirs, added by gel in tetrafluoroethylene stainless steel cauldron, dynamic still rotating speed is 50rpm, crystallization 2 days in 180 DEG C of baking ovens.Product suction filtration, dries.Through X-ray diffraction analysis, it consists of ZSM-22 molecular sieve and crystobalite to the product obtained.
ZSM-22 is synthesized under embodiment 12 relative short time crystallization condition
The preparation of initial silicon alumina gel is with embodiment 1.ZSM-22 zeolite molecular sieve preparation process is as follows: after the gelling system of embodiment 1 preparation stirs, added by gel in tetrafluoroethylene stainless steel cauldron, dynamic still rotating speed is 50rpm, crystallization 1 day in 150 DEG C of baking ovens.Product suction filtration, dries.Through X-ray diffraction analysis, it consists of amorphous and ZSM-22 molecular sieve to the product obtained.
ZSM-22 is synthesized under the relatively long-time crystallization condition of embodiment 13
The preparation of initial silicon alumina gel is with embodiment 1.ZSM-22 zeolite molecular sieve preparation process is as follows: after the gelling system of embodiment 1 preparation stirs, added by gel in tetrafluoroethylene stainless steel cauldron, dynamic still rotating speed is 50rpm, crystallization 4 days in 150 DEG C of baking ovens.Product suction filtration, dries.Through X-ray diffraction analysis, it consists of crystobalite and ZSM-22 molecular sieve to the product obtained.
The above, it is only several case study on implementation of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with better case study on implementation, but and be not used to limit the present invention, any those skilled in the art, are not departing within the scope of technical solution of the present invention, when the structure and technology contents that can utilize above-mentioned announcement are made a little change or be modified to the equivalent case study on implementation of equivalent variations.But every content not departing from technical solution of the present invention, any simple modification done above case study on implementation according to technical spirit of the present invention, equivalent variations and modification, all still belong within the scope of technical solution of the present invention.
Claims (2)
1., without organic formwork and the method preparing ZSM-22 molecular sieve without crystal seed synthesis, it is characterized in that, specifically comprise the steps:
(1) remove after ionized water and alkali source mix, then get Tai-Ace S 150 and add, after then adding silicon source under agitation, continue to stir until dissolution homogeneity forms silica-alumina gel;
Described alkali source is potassium hydroxide or sodium hydroxide; Described silicon source is tetraethyl orthosilicate or white carbon black; And when ensureing reaction, Component molar proportioning meets, SiO
2: Al
2o
3: K
2o:H
2o is 1:0.004 ~ 0.035:0.03 ~ 0.25:5 ~ 100, or SiO
2: Al
2o
3: Na
2o:H
2o is 1:0.004 ~ 0.035:0.03 ~ 0.25:5 ~ 100;
(2) silica-alumina gel obtained in step (1) is placed in reactor and carries out crystallization, the temperature of reaction of crystallization is 140 ~ 180 DEG C, and the reaction times is 1 ~ 4 day; Obtain product after crystallization completes, by product suction filtration, oven dry, namely obtain ZSM-22 molecular screen primary powder.
2. according to claim 1 without organic formwork and the method preparing ZSM-22 molecular sieve without crystal seed synthesis, it is characterized in that, described obtained ZSM-22 molecular screen primary powder is bar-shaped ZSM-22 molecular sieve, and crystal grain length is between 1 ~ 5um.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271286A (en) * | 2015-10-10 | 2016-01-27 | 吉林大学 | Method for synthesis of Cr-Al-ZSM-22 molecular sieve from modified diatomite |
| CN107285332A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The synthetic method of ZSM-22 molecular sieves and its ZSM-22 molecular sieves of synthesis |
| CN110980762A (en) * | 2019-11-26 | 2020-04-10 | 中触媒新材料股份有限公司 | Preparation method of ZSM-35 with special morphology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962194A (en) * | 2010-09-07 | 2011-02-02 | 浙江大学 | Method for preparing ZSM-34 and heteroatomic substitution molecular sieve thereof by direct synthesis method |
| 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 |
| CN103101924A (en) * | 2013-02-01 | 2013-05-15 | 浙江大学 | Method for preparing ZSM-22 molecular sieve by using seed crystal synthesis method |
-
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- 2015-02-11 CN CN201510072221.4A patent/CN104671252A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962194A (en) * | 2010-09-07 | 2011-02-02 | 浙江大学 | Method for preparing ZSM-34 and heteroatomic substitution molecular sieve thereof by direct synthesis method |
| 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 |
| CN103101924A (en) * | 2013-02-01 | 2013-05-15 | 浙江大学 | Method for preparing ZSM-22 molecular sieve by using seed crystal synthesis method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271286A (en) * | 2015-10-10 | 2016-01-27 | 吉林大学 | Method for synthesis of Cr-Al-ZSM-22 molecular sieve from modified diatomite |
| CN107285332A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The synthetic method of ZSM-22 molecular sieves and its ZSM-22 molecular sieves of synthesis |
| CN107285332B (en) * | 2016-04-12 | 2022-08-12 | 中国石油化工股份有限公司 | Synthesis method of ZSM-22 molecular sieve and ZSM-22 molecular sieve synthesized by same |
| CN110980762A (en) * | 2019-11-26 | 2020-04-10 | 中触媒新材料股份有限公司 | Preparation method of ZSM-35 with special morphology |
| CN110980762B (en) * | 2019-11-26 | 2021-11-02 | 中触媒新材料股份有限公司 | Preparation method of ZSM-35 with special morphology |
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