CN104944436A - Method for quickly synthesizing Ti-MWW molecular sieve - Google Patents
Method for quickly synthesizing Ti-MWW molecular sieve Download PDFInfo
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- CN104944436A CN104944436A CN201510329456.7A CN201510329456A CN104944436A CN 104944436 A CN104944436 A CN 104944436A CN 201510329456 A CN201510329456 A CN 201510329456A CN 104944436 A CN104944436 A CN 104944436A
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Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for quickly synthesizing a Ti-MWW molecular sieve. According to the method, a sealed reaction kettle is enabled to rotate along a horizontal rotating shaft, ageing is carried out at a certain temperature for a period of time, rotating crystallization is carried out at a certain temperature for a period of time, and the rotating rate, ageing temperature, ageing time, crystallization temperature and crystallization time are adjusted reasonably, so that the purpose of quickly synthesizing Ti-MWW molecular sieve raw powder is realized, the synthesis time of the Ti-MWW molecular sieve is shortened greatly, energy consumption is reduced greatly, the production cost is reduced, moreover, the advantages that operation is simple and easy, the repeatability is good and the yield is high are realized.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to a kind of method of Fast back-projection algorithm Ti-MWW molecular sieve.
Background technology
Ti-MWW molecular sieve is the most effective titanium-silicon molecular sieve catalyst in current epoxidation reaction of olefines (Catalysis Surveys from Asia, 2004,8 (2), 137).The preparation of Ti-MWW molecular sieve is at first at Chemistry Letters, 2000, open report on 774, The Journal of Physical Chemistry B, 2001,105,2897 play-by-play preparation process: (one) prepare the mixing solutions of template and water and be divided into 2 parts; (2) titanium source and boron source are joined in the solution divided equally respectively, then in the mixed system formed, add silicon source respectively, after obtaining homogenous gel-like products, by the two kinds of gel mixing formed; (3) mixed gel obtained is placed in closed reactor crystallization 7 days under the stir speed (S.S.) of 100rpm, obtains Ti-MWW molecular screen primary powder; (4) with acid solution, Ti-MWW molecular screen primary powder is processed, obtain product Ti-MWW molecular sieve finally by roasting.This method process is complicated, and technical process is long, and production cost is high, is unfavorable for suitability for industrialized production and application.CN1466545A discloses a kind of production method of titanosilicate catalyst, and the method by using the oxidizing reaction of this catalyzer to produce oxygenated compound, and preparation process is substantially with Chemistry Letters, 2000:774.
CN1686795A discloses a kind of method that a step becomes to compose Ti-MWW molecular sieve, and preparation process is: by silicon source, titanium source, boron source, template, fluorine source and water Homogeneous phase mixing plastic, and hydrothermal crystallizing 5 hours ~ 20 days, obtains Ti-MWW molecular screen primary powder.This synthetic method process is relatively simple, but needs to add fluorine source, both adds cost, and turn increases the corrodibility to equipment.
CN101012062A discloses one and introduce tensio-active agent in Ti-MWW Crystallization of Zeolite process, and hydrothermal crystallizing prepares the method for Ti-MWW molecular screen primary powder for 3 ~ 10 days.Tensio-active agent add the activity that improve catalyzer, but too increase production cost, crystallization time is long simultaneously adds energy consumption and production cost.
In sum, up to now, also do not have bibliographical information to pass through to control reactor and rotate ageing and rotate crystallization, shorten the method that generated time reaches Fast back-projection algorithm Ti-MWW molecular screen primary powder.
Summary of the invention
The object of the present invention is to provide a kind of method of Fast back-projection algorithm Ti-MWW molecular screen primary powder.The program makes closed reactor rotate along horizontal rotating shaft, first rotate ageing for some time at a certain temperature, rotate crystallization for some time at a certain temperature again, reasonable adjusting slewing rate, Aging Temperature, digestion time, crystallization temperature and crystallization time, the object of Fast back-projection algorithm Ti-MWW molecular screen primary powder can be reached, substantially reduce the generated time of Ti-MWW molecular sieve, greatly reduce energy consumption, save production cost, there is the advantage that operation is simple, reproducible, productive rate is high simultaneously.
The technical scheme reaching above-mentioned technical purpose provided by the present invention is as follows.
A method for Fast back-projection algorithm Ti-MWW molecular sieve, comprises the steps:
1) mixed raw material is become reaction gel.
Concrete, the synthetic method in reaction gel is: under room temperature, by organic amine, water, titanium source, boron source and silicon source by mole composition (0.002 ~ 0.5) TiO
2: (0.2 ~ 10.0) SiO
2: (0.01 ~ 10.0) B
2o
3: (0.1 ~ 10.0) organic amine: (1 ~ 1000) H
2o Homogeneous phase mixing makes gel, and described titanium source is tetralkyl titanate, halogenated titanium or titanium oxide, and described silicon source is silicon-dioxide, silicon sol or tetraethoxy, and described boron source is boric acid or borate, and described organic amine is piperidines or hexamethylene imine.
