CN102616806B - Method for preparing high-performance titanium and silicon molecular sieve - Google Patents
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Abstract
The invention relates to a method for preparing a high-performance titanium and silicon molecular sieve. The method comprises the following steps of: 1) uniformly mixing tetrapropylammonium bromide, ammonium fluoride, water and a hydrogen peroxide solution to obtain a clarified solution A; 2) under the condition of stirring, adding a titanium source into the solution A, adjusting the pH to be 10 to 13 by using ammonia water, and ageing until a light yellow clarified solution B is formed; 3) adding a silicon source into the solution B, and uniformly mixing to obtain crystallized mother liquor C; and 4) crystallizing the crystallized mother liquor C at the temperature of between 130 and 190 DEG C and self-generated pressure for 10 to 100 hours, and separating to obtain the solid titanium and silicon molecular sieve product. According to the method, the problems of high production cost and low catalysis performance of the titanium molecular sieve in the prior art are well solved; and the method for assisting in synthesizing the titanium and silicon molecular sieve by using low-water-ratio ammonium fluoride can be applied to industrial production of the titanium and silicon molecular sieve.
Description
Technical field
The present invention relates to a kind of preparation method of high-performance HTS, belong to the synthetic field of inorganic materials.
Background technology
Nineteen eighty-three, first US Patent No. 4410501 has reported that the success of titanium-silicon molecular sieve TS-1 is synthetic.Similar to current widely used ZSM-5 molecular sieve, this material also has MFI topological framework, its pore passage structure can hold entering of most side chains and monocycle organic molecule, in conjunction with its efficient catalysis hydrogen peroxide, carry out the characteristic of oxidizing reaction, this molecular sieve has purposes widely at numerous areas such as petrochemical complex, fine chemistry industries, and future market development potentiality is huge.
The classical synthesis path of TS-1 molecular sieve is that tetraethyl orthosilicate, tetrabutyl titanate, TPAOH and appropriate water are mixed to crystallization, wherein expensive as the TPAOH of template (being structure directing agent) and consumption is large, cause TS-1 Zeolite synthesis high cost, restricted application and the popularization of this material.
In the last thirty years, researchist has dropped into a large amount of energy in the low-cost synthetic technology exploitation of TS-1, and makes great progress.As patent EP0543247A1 is used more cheap 4-propyl bromide as template, take ammoniacal liquor as alkali source, silica gel as silicon source, tetrabutyl titanate is titanium source, with hydrogen peroxide, promotes the dispersed of titanium source, successfully synthesizes the TS-1 molecular sieve of high-crystallinity.Patent CN1375455A is template with 4-propyl bromide equally, take organic amine as alkali source, adopts variable temperature crystallization technique, synthesizes the HTS that crystal grain is less, and its catalytic epoxidation of propone performance is better than larger crystal molecular sieve; And patent CN101913620A has done improvement to it, by adding the method for nanosized seeds, shortened generated time.Patent CN1751996A has reported a kind of synthetic method of HTS, adopts methyl ethyl diketone or diethanolamine complexing agent and stablizes titanium source in conjunction with alcoholic solvent, synthesizes equally the uniform TS-1 product of size distribution in cheap material system.
In addition, also has the report that improves low cost titanium molecular sieve catalysis performance by aftertreatment or secondary crystallization, as patent CN101767036A is used a small amount of template, has also synthesized HTS with inorganic alkali source, then use the solution-treated product of acid and hydrogen peroxide, re-use ammonium salt, ammoniacal liquor or TPAOH solution product is carried out to crystallization again, the product obtaining has the advantages that particle is large, activity is high and catalytic performance is stable.Patent CN102311128A adopts the hydrolyzed solution in He Tai source, silicon source under saturated steam condition, HTS to be processed, and its catalytic activity has also obtained remarkable improvement.
Though aforesaid method has obtained the HTS product of synthetic cost, yet its catalytic activity is still not ideal enough, need to just can reach the requirement of application by further processing.
