CN102951656B - Method for synthesizing even-grained ZSM-5 molecular sieves - Google Patents
Method for synthesizing even-grained ZSM-5 molecular sieves Download PDFInfo
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- CN102951656B CN102951656B CN201210389572.4A CN201210389572A CN102951656B CN 102951656 B CN102951656 B CN 102951656B CN 201210389572 A CN201210389572 A CN 201210389572A CN 102951656 B CN102951656 B CN 102951656B
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Abstract
A method for synthesizing even-grained ZSM-5 molecular sieves belongs to the technical field of catalyst preparation. The method comprises the steps of: firstly, preparing seed crystal mixed solution by a coprecipitation method: controlling the PH value of the precipitate to the range of 8-11 during coprecipitation, grinding the precipitate to certain fineness by using grinding equipment after precipitation, and then obtaining the seed crystal mixed solution through crystallization; and preparing the ZSM-5 molecular sieves: firstly preparing the precipitate mixture by the coprecipitation method, adding the seed crystal mixed solution in a certain proportion, and obtaining the even-grained ZSM-5 molecular sieves through crystallization, filtering, washing and calcination. The method is capable of preparing the ZSM-5 molecular sieves of special granularity to meet the catalytic reaction requirements according to different reaction requirements.
Description
Technical field
The synthetic method that the present invention relates to a kind of uniform particles ZSM-5 molecular sieve, belongs to catalyst preparation technical field.
Background technology
ZSM-5 zeolite molecular sieve is a kind of important catalyst component, first by Mobil oil company of U.S. invention (USP 3702886,1972), oneself is widely used ZSM-5 by warp in the petrochemical process such as shape selective catalysis, isomerization, disproportionation, alkylation.But along with the continuous expansion of application, different reaction systems has different requirements to the particle diameter of ZSM-5 zeolite catalytic material, the ZSM-5 zeolite molecular sieve size distribution that general synthetic method synthesizes is wider, all there is generation from the micron-sized particle of nano level to ten, can not meet the granularity requirement of specific reaction to catalyzer.When the type of selecting requires when high, to require most reactions to complete in duct, for being controlled at the consistence in reaction times in hole, require molecular sieve to there is uniform distribution of particle sizes.In the field such as fine chemistry industry, under increasing macromole or liquid phase, react in addition, require large duct, existing ZSM-5 zeolite molecular sieve arctation, the diffusional resistance of reactant or product is large, is not suitable for this reaction.Little crystal grain zeolite increases outside surface number of acid sites because outside surface increases, and because internal surface the evolving path shortens, makes catalytic activity higher again, increases macromolecular conversion capability.Therefore synthetic different grain sizes and evengranular ZSM-5 zeolite molecular sieve are important topics in the synthetic field of zeolite molecular sieve.
In Japanese Patent 52-43800/1977, propose to produce taking alcohol as template the ZSM-5 zeolite molecular sieve of larger particles, distribution of particle sizes is mainly at 1-10 micron, but also contains the following sieve particle in 1 micron of 10% left and right.In Japanese Patent 57-7818/1982, propose to prepare taking amino alcohol replacement 4-propyl bromide as template the ZSM-5 zeolite molecular sieve of little crystal grain, distribution of particle sizes is mainly at 0.1 ~ 0.5 micron, but 1 micron of above sieve particle accounts for 15% left and right.In addition, also propose to use the patent application of ZSM-5 seed production ZSM-5 zeolite.In United States Patent (USP) 4175114, add ZSM-5 crystal seed to reduce the consumption of expensive tetrapropyl ammonium salt, the crystal seed of 5% left and right is joined in the middle of sodium silicate solution, then the aluminium source that is added with a small amount of template is joined in the middle of silicon solution, make ZSM-5 molecular sieve through crystallization, filtration, washing, roasting.In Japanese Patent 60-71519/1985 and 60-77123/1985, part recycles ZSM-5 crystal seed and produces the ZSM-5 molecular sieve of specified particle size, does not all reach desirable object.There is in addition the particle diameter that adopts specific material to limit ZSM-5 molecular sieve, as (chem commn, 1999: 673 ~ 674) such as Madsen adopt carbon black as restriceted envelope material, synthesize the ZSM-5 molecular sieve of 20 ~ 40 nm.It is larger that synthetic nano zeolite is affected by the pore size distribution of inert media, to inertia mesoporous material require high; Also must ensure that synthetic liquid enters the mesoporous inside of inert media completely, reduces the residual quantity outside hole; Inert media large usage quantity, and need take roasting method to remove, cost is high.