2) reaction gel is placed in closed reactor, afterwards, then closed reactor is carried out rotation ageing around horizontal rotating shaft rotation and rotates crystallization, obtain molecular sieve crystalline flour, wherein, the time sum of rotating ageing and rotation crystallization is more than or equal to 63 hours, is less than or equal to 90 hours.Preferably, the time sum of rotating ageing and rotation crystallization is more than or equal to 72 hours, is less than or equal to 84 hours.
Wherein:
Concrete, the rotating speed of described rotation ageing is 10 ~ 40 revs/min.
Concrete, the Aging Temperature of described rotation ageing is 25 ~ 150 DEG C.
Preferably, the first paragraph of 25 ~ 100 DEG C that the described rotation ageing propelling comprised along with the time is carried out rotates ageing, the second segment of 110 ~ 150 DEG C rotates ageing.By to the precise controlling rotating ageing process, the uniformity coefficient of size distribution can be improved.
Preferably, the digestion time that described first paragraph rotates ageing is 5 ~ 16 hours, and the digestion time that second segment rotates ageing is 5 ~ 20 hours.
Concrete, the rotating speed of described rotation crystallization is 25 ~ 60 revs/min.
Concrete, the crystallization temperature of described rotation crystallization is 150 ~ 200 DEG C.
Preferably, the first paragraph of 150 ~ 170 DEG C that the propelling comprised along with the time of described rotation crystallization is carried out rotates crystallization, the second segment of 150 ~ 200 DEG C rotates crystallization.By to the precise controlling rotating crystallization process, can grain growing be promoted, improve Ti-MWW molecular screen primary powder crystallization rate.
Preferably, the crystallization time that described first paragraph rotates crystallization is 19 ~ 36 hours, and the crystallization time that second segment rotates crystallization is 20 ~ 36 hours.
Preferably, the packing volume percentage ratio of reaction gel in closed reactor is 10 ~ 85%.
In conventional hydrothermal crystallization method, be load in closed reactor by reaction gel, electric mixer is rapid stirring vertically, as shown in Figure 1.Although reaction gel is in gas-solid-liquid three-phase coexistence state in closed reactor under synthesis temperature, due to action of gravity, most of gel, still in the bottom of reactor, is unfavorable for the homoepitaxial of nucleus, thus causes crystallization time to extend.
And in the method that provided Fast back-projection algorithm Ti-MWW molecular sieve is provided, as shown in Figure 2, the closed reactor that reaction gel is housed rotates ageing around horizontal rotating shaft 1 and rotates crystallization, reaction mixture is made to obtain mixing full and uniform to the limit, with time modulation slewing rate, Aging Temperature, digestion time, crystallization temperature and crystallization time, simultaneously, the control of further refinement is rotated ageing and rotates crystallization process, can reach the object greatly shortening Ti-MWW molecular screen primary powder generated time.
3) by step 2) the molecular sieve crystalline flour that obtains successively after filtration, washing, dry, obtain molecular screen primary powder.
4) by step 3) after the molecular screen primary powder that obtains carries out acid treatment, successively after filtration, washing, dry, roasting, obtain product Ti-MWW molecular sieve.
Concrete, it is characterized in that acid treatment working concentration is mineral acid or the organic acid of 2mol/L, catalyzer and mineral acid or organic acid by weight 1:50 mixing, at 80 DEG C of backflow 20h.
Concrete, described roasting is 550 DEG C of roasting 8h, obtains product Ti-MWW molecular sieve.
Present invention also offers and synthesize according to aforesaid method the Ti-MWW molecular sieve obtained.
At present, based on prior art, the Ti-MWW product synthesizing final performance maturation up to standard generally at least needs the time of 7 days.By the systematic study to solution problems of the prior art, contriver finds: by controlling rotating around horizontal rotating shaft of closed reactor, control ageing and crystallization process, reaction mixture can be made to obtain to greatest extent in ageing and crystallization process, full and uniform mixing, to promote the nucleation of molecular sieve nucleus fast and high quality, thus significantly shorten the generated time of Ti-MWW molecular screen primary powder, from the time of about general 7 days, significantly shorten to 63-90 hour.From the angle of actual production, especially for situation about producing in enormous quantities, the shortening of so significant time, self-evident to the meaning of large-scale production.
Therefore, generally compared with prior art, the present invention has following remarkable advantage: generated time is short, save energy, and operation is simple, reproducible, and productive rate is high, is beneficial to suitability for industrialized production and application.