Summary of the invention
Technical problem to be solved by this invention is the problem that in prior art, production cost is high, product catalytic performance is not good, and a kind of method of low water ratio, Neutral ammonium fluoride auxiliary crystallization synthesis of titanium silicon molecular sieve is provided.Consumption of template agent in the method is few, and productive rate is high, and synthetic zeolite product has that particle diameter is moderate, the poor feature of extra-framework titanium, has good catalytic performance while being applied to hydrogen peroxide oxidation reaction.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of high-performance HTS, comprises the following steps:
1) 4-propyl bromide, Neutral ammonium fluoride, water and hydrogen peroxide solution are mixed, obtain settled solution A;
2) under agitation condition, in solution A, add titanium source, with ammoniacal liquor, regulate pH to 10～13, ageing is to forming faint yellow settled solution B;
3) silicon source is added in solution B, after mixing, obtain crystallization mother liquor C;
4) by crystallization mother liquor C crystallization 10～100 hours under 130～190 ℃, autogenous pressure, be then isolated to solid titanium si molecular sieves product.
In technique scheme, titanium source is selected from one or more in tetrabutyl titanate, positive tetraethyl titanate, titanium tetrafluoride and ammonium titanium fluoride; Silicon source is selected from one or more in silicon sol, tetraethyl orthosilicate and white carbon black; In crystallization mother liquor, the mol ratio of silicon-dioxide and 4-propyl bromide is 1:0.06 ~ 0.30; In crystallization mother liquor, the mol ratio of silicon-dioxide and titanium dioxide is 1:0.005 ~ 0.060; In crystallization mother liquor, the mol ratio of silicon-dioxide and Neutral ammonium fluoride is 1:0.05 ~ 0.30; In crystallization mother liquor, the mol ratio of titanium dioxide and hydrogen peroxide is 1:1 ~ 8; In crystallization mother liquor, the mol ratio of silicon-dioxide and water is 1:10 ~ 30.For shortening crystallization time, can in crystallization mother liquor, add crystal seed, crystal seed is the molecular sieve with MFI structure, it is 0.1wt%～10wt% that crystal seed be take silicon-dioxide shared weight ratio in crystallization mother liquor.
In above-mentioned HTS preparation method, use more cheap organic formwork agent 4-propyl bromide and inorganic alkali source ammoniacal liquor, and synthesize than under condition at lower water silicon, product yield increases substantially, thereby synthetic cost is effectively controlled; And denseer synthetic system easily obtains the micron-level molecular sieve product that crystal grain is relatively little, under the effect of mineralizer fluorion, can guarantee good degree of crystallinity again, therefore product performance are improved; In addition, fluorion, as mineralizer, has not only been accelerated the crystallization rate in silicon source, can also activate titanium source and the ratio that makes titanium enter skeleton improves, extra-framework titanium reduces thereupon, and synthetic HTS product can remove extra-framework titanium without aftertreatment just can obtain good catalytic performance.
Embodiment
Below by embodiment, the invention will be further described.But embodiment does not limit the scope of the present invention.
comparative example 1
Take 50g tetraethyl orthosilicate (TEOS, SiO
2content > 28 wt %) and 5g tetrabutyl titanate (TBOT, TiO
2content > 23 wt %), add 57g TPAOH solution (TPAOH content is 25wt%) after mixing, be stirred to formation homogeneous latex emulsion, mole proportioning of its composition is 1 SiO
2: 0.06 TiO
2: 0.30 TPA
+: 10H
2o.Above-mentioned emulsion is transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, dynamic crystallization is 24 hours at 100 ℃, obtains nano-scale TS-1 dispersion liquid.Product obtains solid phase prod after centrifugation, washing, will it in baking oven 120 ℃ dry 6 hours, then in 550 ℃ of roastings 4 hours with removal template, obtain the former powder A of nano-titanium si molecular sieves.