Summary of the invention
In order to overcome problems of the prior art, the invention provides a kind of synthetic method of uniform particles ZSM-5 molecular sieve, the method should be able to be synthesized the ZSM-5 zeolite molecular sieve of uniform crystal particles fast, building-up process adopts the synthetic material of conventional ZSM-5 zeolite molecular sieve, do not need mesoporous material etc. as Size of Zeolite restrictive substance, without long-time low temperature aging, and operation is simple, generated time is short, whole building-up process only needs 15 ~ 30 hours, and gained ZSM-5 zeolite crystal size evenly.
The technical solution used in the present invention is: the synthesis step that a kind of synthetic method of uniform particles ZSM-5 molecular sieve adopts comprises:
A. use He Lv source, silicon source and organic formwork agent, adopt the method for co-precipitation to prepare slurry, slurry mol ratio is: Na
2o: SiO
2: A1
2o
3: H
2o:Q=(3 ~ 30): (20 ~ 200): 1: (20 ~ 250): (0.1 ~ 2), Q is organic formwork agent, with after grinding plant ground slurry, the diameter of micelle is less than 1 micron, then packing band into stirs in high pressure water heating kettle, crystallization is prepared crystal seed mixed liquor A, and crystallization temperature is 100 ~ 200 DEG C, and crystallization time is 2 ~ 10h;
B. adopt He Lv source, same silicon source, the method that adopts co-precipitation is by must ratio preparing product mixed liquid B, and the mol ratio that Product mix liquid B always forms is: Na
2o: SiO
2: A1
2o
3: H
2o=(3 ~ 30): (20 ~ 200): 1: (20 ~ 250);
C. in Product mix liquid B, add crystal seed mixed liquor A, SiO in crystal seed mixed liquor A add-on and Product mix liquid B
2mass ratio be (10 ~ 40): 100; Then rapid stirring certain hour, after stirring, reaction mixture is put into water heating kettle and carried out crystallization, crystallization time is 5 ~ 60h, and crystallization temperature is 120 ~ 200 DEG C, the product that crystallization obtains, through washing, centrifugal, dry, roasting, just obtains uniform particles ZSM-5 zeolite molecular sieve.
Described silicon source is selected from a kind of of water glass, silicon sol or water glass or their mixture.
Described aluminium source is selected from a kind of of Tai-Ace S 150, aluminum chloride, aluminum phosphate or sodium aluminate or their mixture.
Described organic formwork agent is selected from a kind of or its mixture in 4-propyl bromide, TPAOH, quadrol, n-Butyl Amine 99, hexanediamine, dimethyl urea.
When the method for described co-precipitation is prepared crystal seed mixed liquor A and Product mix liquid B, the pH value of co-precipitation is controlled at 8.0 ~ 11.0.
Described grinding plant is colloidal mill, ball mill, mulser or shears.
The invention has the beneficial effects as follows: first the synthetic method of this uniform particles ZSM-5 molecular sieve adopts coprecipitation method to prepare crystal seed mixed solution, when co-precipitation, controlling precipitation pH value is 8 ~ 11, after precipitation, adopt grinding plant to be ground to certain fineness to throw out, then crystallization makes crystal seed mixed solution; The preparation of product ZSM-5 molecular sieve, first makes precipitation mixture by coprecipitation method, adds a certain proportion of crystal seed mixed solution, obtains the ZSM-5 molecular sieve of uniform granularity through the roasting of crystallization filtration washing.Can be according to differential responses requirement, prepare specified particle size ZSM-5 molecular sieve and meet the requirement of catalyzed reaction.Can synthesize fast the ZSM-5 zeolite molecular sieve of uniform crystal particles, building-up process adopts the synthetic material of conventional ZSM-5 zeolite molecular sieve, do not need mesoporous material etc. as Size of Zeolite restrictive substance, without long-time low temperature aging, and operation is simple, generated time is short, and whole building-up process only needs 15 ~ 30 hours, and gained ZSM-5 zeolite crystal size evenly.Feature is that the preparation of ZSM-5 molecular sieve just adds organic formwork agent time prepared by crystal seed mixed solution, only contains very small amount of organic formwork agent in the middle of final product; And can, easily by regulating the add-on of reaction conditions and organic formwork agent, finally control the globule size of ZSM-5 molecular sieve, the ZSM-5 Size of Zeolite of production is even, is applicable to the requirement of specific reaction to ZSM-5 molecular sieve.
