CN102616806A - Method for preparing high-performance titanium and silicon molecular sieve - Google Patents

Method for preparing high-performance titanium and silicon molecular sieve Download PDF

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CN102616806A
CN102616806A CN2012101166838A CN201210116683A CN102616806A CN 102616806 A CN102616806 A CN 102616806A CN 2012101166838 A CN2012101166838 A CN 2012101166838A CN 201210116683 A CN201210116683 A CN 201210116683A CN 102616806 A CN102616806 A CN 102616806A
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titanium
mother liquor
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CN102616806B (en
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夏建超
夏娟
文怀有
谈赟
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Shanghai Novel Chemical Technology Co Ltd
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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

A kind of preparation method of high-performance HTS
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, U.S. Pat 4410501 has reported that at first the success of titanium-silicon molecular sieve TS-1 is synthetic.Similar with present widely used ZSM-5 molecular sieve; This material also has the MFI topological framework; Its pore passage structure can hold the entering of most side chains and monocycle organic molecule; In conjunction with its efficiently the catalysis ydrogen peroxide 50 carry out the characteristic of oxidizing reaction, this molecular sieve has purposes widely at numerous areas such as petrochemical complex, fine chemistry industries, the future market development potentiality is huge.
The classical synthesis path of TS-1 molecular sieve is that positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH and an amount of water are mixed crystallization; Wherein cost an arm and a leg as the TPAOH of template (being structure directing agent) and consumption big; Cause the synthetic cost of TS-1 molecular sieve too high, restricted the application and the popularization of this material.
In the last thirty years, the researchist has dropped into a large amount of energy in the low-cost synthetic technology exploitation of TS-1, and has obtained very big progress.Using cheap 4-propyl bromide as template like patent EP0543247A1, is that alkali source, silica gel are that silicon source, tetrabutyl titanate are the titanium source with ammoniacal liquor, with the homodisperse in ydrogen peroxide 50 promotion titanium source, successfully synthesizes the TS-1 molecular sieve of high-crystallinity.Patent CN1375455A uses 4-propyl bromide to be template equally, is alkali source with the organic amine, adopts variable temperature crystallization technology, synthesizes the less HTS of crystal grain, and its catalytic epoxidation of propone performance is superior to big crystal grain molecular sieve; And patent CN101913620A has done improvement to it, has shortened generated time through the method for adding the nanometer crystal seed.Patent CN1751996A has reported a kind of compound method of HTS, adopts methyl ethyl diketone or diethylolamine complexing agent and combines alcoholic solvent to stablize the titanium source, in the material system of cheapness, synthesizes the uniform TS-1 product of size distribution equally.
In addition; Also has the report that improves low cost titanium molecular sieve catalysis performance through aftertreatment or secondary crystallization; Use a small amount of template, also synthesized HTS like patent CN101767036A with inorganic alkali source; Then use the solution-treated product of acid and ydrogen peroxide 50, re-use ammonium salt, ammoniacal liquor or TPAOH solution product is carried out crystallization again, the product that obtains has big, active height of particle and the stable characteristics of catalytic performance.Patent CN102311128A then adopts the hydrolyzed solution in silicon source and titanium source under the moist steam condition, HTS to be handled, and its catalytic activity has also obtained remarkable improvement.
Though aforesaid method has obtained the HTS product that synthetic cost reduces, yet its catalytic activity is still not ideal enough, need just can reach the requirement of application through further processing.
Summary of the invention
Technical problem to be solved by this invention is high, the not good problem of product catalytic performance of production cost in the prior art, and the method for a kind of low water ratio, Neutral ammonium fluoride auxiliary crystallization synthesis of titanium silicon molecular sieve is provided.Consumption of template agent in this method is few, and productive rate is high, and the synthetic zeolite product has that particle diameter is moderate, the poor characteristics of extra-framework titanium, and good catalytic performance is arranged when being applied to the hydrogen peroxide oxidation reaction.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of preparation method of high-performance HTS may further comprise the steps:
1) 4-propyl bromide, Neutral ammonium fluoride, water and hydrogen peroxide solution are mixed, obtain settled solution A;
2) under the agitation condition, in solution A, add the titanium source, regulate pH to 10～13 with ammoniacal liquor, ageing is to forming faint yellow settled solution B;
3) the silicon source is added in the solution B, obtain crystallization mother liquor C after mixing;
4) with crystallization mother liquor C crystallization 10～100 hours under 130～190 ℃, autogenous pressure, obtain solid titanium si molecular sieves product through separating then.