Figure of description
Fig. 1 is the alr mode of electric mixer vertically rapid stirring in prior art.
Fig. 2 is the front view of alr mode in the method for Fast back-projection algorithm Ti-MWW molecular screen primary powder provided by the present invention.
In Fig. 2,1 is horizontal rotating shaft, and 2 is connecting rod, and 3 is closed reactor.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Below, all embodiments all operate by the operation steps of technique scheme.
Embodiment 1
Under room temperature, joined by a certain amount of organic amine in certain water gaging, stir after half an hour, then add titanium source, boron source add a certain amount of silicon source after stirring again successively, obtained reaction gel, gel mole consists of 0.04TiO
2: 1.0SiO
2: 0.67B
2o
3: 1.5 organic amines: 25.0H
2o.As shown in Figure 2, reaction gel is placed in closed reactor 3, closed reactor 3 is fixed on the horizontal rotating shaft 1 of homogeneous reactor by connecting rod 2, regulates slewing rate to be 10 revs/min.First 80 DEG C of ageings 12 hours, then slewing rate is regulated to be 30 revs/min, 120 DEG C of ageings 12 hours, slewing rate is regulated to be 40 revs/min again, 170 DEG C of crystallization 30 hours, then slewing rate is regulated to be 60 revs/min, 170 DEG C of crystallization 30 hours, after filtration, washing, drying, obtain Ti-MWW molecular screen primary powder, described titanium source is tetrabutyl titanate, and described silicon source is silicon-dioxide, described boron source is boric acid, and described organic amine is piperidines.Being 2mol/L nitric acid by the molecular screen primary powder obtained and concentration mix by weight for 1:50,80 DEG C of backflows 20 hours, after filtration, washs, drying, obtains acid-treated product; Again by acid-treated product in 550 DEG C of roastings 8 hours, obtain product Ti-MWW molecular sieve.
In other examples, according to technical scheme provided by the present invention, adjust in given scope the proportioning of raw material, the performance of the product obtained is suitable.
Embodiment 2 ~ 10
Except for the following differences, all the other are all with embodiment 1 for implementation process.
Table 1
The catalytic activity of synthesized Ti-MWW molecular sieve is evaluated with chloro propylene epoxidation reaction.Catalytic reaction condition is: catalyzer 0.2 gram, 3.9 grams, acetone, propenyl chloride 2.295 grams, hydrogen peroxide (mass concentration 27.3%) 3.73 grams.Detailed process is, joins in twoport flask successively by catalyzer, solvent and reactant, under agitation, hydrogen peroxide is equally divided into four parts, joins successively in reactor in 30 minutes, and 60 DEG C are reacted 8 hours.Result is as shown in table 2.
Table 2
| Propenyl chloride transformation efficiency % | Epoxy selectivity % | |
| Embodiment 1 | 96.0 | 99.9 |
| Embodiment 2 | 85.3 | 99.9 |
| Embodiment 3 | 95.5 | 99.9 |
| Embodiment 4 | 80.9 | 99.9 |
| Embodiment 5 | 93.4 | 99.9 |
| Embodiment 6 | 71.7 | 100 |
| Embodiment 7 | 64.6 | 100 |
| Embodiment 8 | 43.2 | 99.8 |
| Embodiment 9 | 75.1 | 100 |
| Embodiment 10 | 69.8 | 98.9 |
The foregoing is only better embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a method for Fast back-projection algorithm Ti-MWW molecular sieve, is characterized in that, comprises the steps:
1) mixed raw material is become reaction gel;
2) by step 1) reaction gel that obtains is placed in closed reactor, afterwards, again closed reactor is rotated around horizontal rotating shaft and carry out rotation ageing and rotate crystallization, obtain molecular sieve crystalline flour, wherein, the time sum of rotating ageing and rotation crystallization is more than or equal to 63 hours and is less than or equal to 90 hours;
3) by step 2) the molecular sieve crystalline flour that obtains successively after filtration, washing, dry, obtain molecular screen primary powder;
4) by step 3) after the molecular screen primary powder that obtains carries out acid treatment, successively after filtration, washing, dry, roasting, obtain product Ti-MWW molecular sieve.
2. the method for Fast back-projection algorithm Ti-MWW molecular sieve according to claim 1, is characterized in that: the rotating speed of described rotation ageing is 10 ~ 40 revs/min.
3. the method for Fast back-projection algorithm Ti-MWW molecular sieve according to claim 2, is characterized in that: the Aging Temperature of described rotation ageing is 25 ~ 150 DEG C.
4. the method for Fast back-projection algorithm Ti-MWW molecular sieve according to claim 3, is characterized in that, the first paragraph of 25 ~ 100 DEG C that the described rotation ageing propelling comprised along with the time is carried out rotates ageing, the second segment of 110 ~ 150 DEG C rotates ageing.