comparative example 2
Take 15g 4-propyl bromide (TPABr content > 99wt%), be dissolved in 50g water, add 2.4g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add 4g tetrabutyl titanate (TBOT, TiO
2content > 23 wt %), with strong aqua (NH
3content is 25wt%) regulate pH to 11, stir to clarify, then add 36g silicon sol (SiO
2content is 31.4wt%), make up water is 1 SiO to forming mole proportioning
2: 0.06 TiO
2: 0.30 TPA
+: 0.24 H
2o
2: 40H
2the crystallization mother liquor of O, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, dynamic crystallization is 48 hours at 170 ℃, product after filtration, after washing in 120 ℃ dry 6 hours, then at 550 ℃, roasting obtains the former powder B of micron order HTS to remove template in 4 hours.
embodiment 1
Take 15g 4-propyl bromide (TPABr content > 99 wt %), be dissolved in 25g water, add 2.4g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add 4g tetrabutyl titanate (TBOT, TiO
2content > 23 wt %), with strong aqua (NH
3content is 25wt%) regulate pH to 11, stir to clarify, then add 36g silicon sol (SiO
2content is 31.4wt%), make up water is 1 SiO to forming mole proportioning
2: 0.06 TiO
2: 0.30 TPA
+: 0.24 H
2o
2: 25H
2the crystallization mother liquor of O, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, dynamic crystallization is 48 hours at 170 ℃, product after filtration, after washing in 120 ℃ dry 6 hours, then at 550 ℃, roasting obtains the former powder C of HTS to remove template in 4 hours.
embodiment 2
Take 5g 4-propyl bromide (TPABr content >99 wt %), be dissolved in 15g water, add 2.4g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add 4g tetrabutyl titanate (TBOT, TiO
2content > 23 wt %), with strong aqua (NH
3content is 25wt%) regulate pH to 12, stir to clarify, then add 36g silicon sol (SiO
2content is 31.4wt%), make up water is 1 SiO to forming mole proportioning
2: 0.06 TiO
2: 0.10 TPA
+: 0.24 H
2o
2: 25H
2the crystallization mother liquor of O, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, dynamic crystallization is 48 hours at 170 ℃, product after filtration, after washing in 120 ℃ dry 6 hours, then at 550 ℃, roasting obtains the former powder D of HTS to remove template in 4 hours.
embodiment 3
Take 5g 4-propyl bromide (TPABr content > 99 wt %) and 1.4g Neutral ammonium fluoride (NH
4f content > 99wt%), be dissolved in 15g water, add 2.4g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add 4g tetrabutyl titanate (TBOT, TiO
2content > 23 wt %), with strong aqua (NH
3content is 25wt%) regulate pH to 12, stir to clarify, then add 36g silicon sol (SiO
2content is 31.4wt%), make up water is 1 SiO to forming mole proportioning
2: 0.06 TiO
2: 0.10 TPA
+: 0.20 F
-: 0.24 H
2o
2: 25H
2the crystallization mother liquor of O, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, dynamic crystallization is 48 hours at 170 ℃, product after filtration, after washing in 120 ℃ dry 6 hours, then at 550 ℃, roasting obtains the former powder E of HTS to remove template in 4 hours.
embodiment 4
Take 5g 4-propyl bromide (TPABr content > 99 wt %>) and 0.7g Neutral ammonium fluoride (NH
4f content > 99wt%), be dissolved in 15g water, add 0.4g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add 2g tetrabutyl titanate (TBOT, TiO
2content > 23 wt %), with strong aqua (NH
3content is 25wt%) regulate pH to 12, stir to clarify, then add 36g silicon sol (SiO
2content is 31.4wt%), make up water is 1 SiO to forming mole proportioning
2: 0.03 TiO
2: 0.10 TPA
+: 0.10 F
-: 0.04 H
2o
2: 15H
2the crystallization mother liquor of O, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, dynamic crystallization is 48 hours at 170 ℃, product after filtration, after washing in 120 ℃ dry 6 hours, then at 550 ℃, roasting obtains the former powder F of HTS to remove template in 4 hours.
embodiment 5,6
Take 5g 4-propyl bromide (TPABr content > 99 wt %) and 0.7g Neutral ammonium fluoride (NH
4f> 99wt%), be dissolved in 15g water, add 0.4g hydrogen peroxide solution (H
2o
2content is 27wt%), corresponding 1g and 0.4g tetrabutyl titanate (TBOT, the TiO of adding under agitation condition
2content > 23wt%), other steps are with embodiment 4, and the former powder of the corresponding HTS obtaining is designated as G and H.