In the technique scheme, the titanium source is selected from one or more in tetrabutyl titanate, positive tetraethyl titanate, titanium tetrafluoride and the ammonium titanium fluoride; The silicon source is selected from one or more in silicon sol, positive tetraethyl orthosilicate and the WHITE CARBON BLACK; The mol ratio of silicon-dioxide and 4-propyl bromide is 1:0.06 ~ 0.30 in the crystallization mother liquor; The mol ratio of silicon-dioxide and titanium oxide is 1:0.005 ~ 0.060 in the crystallization mother liquor; The mol ratio of silicon-dioxide and Neutral ammonium fluoride is 1:0.05 ~ 0.30 in the crystallization mother liquor; The mol ratio of titanium oxide and ydrogen peroxide 50 is 1:1 ~ 8 in the crystallization mother liquor; The mol ratio of silicon-dioxide and water is 1:10 ~ 30 in the crystallization mother liquor.For shortening crystallization time, can in crystallization mother liquor, add crystal seed, crystal seed is the molecular sieve with MFI structure, crystal seed is 0.1wt%～10wt% in silicon-dioxide shared weight ratio in crystallization mother liquor.
In above-mentioned HTS preparation method, use cheap organic formwork agent 4-propyl bromide and inorganic alkali source ammoniacal liquor, and synthesize than under the condition at lower water silicon, product yield increases substantially, thereby synthetic cost is effectively controlled; And denseer synthetic system obtains the less relatively micron order zeolite product of crystal grain easily, under the effect of mineralizer fluorion, can guarantee good percent crystallinity again, and therefore product performance are improved; In addition; Fluorion has not only been accelerated the crystallization rate in silicon source as mineralizer, can also activation titanium source and the ratio that makes titanium get into 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
Through embodiment the present invention is described further below.But embodiment does not limit the scope of the present invention.
Comparative example 1
Take by weighing the positive tetraethyl orthosilicate of 50g (TEOS, SiO 2Han Liang>28 wt %) and 5g tetrabutyl titanate (TBOT, TiO 2Han Liang>23 wt %), mix the back and add 57g TPAOH solution (TPAOH content is 25wt%), be stirred to the formation homogeneous latex emulsion, the 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, 100 ℃ of following dynamic crystallizations 24 hours obtain nanometer TS-1 dispersion liquid.Product obtains solid phase prod after spinning, washing, will it 120 ℃ of drying 6 hours in baking oven, then in 550 ℃ of roastings 4 hours with the removal template, obtain the former powder A of nanometer HTS.
Comparative example 2
Take by weighing 15g 4-propyl bromide (TPABr Han Liang>99wt%), be dissolved in the 50g water, add 2.4g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds 4g tetrabutyl titanate (TBOT, TiO down 2Han Liang>23 wt %), with strong aqua (NH 3Content is 25wt%) regulate pH to 11, stir to clarify, add 36g silicon sol (SiO then 2Content is 31.4wt%), make up water is 1 SiO to forming the mole proportioning 2: 0.06 TiO 2: 0.30 TPA +: 0.24 H 2O 2: 40H 2The crystallization mother liquor of O; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, 170 ℃ of following dynamic crystallizations 48 hours, product through filter, after the washing in 120 ℃ of dryings 6 hours; Then 550 ℃ of following roastings 4 hours to remove template, obtain the former powder B of micron order HTS.
Embodiment 1
Take by weighing 15g 4-propyl bromide (TPABr Han Liang>99 wt %), be dissolved in the 25g water, add 2.4g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds 4g tetrabutyl titanate (TBOT, TiO down 2Han Liang>23 wt %), with strong aqua (NH 3Content is 25wt%) regulate pH to 11, stir to clarify, add 36g silicon sol (SiO then 2Content is 31.4wt%), make up water is 1 SiO to forming the mole proportioning 2: 0.06 TiO 2: 0.30 TPA +: 0.24 H 2O 2: 25H 2The crystallization mother liquor of O; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, 170 ℃ of following dynamic crystallizations 48 hours, product through filter, after the washing in 120 ℃ of dryings 6 hours; Then 550 ℃ of following roastings 4 hours to remove template, obtain the former powder C of HTS.
