CN1751996A - Method of synthesizing titanium silicon molecular sieve using complexig agent to raise titanium source stability - Google Patents
Method of synthesizing titanium silicon molecular sieve using complexig agent to raise titanium source stability Download PDFInfo
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Abstract
A process for synthesizing TiSi molecular sieve by using complexing agent to improve the stability of Ti source includes such steps as adding the alcohol solution of complexed Ti-contained compound to silicon sol containing ammonium tetrapropylbromide, adding ammonia water or organic amine to regulate pH, reaction to obtain mixture, loading it in a sealed stainless steel crystallizer with teflon liner, crystallizing at 120-200 deg.C for 1-7 days, filtering, washing, drying and calcining.
Description
Technical field
The present invention relates to a kind of synthetic method of molecular sieve catalyst, be specifically related to a kind of hydrothermal synthesis method.
Background technology
Since the titanium-silicon molecular sieve TS-1 with MFI structure that US Patent 4410501 discloses synthesizes successfully first, because its excellent catalytic selective oxidation performance has caused people's attention widely.
In the synthetic method of classics, expensive template and harsh synthetic technological condition are the principal elements that hinders its industrial applications always, develop cheap synthetic system and simple process condition and prepare HTS and become a focus.
In the preparation research of HTS, Stud Surf Sci Catal, 1994,84,203 have reported that with 4-propyl bromide (TPABr) be template, with the strong aqua is alkali source, synthesize titanium-silicon molecular sieve TS-1, crystallization temperature is 185 ℃, and crystallization time is 168 hours, thereby reduced the synthetic cost and the Operating Complexity of HTS, but its synthetic zeolite crystal is of a size of 15 μ m * 3 μ m * 1.5 μ m.
The description of EP Appl.0543247 is a template with the 4-propyl bromide, and ammoniacal liquor is done alkali source, and colloid silica is the silicon source, and tetrabutyl titanate is the titanium source after using the hydrogen peroxide complexing, synthesizes through hydro-thermal to obtain the TS-1 that grain-size is 10 μ m.
Zeolite 16 (1996) 108 has reported the method for a kind of synthetic TS-1, with cheap 4-propyl bromide is template, hexanediamine is an alkali source, tetraethyl-estersil salt and tetraethyl-titanic acid ester are respectively silicon source and titanium source, the hydrothermal crystallizing temperature is 180 ℃, crystallization time is 5 days, and the HTS grain-size of preparation is 7 μ m * 2.5 μ m * 0.5 μ m.
It is template that CN 1375455A provides a kind of employing tetraalkyl brometo de amonio, and organic amine is an alkali source, and silicon sol is the silicon source, and the alcoholic solution of titanium tetrachloride is done the titanium source, synthetic by variable temperature crystallization.
The technology that EP Appl.0543247, Zeolite 16 (1996) 108 and CN 1375455A provide all exists the defective of preparation condition harshness, complex process, zeolite crystal size heterogeneity, poor repeatability etc., therefore can not satisfy the needs of industrial applications.
Summary of the invention
Technical problem to be solved by this invention is to disclose a kind of method with complexing agent raising titanium source stability letter one-tenth HTS, to overcome the above-mentioned defective that prior art exists.
Method with complexing agent raising titanium source stability synthesis of titanium silicon molecular sieve of the present invention comprises the steps:
(1) the titanium source is added the silicon source that contains template, 15～30 ℃ were reacted 0.5～2 hour, added alkali source, 50～70 ℃ of reactions 0.5～2 hour, obtained lurid reaction-ure mixture solution;
Said titanium source is the alcoholic solution with the titanium-containing compound of complexing, this solution is made up of titanium-containing compound, pure and mild complexing agent, is a kind of complexing titanium source, after its characteristics are to add moisture, the ratio of water and titanium complex compound does not produce white titanium dioxide (TiO between 0.01～10
2) precipitation;
The mole in titanium source consists of: titanium-containing compound: complexing agent: alcohol=1: 0.1～10: 0.01～5;
Said alcohol is selected from methyl alcohol, ethanol, Virahol or propyl carbinol, and said titanium-containing compound is selected from a kind of in positive tetraethyl titanate, tetrabutyl titanate, titanium tetrachloride or the titanous chloride, and said complexing agent is selected from methyl ethyl diketone or diethanolamine;
Said silicon source is a silicon sol;
SiO in template and the silicon sol
2Meter, mol ratio is SiO
2: template=1: 0.04～0.6;
Silicon sol preferred electron grade silica sol or regular grade silicon sol can adopt commercially available product;
Said template is a 4-propyl bromide;
Said alkali source is selected from ammoniacal liquor or organic amine, a kind of in the preferred methylamine of said organic amine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, diethylamine or the hexanediamine;
The mole of each material consists of in the reaction-ure mixture:
SiO
2/TiO
2＝5～300，TPABr/SiO
2＝0.04～0.6，H
2O/SiO
2＝20～100，OH
-/SiO
2＝0.05～3.0。
TPABr is a 4-propyl bromide;
(2) with the solution of step (1) crystallization 24～168 hours under 120 ℃～200 ℃ temperature under the airtight environment and autogenous pressure, obtain crystallization product, filter, wash, dry, roasting 4～8 hours in 500～650 ℃ of following air atmospheres then, get molecular sieve of the present invention, have following general formula: xTiO
2(1-x) SiO
2, wherein x is a mol ratio, x=Ti/ (Si+Ti), x=0.003-0.05; The HTS grain-size of preparation is 1～10 μ m * 0.4～2 μ m * 0.1～2 μ m.