embodiment 7
Take 5g 4-propyl bromide (TPAB content > 99 wt %) and 2.1g Neutral ammonium fluoride (NH
4f content > 99wt%), be dissolved in 25g water, add 0.9g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add the positive tetraethyl titanate of 1.5g (TEOT, TiO
2content > 33 wt %), with strong aqua (NH
3content is 25wt%) regulate pH to 11, stir to clarify, then add 11.5g white carbon black (SiO
2content > 98wt%), make up water is 1 SiO to forming mole proportioning
2: 0.03 TiO
2: 0.10 TPA
+: 0.30 F
-: 0.09 H
2o
2: 15H
2the crystallization mother liquor of O, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, dynamic crystallization is 72 hours at 170 ℃, product after filtration, after washing in 120 ℃ dry 6 hours, then at 550 ℃, roasting obtains the former powder I of HTS to remove template in 4 hours.
embodiment 8
Take 5g 4-propyl bromide (TPABr content > 99 wt %) and 0.7g Neutral ammonium fluoride (NH
4f content > 99wt%), be dissolved in 25g water, add 0.9g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add 2g tetrabutyl titanate (TBOT, TiO
2content > 23 % by weight), with strong aqua (NH
3content is 25wt%) regulate pH to 11, stir to clarify, then add 40g tetraethyl orthosilicate (TEOS, SiO
2content > 28 wt %), make up water is 1 SiO to forming mole proportioning
2: 0.03 TiO
2: 0.10 TPA
+: 0.10 F
-: 0.09 H
2o
2: 15H
2the crystallization mother liquor of O, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, dynamic crystallization is 48 hours at 170 ℃, product after filtration, after washing in 120 ℃ dry 6 hours, then at 550 ℃, roasting obtains the former powder J of HTS to remove template in 4 hours.
embodiment 9
Take 5g 4-propyl bromide (TPABr content > 99 wt %) and 0.35g Neutral ammonium fluoride (NH
4f content > 99wt%), be dissolved in 15g water, add 0.4g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add 0.7g titanium tetrafluoride (TiF
4content > 98.5wt%), with strong aqua (NH
3content is 25wt%) regulate pH to 12, stir to clarify, then add 36g silicon sol (SiO
2content is 31.4wt%), make up water is 1 SiO to forming mole proportioning
2: 0.03 TiO
2: 0.10 TPA
+: 0.05 F
-: 0.04 H
2o
2: 15H
2the crystallization mother liquor of O, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, dynamic crystallization is 48 hours at 170 ℃, product after filtration, after washing in 120 ℃ dry 6 hours, then at 550 ℃, roasting obtains the former powder K of HTS to remove template in 4 hours.
embodiment 10
Take 5g 4-propyl bromide (TPABr content > 99 wt %) and 0.35g Neutral ammonium fluoride (NH
4f content > 99wt%), be dissolved in 15g water, add 0.4g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add 1.2g ammonium titanium fluoride [(NH4)
2tiF
6content > 98 wt %], with strong aqua (NH
3content is 25wt%) regulate pH to 12, stir to clarify, then add 36g silicon sol (SiO
2content is 31.4wt%), make up water is 1 SiO to forming mole proportioning
2: 0.03 TiO
2: 0.10 TPA
+: 0.05 F
-: 0.04 H
2o
2: 15H
2the crystallization mother liquor of O, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, dynamic crystallization is 48 hours at 170 ℃, product after filtration, after washing in 120 ℃ dry 6 hours, then at 550 ℃, roasting obtains the former powder L of HTS to remove template in 4 hours.