Embodiment
Below by embodiment, the present invention is further illustrated.
embodiment 1
(1) preparation of crystal seed mixed solution
By 167.5g sodium silicate aqueous solution (SiO
2: 21.2 w%, Na
2o:6.32 w%), 8.53gNaOH and 96g water mixes, and makes silicon source mixed solution; Add Tai-Ace S 150 (Al at 220 grams of water
2(SO4) 3.18H
2o) 11.1 grams, sulfuric acid 15.8g, template 4-propyl bromide 5.5g mixes and makes aluminium source mixed solution; By two kinds of mixed solutions co-precipitation under whipped state, keep PH=9.8, after precipitation finishes, stir 0.5h, be then ground to precipitation particle diameter with colloidal mill and be less than 1 micron, mixture SiO
2: A1
2o
3=35, pack band into and stir high pressure water heating kettle, under rapid stirring, 120 DEG C of crystallization 5 hours, products therefrom was crystal seed mixture A.
(2) preparation of Product mix liquid
By 167.5 g sodium silicate aqueous solution (SiO
2: 21.2 w%, Na
2o:6.32 w%), 8.53gNaOH and 96g water mixes, and makes silicon source mixed solution; In 220 grams of water, add Tai-Ace S 150 (Al
2(SO
4) 3.18H
2o) 11.1 grams, sulfuric acid 15.8 g mix and make aluminium source mixed solution; By two kinds of mixed solutions co-precipitation under whipped state, keep PH=9.5, after precipitation finishes, add the above-mentioned crystal seed mixture of 50 g A, stir 0.5h, pack band into and stir high pressure water heating kettle, under rapid stirring 180 DEG C of crystallization 15 hours, then after filtration, after washing, dry, roasting, obtain product ZSM-5 molecular sieve.Granular size and size-grade distribution situation see attached list 1
Embodiment 2
The operation steps that repeats embodiment 1, difference is that silicon source is silicon sol, the results are shown in subordinate list 1.
Embodiment 3
The operation steps that repeats embodiment 1, difference is that aluminium source is aluminum nitrate, the results are shown in subordinate list 1.
Embodiment 4
Repeat the operation steps of embodiment 1, difference is that template adopts n-Butyl Amine 99, the results are shown in subordinate list 1.
Embodiment 5
The operation steps that repeats embodiment 1, difference is that template consumption is 11.0g, the results are shown in subordinate list 1.
Embodiment 6
Repeat the operation steps of embodiment 1, difference is that template adopts quadrol and dimethyl urea, respectively accounts for 50 m%, the results are shown in subordinate list 1.
Embodiment 7
Repeat the operation steps of embodiment 1, difference adopts colloidal mill to grind while being the preparation of crystal seed mixed solution to make deposit seeds thinner, and all particles are all less than 0.5 micron, the results are shown in subordinate list 1.
Embodiment 8
Repeat the operation steps of embodiment 7, when difference is the preparation of crystal seed mixed solution, crystallization time is 10h, the results are shown in subordinate list 1.
Embodiment 9
Repeat the operation steps of embodiment 7, when difference is prepared by product, the add-on of crystal seed mixed solution is 100g, the results are shown in subordinate list 1.
Embodiment 10
Repeat the operation steps of embodiment 8, when difference is prepared by product, crystallization time is 30h, the results are shown in subordinate list 1.
Embodiment 11
The operation steps that repeats embodiment 7, difference is the SiO of crystal seed mixed solution
2: A1
2o
3=60, the SiO of Product mix liquid
2: A1
2o
3=60, the results are shown in subordinate list 1.
Embodiment 12
Repeat the operation steps of embodiment 1, the PH=11.0 of co-precipitation when difference is prepared by crystal seed mixed solution, the PH=10.5 of co-precipitation time prepared by product adds aluminum solutions in silicon solution, the results are shown in subordinate list 1.
comparative example
Repeat embodiment 1, when difference is prepared by crystal seed mixed solution, aluminum solutions is added in silicon solution, after adding, grind without colloidal mill, stir 0.5 hour direct crystallization.Time prepared by product, aluminum solutions is added in silicon solution, then add crystal seed mixed solution, after stirring, crystallization, filtration, washing, oven dry, roasting obtain finished product.The results are shown in subordinate list 1.