Embodiment 2
Take by weighing 5g 4-propyl bromide (TPABr Han Liang>99 wt %), be dissolved in the 15g water, add 2.4g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds 4g tetrabutyl titanate (TBOT, TiO down 2Han Liang>23 wt %), with strong aqua (NH 3Content is 25wt%) regulate pH to 12, stir to clarify, add 36g silicon sol (SiO then 2Content is 31.4wt%), make up water is 1 SiO to forming the mole proportioning 2: 0.06 TiO 2: 0.10 TPA +: 0.24 H 2O 2: 25H 2The crystallization mother liquor of O; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, 170 ℃ of following dynamic crystallizations 48 hours, product through filter, after the washing in 120 ℃ of dryings 6 hours; Then 550 ℃ of following roastings 4 hours to remove template, obtain the former powder D of HTS.
Embodiment 3
Take by weighing 5g 4-propyl bromide (TPABr Han Liang>99 wt %) and 1.4g Neutral ammonium fluoride (NH 4F Han Liang>99wt%), be dissolved in the 15g water, add 2.4g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds 4g tetrabutyl titanate (TBOT, TiO down 2Han Liang>23 wt %), with strong aqua (NH 3Content is 25wt%) regulate pH to 12, stir to clarify, add 36g silicon sol (SiO then 2Content is 31.4wt%), make up water is 1 SiO to forming the 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; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, 170 ℃ of following dynamic crystallizations 48 hours, product through filter, after the washing in 120 ℃ of dryings 6 hours; Then 550 ℃ of following roastings 4 hours to remove template, obtain the former powder E of HTS.
Embodiment 4
Take by weighing 5g 4-propyl bromide (TPABr Han Liang>99 wt %>) and 0.7g Neutral ammonium fluoride (NH 4F Han Liang>99wt%), be dissolved in the 15g water, add 0.4g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds 2g tetrabutyl titanate (TBOT, TiO down 2Han Liang>23 wt %), with strong aqua (NH 3Content is 25wt%) regulate pH to 12, stir to clarify, add 36g silicon sol (SiO then 2Content is 31.4wt%), make up water is 1 SiO to forming the 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; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, 170 ℃ of following dynamic crystallizations 48 hours, product through filter, after the washing in 120 ℃ of dryings 6 hours; Then 550 ℃ of following roastings 4 hours to remove template, obtain the former powder F of HTS.
Embodiment 5,6
Take by weighing 5g 4-propyl bromide (TPABr Han Liang>99 wt %) and 0.7g Neutral ammonium fluoride (NH 4F>99wt%), be dissolved in the 15g water, add 0.4g hydrogen peroxide solution (H 2O 2Content is 27wt%), corresponding adding 1g and 0.4g tetrabutyl titanate (TBOT, TiO under the agitation condition 2Han Liang>23wt%), other steps are with embodiment 4, and the former powder of the corresponding HTS that obtains is designated as G and H.
Embodiment 7
Take by weighing 5g 4-propyl bromide (TPAB Han Liang>99 wt %) and 2.1g Neutral ammonium fluoride (NH 4F Han Liang>99wt%), be dissolved in the 25g water, add 0.9g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds the positive tetraethyl titanate of 1.5g (TEOT, TiO down 2Han Liang>33 wt %), with strong aqua (NH 3Content is 25wt%) regulate pH to 11, stir to clarify, add 11.5g WHITE CARBON BLACK (SiO then 2Han Liang>98wt%), make up water is 1 SiO to forming the 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; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, 170 ℃ of following dynamic crystallizations 72 hours, product through filter, after the washing in 120 ℃ of dryings 6 hours; Then 550 ℃ of following roastings 4 hours to remove template, obtain the former powder I of HTS.
Embodiment 8
Take by weighing 5g 4-propyl bromide (TPABr Han Liang>99 wt %) and 0.7g Neutral ammonium fluoride (NH 4F Han Liang>99wt%), be dissolved in the 25g water, add 0.9g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds 2g tetrabutyl titanate (TBOT, TiO down 2Han Liang>23 weight %), with strong aqua (NH 3Content is 25wt%) regulate pH to 11, stir to clarify, add the positive tetraethyl orthosilicate of 40g (TEOS, SiO then 2Han Liang>28 wt %), make up water is 1 SiO to forming the 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; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, 170 ℃ of following dynamic crystallizations 48 hours, product through filter, after the washing in 120 ℃ of dryings 6 hours; Then 550 ℃ of following roastings 4 hours to remove template, obtain the former powder J of HTS.