embodiment 11,12]
Take 5g 4-propyl bromide (TPABr content > 99wt%) and 0.7g Neutral ammonium fluoride (NH
4f content > 99wt%), be dissolved in 15g water, add 0.9g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add 2g tetrabutyl titanate (TBOT, TiO
2content > 23wt%), with strong aqua (NH
3content is 25wt%) regulate pH to 12, stir to clarify, add 36g silicon sol (SiO
2content is 31.4wt%), make up water is 1 SiO to forming mole proportioning
2: 0.03 TiO
2: 0.10 TPA
+: 0.10 F
-: 0.09 H
2o
2: 15H
2the crystallization mother liquor of O, more corresponding 0.1g and the former powder A(SiO of 1.2g HTS of adding respectively
2content is 89wt%) to make crystal seed, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, at 170 ℃, dynamic crystallization is 24 hours, product after filtration, dry 6 hours in 120 ℃ after washing, then at 550 ℃ roasting 4 hours to remove template, the corresponding former powder M of HTS and the N of obtaining.
embodiment 13,14]
Take 5g 4-propyl bromide (TPABr content > 99wt%) and 0.7g Neutral ammonium fluoride (NH
4f content > 99wt%), be dissolved in 15g water, add 0.9g hydrogen peroxide solution (H
2o
2content is 27wt%), under agitation condition, add 2g tetrabutyl titanate (TBOT, TiO
2content > 23 wt %), with strong aqua (NH
3content is 25wt%) regulate pH to 12, stir to clarify, add 36g silicon sol (SiO
2content is 31.4wt%), make up water is 1 SiO to forming mole proportioning
2: 0.03 TiO
2: 0.10 TPA
+: 0.10 F
-: 0.09 H
2o
2: 15H
2the crystallization mother liquor of O, the more corresponding former powder F(SiO of 1.2g HTS that adds respectively
2content is 89wt%) and commercially available high silica ZSM-5 molecular sieve (SiO
2content is 93wt%) to make crystal seed, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, at 170 ℃, dynamic crystallization is 24 hours, product after filtration, dry 6 hours in 120 ℃ after washing, then at 550 ℃ roasting 4 hours to remove template, the corresponding former powder O of HTS and the P of obtaining.
embodiment 15-17]
The proportioning raw materials of employing as described in embodiment 13, adds the former powder F(SiO of 1.2g HTS
2content is 89wt%) to make crystal seed, after mixing, be transferred in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, respectively corresponding to dynamic crystallization at dynamic crystallization at dynamic crystallization at 140 ℃ 96 hours, 155 ℃ 48 hours and 185 ℃ 18 hours, product after filtration, dry 6 hours in 120 ℃ after washing, then at 550 ℃ roasting 4 hours to remove template, the corresponding former powder Q of HTS, R and the S of obtaining.
embodiment 18]
Use x-ray powder diffraction to analyze above-mentioned HTS, instrument model is that Rigaku(is of science) Geigerflex.Degree of crystallinity is according in spectrogram 23.0
o, 23.6
o, 23.9
oand 24.3
othe relative peak height at place calculates, and best its degree of crystallinity of sample of the crystallization of take is 100%, and gained crystallinity data is listed in table 1.
embodiment 19]
The former powder of above-mentioned HTS is used for to pimelinketone oximate reaction evaluating, its step is as follows: accurately take the former powder of 0.25g HTS, 1.40g pimelinketone, the 16.60g trimethyl carbinol and 15.70g distilled water, join successively in the glass reactor with condensing reflux, open magnetic agitation, then be sequentially added into 1.60g hydrogen peroxide (H
2o
2content is 27wt%) and 2.00g ammoniacal liquor, 75 ℃ of reactions, after 2 hours, add the toluene of about 0.14g through accurately weighing as internal standard substance, sampling analysis then, gained response data is listed in table 1.