Subordinate list 1
Claims (5)
1. a synthetic method for uniform particles ZSM-5 molecular sieve, is characterized in that: the synthesis step that described method adopts comprises:
A. use He Lv source, silicon source and organic formwork agent, adopt the method for co-precipitation to prepare slurry, slurry mol ratio is: Na
2o:SiO
2: A1
2o
3: H
2o:Q=(3～30): (20～200): 1:(20～250): (0.1～2), Q is organic formwork agent, with after grinding plant ground slurry, the diameter of micelle is less than 1 micron, then packing band into stirs in high pressure water heating kettle, crystallization is prepared crystal seed mixed liquor A, and crystallization temperature is 100～200 DEG C, and crystallization time is 2～10h;
B. adopt He Lv source, same silicon source, the method that adopts co-precipitation is by must ratio preparing product mixed liquid B, and the mol ratio that Product mix liquid B always forms is: Na
2o:SiO
2: A1
2o
3: H
2o=(3～30): (20～200): 1:(20～250);
C. in Product mix liquid B, add crystal seed mixed liquor A, SiO in crystal seed mixed liquor A add-on and Product mix liquid B
2mass ratio be (10～40): 100, the pH value of described crystal seed mixed liquor A and Product mix liquid B co-precipitation is controlled at 8.0～11.0; Then rapid stirring certain hour, after stirring, reaction mixture is put into water heating kettle and carried out crystallization, crystallization time is 5～60h, and crystallization temperature is 120～200 DEG C, the product that crystallization obtains, through washing, centrifugal, dry, roasting, just obtains uniform particles ZSM-5 zeolite molecular sieve.
2. the synthetic method of uniform particles ZSM-5 molecular sieve according to claim 1, is characterized in that: described silicon source is selected from a kind of of water glass, silicon sol or water glass or their mixture.
3. the synthetic method of uniform particles ZSM-5 molecular sieve according to claim 1, is characterized in that: described aluminium source is selected from a kind of of Tai-Ace S 150, aluminum chloride, aluminum phosphate or sodium aluminate or their mixture.
4. the synthetic method of uniform particles ZSM-5 molecular sieve according to claim 1, is characterized in that: described organic formwork agent is selected from a kind of or its mixture in 4-propyl bromide, TPAOH, quadrol, n-Butyl Amine 99, hexanediamine, dimethyl urea.
5. the synthetic method of uniform particles ZSM-5 molecular sieve according to claim 1, is characterized in that: described grinding plant is colloidal mill, ball mill, mulser or shears.
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| CN107282087A (en) * | 2016-04-01 | 2017-10-24 | 神华集团有限责任公司 | A kind of high silica ZSM-5 molecular sieve and its preparation method and application |
Families Citing this family (6)
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|---|---|---|---|---|
| CN103848440B (en) * | 2013-10-24 | 2018-02-16 | 碗海鹰 | The molecular sieves of high-specific surface area ZSM 5 and preparation method |
| CN103626203B (en) * | 2013-10-24 | 2018-02-09 | 碗海鹰 | A kind of preparation of nanometer of molecular sieve of ZSM 5 |
| CN104355318B (en) * | 2014-09-26 | 2016-06-22 | 大连瑞克科技有限公司 | A kind of synthetic method of nano-ZSM-5 molecular sieve |
| CN104556135B (en) * | 2015-01-28 | 2017-01-25 | 中国石油大学(北京) | Hydrothermal synthesis system for synthesizing ZSM-5 zeolite molecular sieve and application thereof |
| CN107640777A (en) * | 2017-09-05 | 2018-01-30 | 华南理工大学 | A kind of method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction |
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| CN101723402A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for synthesizing core-shell type zeolite molecular sieve |
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Inventor after: Deng Shaoliang Inventor after: Zhou Huanwen Inventor after: Cao Honggang Inventor after: Qiao Chuan Inventor after: Qu Xueqin Inventor before: Deng Shaoliang Inventor before: Zhou Huanwen Inventor before: Qiao Chuan Inventor before: Qu Xueqin |
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Address after: 116052 327 Shun Le street, Lushun Economic Development Zone, Dalian, Liaoning Patentee after: Dalian Ruike Technology Co.,Ltd. Address before: 116052 327 Shun Le street, Lushun Economic Development Zone, Dalian, Liaoning Patentee before: DALIAN RUIKE SCIENCE & TECHNOLOGY Co.,Ltd. |