5. the method for Fast back-projection algorithm Ti-MWW molecular sieve according to claim 4, is characterized in that: the digestion time that described first paragraph rotates ageing is 5 ~ 16 hours, and the digestion time that second segment rotates ageing is 5 ~ 20 hours.
6. the method for Fast back-projection algorithm Ti-MWW molecular sieve according to claim 1, is characterized in that: the rotating speed of described rotation crystallization is 25 ~ 60 revs/min.
7. the method for Fast back-projection algorithm Ti-MWW molecular sieve according to claim 6, is characterized in that: the crystallization temperature of described rotation crystallization is 150 ~ 200 DEG C.
8. the method for Fast back-projection algorithm Ti-MWW molecular sieve according to claim 7, is characterized in that: the first paragraph of 150 ~ 170 DEG C that the propelling comprised along with the time of described rotation crystallization is carried out rotates crystallization, the second segment of 150 ~ 200 DEG C rotates crystallization.
9. the method for Fast back-projection algorithm Ti-MWW molecular sieve according to claim 1 according to Claim 8, is characterized in that: the crystallization time that described first paragraph rotates crystallization is 19 ~ 36 hours, and the crystallization time that second segment rotates crystallization is 20 ~ 36 hours.
10. according to the method for the arbitrary described Fast back-projection algorithm Ti-MWW molecular sieve of claim 1 to 9, it is characterized in that, step 1) in the synthetic method of reaction gel be: under room temperature, by organic amine, water, titanium source, boron source and silicon source by mole composition (0.002 ~ 0.5) TiO
2: (0.2 ~ 10.0) SiO
2: (0.01 ~ 10.0) B
2o
3: (0.1 ~ 10.0) organic amine: (1 ~ 1000) H
2o Homogeneous phase mixing makes gel, and described titanium source is tetralkyl titanate, halogenated titanium or titanium oxide, and described silicon source is silicon-dioxide, silicon sol or tetraethoxy, and described boron source is boric acid or borate, and described organic amine is piperidines or hexamethylene imine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329909A (en) * | 2015-11-30 | 2016-02-17 | 湖北大学 | Method for synthesizing Ti-MWW molecular sieve hollow sphere with high external specific surface area |
| CN105645430A (en) * | 2016-02-25 | 2016-06-08 | 湖北大学 | Crystal-seed method for rapidly synthesizing Ti-MWW molecular sieves through rotation |
| CN106365175A (en) * | 2016-08-22 | 2017-02-01 | 天津大学 | Microwave assisted method for synthesizing CHA molecular sieve from gangue |
| CN108212206A (en) * | 2017-12-29 | 2018-06-29 | 中触媒新材料股份有限公司 | A kind of magnetic coupling Ti-MWW microsphere zeolite catalyst preparation methods |
| CN109678171A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | High external surface area, high skeleton Ti content Ti-MWW molecular sieve and preparation method thereof and catalytic applications |
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2015
- 2015-06-15 CN CN201510329456.7A patent/CN104944436A/en active Pending
Non-Patent Citations (1)
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| 文建军: "动态晶化法合成小晶粒NaY分子筛的研究", 《湖南师范大学自然科学学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329909A (en) * | 2015-11-30 | 2016-02-17 | 湖北大学 | Method for synthesizing Ti-MWW molecular sieve hollow sphere with high external specific surface area |
| CN105645430A (en) * | 2016-02-25 | 2016-06-08 | 湖北大学 | Crystal-seed method for rapidly synthesizing Ti-MWW molecular sieves through rotation |
| CN105645430B (en) * | 2016-02-25 | 2019-03-01 | 湖北大学 | A kind of method of crystal seed method rotation rapid synthesis Ti-MWW molecular sieve |
| CN106365175A (en) * | 2016-08-22 | 2017-02-01 | 天津大学 | Microwave assisted method for synthesizing CHA molecular sieve from gangue |
| CN106365175B (en) * | 2016-08-22 | 2018-07-24 | 天津大学 | A kind of method of microwave radiation technology gangue synthesis CHA molecular sieves |
| CN109678171A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | High external surface area, high skeleton Ti content Ti-MWW molecular sieve and preparation method thereof and catalytic applications |
| CN109678171B (en) * | 2017-10-19 | 2024-03-29 | 中国石油化工股份有限公司 | Ti-MWW molecular sieve with high external surface area and high framework titanium content, and preparation method and catalytic application thereof |
| CN108212206A (en) * | 2017-12-29 | 2018-06-29 | 中触媒新材料股份有限公司 | A kind of magnetic coupling Ti-MWW microsphere zeolite catalyst preparation methods |
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