The transformation efficiency of above-mentioned reaction evaluating and selective calculation method are as follows:
Table 1
| Sample number into spectrum | Degree of crystallinity (%) | Transformation efficiency (%) | Selectivity (%) |
| A | 84 | 76.2 | 92.7 |
| B | 97 | 65.6 | 93.5 |
| C | 73 | 63.1 | 93.2 |
| D | 56 | 60.0 | 94.6 |
| E | 92 | 73.4 | 94.1 |
| F | 90 | 75.9 | 93.8 |
| G | 93 | 69.2 | 95.3 |
| H | 96 | 61.4 | 97.1 |
| I | 91 | 71.3 | 96.5 |
| J | 95 | 82.9 | 95.8 |
| K | 97 | 76.1 | 94.5 |
| L | 93 | 74.8 | 96.4 |
| M | 95 | 86.7 | 95.2 |
| N | 100 | 91.3 | 96.9 |
| O | 98 | 88.4 | 96.7 |
| P | 93 | 81.2 | 91.8 |
| Q | 89 | 88.6 | 94.2 |
| R | 97 | 92.7 | 95.5 |
| S | 99 | 79.8 | 97.2 |
1 column data of comparison sheet is known, adopt Neutral ammonium fluoride auxiliary crystallization method of the present invention, can the low water silicon that uses a small amount of organic formwork agent than synthetic system in, obtain well-crystallized's HTS, and can make the catalytic oxidation performance of product significantly improve, in the reaction process of catalysis of pimelinketone oximate, the pimelinketone transformation efficiency that is up to 92.7% and the cyclohexanone-oxime selectivity that is up to 97.2% have been obtained.
Claims (4)
1. a preparation method for high-performance HTS, is characterized in that the method comprises the following steps:
1) 4-propyl bromide, Neutral ammonium fluoride, water and hydrogen peroxide solution are mixed, obtain settled solution A;
2) under agitation condition, in solution A, add titanium source, with ammoniacal liquor, regulate pH to 10～13, ageing is to forming faint yellow settled solution B;
3) silicon source is added in solution B, after mixing, obtain crystallization mother liquor C;
4) by crystallization mother liquor C crystallization 10～100 hours under 130～190 ℃, autogenous pressure, be then isolated to solid titanium si molecular sieves product;
In crystallization mother liquor, the mol ratio of silicon-dioxide and 4-propyl bromide is 1:0.06～0.30; In crystallization mother liquor, the mol ratio of silicon-dioxide and titanium dioxide is 1:0.005～0.060; In crystallization mother liquor, the mol ratio of silicon-dioxide and Neutral ammonium fluoride is 1:0.05～0.30;
In crystallization mother liquor, the mol ratio of titanium dioxide and hydrogen peroxide is 1:1～8; In crystallization mother liquor, the mol ratio of silicon-dioxide and water is 1:10～30.
2. the preparation method of a kind of high-performance HTS according to claim 1, is characterized in that titanium source is selected from one or more in tetrabutyl titanate, positive tetraethyl titanate, titanium tetrafluoride and ammonium titanium fluoride.
3. the preparation method of a kind of high-performance HTS according to claim 1, is characterized in that silicon source is selected from one or more in silicon sol, tetraethyl orthosilicate and white carbon black.
4. the preparation method of a kind of high-performance HTS according to claim 1, it is characterized in that: in crystallization mother liquor, add crystal seed, crystal seed is the molecular sieve with MFI structure, and it is 0.1wt%～10wt% that crystal seed be take silicon-dioxide shared weight ratio in crystallization mother liquor.
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| CN104556115B (en) * | 2013-10-29 | 2017-02-15 | 中国石油化工股份有限公司 | Titanium silicalite molecular sieve synthesizing method |
| CN104815689B (en) * | 2015-03-17 | 2018-03-06 | 河南中宏清洁能源股份有限公司 | A kind of HPPO Catalyst Productions technological process |
| CN106185974B (en) * | 2016-07-07 | 2019-02-05 | 昆明理工大学 | A kind of preparation method of titanium-silicon molecular sieve TS-1 |
| CN106542549B (en) * | 2016-11-24 | 2018-10-26 | 山西大学 | A kind of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 and preparation method thereof |
| CN107792863B (en) * | 2017-11-28 | 2019-10-22 | 上海绿强新材料有限公司 | The synthetic method of catalyzing hydrogen peroxide oxidation reaction titanium-silicon molecular sieve TS-1 |
| CN113443635B (en) * | 2020-03-26 | 2023-02-10 | 中国石油天然气股份有限公司 | Titanium-containing Beta molecular sieve and synthesis method thereof |
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| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
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