Embodiment 9
Take by weighing 5g 4-propyl bromide (TPABr Han Liang>99 wt %) and 0.35g Neutral ammonium fluoride (NH 4F Han Liang>99wt%), be dissolved in the 15g water, add 0.4g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds 0.7g titanium tetrafluoride (TiF down 4Han Liang>98.5wt%), with strong aqua (NH 3Content is 25wt%) regulate pH to 12, stir to clarify, add 36g silicon sol (SiO then 2Content is 31.4wt%), make up water is 1 SiO to forming the 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; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, 170 ℃ of following dynamic crystallizations 48 hours, product through filter, after the washing in 120 ℃ of dryings 6 hours; Then 550 ℃ of following roastings 4 hours to remove template, obtain the former powder K of HTS.
Embodiment 10
Take by weighing 5g 4-propyl bromide (TPABr Han Liang>99 wt %) and 0.35g Neutral ammonium fluoride (NH 4F Han Liang>99wt%), be dissolved in the 15g water, add 0.4g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds the 1.2g ammonium titanium fluoride [(NH4) down 2TiF 6Han Liang>98 wt %], with strong aqua (NH 3Content is 25wt%) regulate pH to 12, stir to clarify, add 36g silicon sol (SiO then 2Content is 31.4wt%), make up water is 1 SiO to forming the 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; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene, 170 ℃ of following dynamic crystallizations 48 hours, product through filter, after the washing in 120 ℃ of dryings 6 hours; Then 550 ℃ of following roastings 4 hours to remove template, obtain the former powder L of HTS.
Embodiment 11,12]
Take by weighing 5g 4-propyl bromide (TPABr Han Liang>99wt%) with 0.7g Neutral ammonium fluoride (NH 4F Han Liang>99wt%), be dissolved in the 15g water, add 0.9g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds 2g tetrabutyl titanate (TBOT, TiO down 2Han Liang>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 the 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 is distinguished corresponding adding 0.1g and the former powder A of 1.2g HTS (SiO again 2Content is 89wt%) to make crystal seed; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene; 170 ℃ of following dynamic crystallizations 24 hours; Product through filter, the washing back is in 120 ℃ of dryings 6 hours, then 550 ℃ of following roastings 4 hours with removal template, corresponding former powder M of HTS and the N of obtaining.
Embodiment 13,14]
Take by weighing 5g 4-propyl bromide (TPABr Han Liang>99wt%) with 0.7g Neutral ammonium fluoride (NH 4F Han Liang>99wt%), be dissolved in the 15g water, add 0.9g hydrogen peroxide solution (H 2O 2Content is 27wt%), agitation condition adds 2g tetrabutyl titanate (TBOT, TiO down 2Han Liang>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 the 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 is distinguished the former powder F of corresponding adding 1.2g HTS (SiO again 2Content is 89wt%) and commercially available high silica ZSM-5 molecular sieve (SiO 2Content is 93wt%) to make crystal seed; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene; 170 ℃ of following dynamic crystallizations 24 hours; Product through filter, the washing back is in 120 ℃ of dryings 6 hours, then 550 ℃ of following roastings 4 hours with removal template, corresponding former powder O of HTS and the P of obtaining.
Embodiment 15-17]
The proportioning raw materials that employing such as embodiment 13 are said adds the former powder F of 1.2g HTS (SiO 2Content is 89wt%) to make crystal seed; Be transferred to after mixing in the stainless steel crystallizing kettle of inner liner polytetrafluoroethylene; Respectively corresponding to 96 hours, 155 ℃ following dynamic crystallizations of 140 ℃ of following dynamic crystallizations 48 hours and 185 ℃ of following dynamic crystallizations 18 hours; Product through filter, the washing back is in 120 ℃ of dryings 6 hours, then 550 ℃ of following roastings 4 hours with removal template, the corresponding former powder Q of HTS, R and the S of obtaining.
Embodiment 18]
Use x-ray powder diffraction that above-mentioned HTS is analyzed, used instrument model is Rigaku (Neo-Confucianism) Geigerflex.Percent crystallinity is according in the spectrogram 23.0 o, 23.6 o, 23.9 oAnd 24.3 oThe relative peak height at place calculates, and sample its percent crystallinity best with crystallization is 100%, and the gained crystallinity data is listed in table 1.
Embodiment 19]
The former powder of above-mentioned HTS is used for pimelinketone oximate reaction evaluating; Its step is following: accurately take by weighing the former powder of 0.25g HTS, 1.40g pimelinketone, the 16.60g trimethyl carbinol and 15.70g zero(ppm) water; Join successively in the glass reactor of band condensing reflux; Open magnetic agitation, be sequentially added into 1.60g ydrogen peroxide 50 (H again 2O 2Content is 27wt%) and 2.00g ammoniacal liquor, add toluene that about 0.14g warp accurately weighs after 2 hours as internal standard substance 75 ℃ of reactions, sampling analysis then, the gained response data is listed in table 1.
The transformation efficiency of above-mentioned reaction evaluating and selectivity method of calculation are following:
Figure 2012101166838100002DEST_PATH_IMAGE001
Table 1
Sample number into spectrum Percent 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 can be 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 the catalytic oxidation performance of product is significantly improved; In the reaction process of catalysis of pimelinketone oximate, obtained to be up to 92.7% pimelinketone transformation efficiency and be up to 97.2% OxiKhim-Styrol selectivity.

Claims (9)

1. the preparation method of a high-performance HTS is characterized in that this method may further comprise the steps:
4-propyl bromide, Neutral ammonium fluoride, water and hydrogen peroxide solution are mixed, obtain settled solution A;
Under the agitation condition, in solution A, add the titanium source, regulate pH to 10～13 with ammoniacal liquor, ageing is to forming faint yellow settled solution B;
The silicon source is added in the solution B, obtain crystallization mother liquor C after mixing;
With crystallization mother liquor C crystallization 10～100 hours under 130～190 ℃, autogenous pressure, obtain solid titanium si molecular sieves product through separating then.
2. the preparation method of a kind of high-performance HTS according to claim 1 is characterized in that the titanium source is selected from one or more in tetrabutyl titanate, positive tetraethyl titanate, titanium tetrafluoride and the ammonium titanium fluoride.
3. the preparation method of a kind of high-performance HTS according to claim 1 is characterized in that the silicon source is selected from one or more in silicon sol, positive tetraethyl orthosilicate and the WHITE CARBON BLACK.
4. the preparation method of a kind of high-performance HTS according to claim 1 is characterized in that the mol ratio of silicon-dioxide and 4-propyl bromide is 1:0.06 ~ 0.30 in the crystallization mother liquor.
5. the preparation method of a kind of high-performance HTS according to claim 1 is characterized in that the mol ratio of silicon-dioxide and titanium oxide is 1:0.005 ~ 0.060 in the crystallization mother liquor.
6. the preparation method of a kind of high-performance HTS according to claim 1 is characterized in that the mol ratio of silicon-dioxide and Neutral ammonium fluoride is 1:0.05 ~ 0.30 in the crystallization mother liquor.
7. the preparation method of a kind of high-performance HTS according to claim 1 is characterized in that the mol ratio of titanium oxide and ydrogen peroxide 50 is 1:1 ~ 8 in the crystallization mother liquor.
8. the preparation method of a kind of high-performance HTS according to claim 1 is characterized in that the mol ratio of silicon-dioxide and water is 1:10 ~ 30 in the crystallization mother liquor.
9. 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 crystal seed is 0.1wt%～10wt% in 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
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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
CN106185974A (en) * 2016-07-07 2016-12-07 昆明理工大学 A kind of preparation method of HTS TS 1
CN106542549A (en) * 2016-11-24 2017-03-29 山西大学 A kind of fluorine richness titanium phosphate aluminum molecular screen F TAPO 5 and preparation method thereof
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
CN107792863A (en) * 2017-11-28 2018-03-13 上海绿强新材料有限公司 Catalyzing hydrogen peroxide oxidation reaction HTS TS 1 synthetic method
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
CN113443635A (en) * 2020-03-26 2021-09-28 中国石油天然气股份有限公司 Titanium-containing Beta molecular sieve and synthesis method thereof
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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