Preferred version is before crystallization process the silicon source to be mixed with template, and then mix with the titanium source.
The present invention is by improving the stability in its titanium source to adding complexing agent in the molecular sieve presoma titanium source, simplified the synthetic processing condition greatly, and utilized cheap material system, it is good to repeat preparation property, and institute's synthetic molecular sieve crystallinity height, the grain size homogeneous.Lay a good foundation to reducing synthetic cost of HTS and further industrial application.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 gained sample.
Fig. 2 is the amplification 5 * 10 of embodiment 1 gained sample
3Stereoscan photograph doubly.
Fig. 3 is the amplification 2 * 10 of embodiment 1 gained sample
4Stereoscan photograph doubly.
Fig. 4 is the amplification 5 * 10 of embodiment 2 gained samples
3Stereoscan photograph doubly.
Fig. 5 is the amplification 2 * 10 of embodiment 2 gained samples
4Stereoscan photograph doubly.
Embodiment
The following examples will the present invention is further illustrated.In following each example, used 4-propyl bromide is the analytical pure level product of Beijing emerging good fortune fine chemistry institute, used regular grade silicon sol and electronic-grade silica sol are silicon sol portion of Shanghai daughter nucleus institute of Chinese Academy of Sciences product, and all the other reagent are commercially available chemically pure reagent.
Embodiment 1
Virahol 10ml with after tetrabutyl titanate 2.2g mixes, and is added methyl ethyl diketone 1.9g, mix and form light yellow clear solution, stand-by as the titanium source; Taking by weighing 4-propyl bromide 2.3g is dissolved in the 80ml water, and join in the silicon source of regular grade silicon sol of 24.5g, formation contains the silicon source of template, and stirs 1 hour down at 15 ℃, then the titanium source is joined in the above-mentioned solution, continue to stir 1 hour, keep clarification, and after adding n-Butyl Amine 99 3.5g, solution continues to keep clarification, in 70 ℃ water-bath, continue to stir 1 hour, form somewhat lurid solution at last.This solution changed over to have in the teflon-lined stainless steel sealing crystallizing kettle, constant temperature is 3 days under 175 ℃ temperature and autogenous pressure, obtains the mixture of crystallization product; This mixture is filtered, is washed with water to neutrality, and in 110 ℃ of dryings 1 hour, and 650 ℃ of following air atmosphere roastings 4 hours, the TS-1 molecular sieve.Its XRD crystalline phase figure amplifies 5 * 10 as shown in Figure 1
3Doubly with 2 * 10
4Stereoscan photograph doubly respectively as shown in Figures 2 and 3.The HTS grain-size of preparation is 3 μ m * 0.8 μ m * 0.3 μ m.
Embodiment 2
Virahol 30ml with after tetrabutyl titanate 1.27g mixes, and is added methyl ethyl diketone 0.04g, mix and form light yellow clear solution, stand-by as the titanium source; Taking by weighing 4-propyl bromide 4.5g is dissolved in the 83ml water, and join in the silicon source of regular grade silicon sol of 74.7g, formation contains the silicon source of template, and stirs 1 hour down at 25 ℃, then the titanium source is joined in the above-mentioned solution, continue to stir 1 hour, keep clarification, and after adding n-Butyl Amine 99 1.36g, solution continues to keep clarification, in 60 ℃ water-bath, continue to stir 1 hour, form somewhat lurid solution at last.This solution changed over to have in the teflon-lined stainless steel sealing crystallizing kettle, constant temperature is 3 days under 175 ℃ temperature and autogenous pressure, obtains the mixture of crystallization product; This mixture is filtered, is washed with water to neutrality, and in 110 ℃ of dryings 1 hour, and 500 ℃ of following air atmosphere roastings 8 hours, the TS-1 molecular sieve.Its XRD crystalline phase figure and Fig. 1 are similar, amplify 5 * 10
3Doubly with 2 * 10
4Stereoscan photograph doubly respectively as shown in Figure 4 and Figure 5.The HTS grain-size of preparation is 5 μ m * 1 μ m * 0.3 μ m.
Embodiment 3
Propyl carbinol 20ml with after positive tetraethyl titanate 2.1g mixes, and is added methyl ethyl diketone 4.41g, mix the light yellow clear solution of formation, stand-by as the titanium source; Taking by weighing 4-propyl bromide 42.7g is dissolved in the 150ml water, and join in the silicon source of electronic-grade silica sol of 53.5g, form the silicon source that contains template, and stirred 1 hour down at 30 ℃, then the titanium source is joined in the above-mentioned solution, continue to stir 1 hour, and add water 300ml, keep clarification, and after adding 28% ammoniacal liquor 48.7g, solution continues to keep clarification, continues to stir 1 hour in 60 ℃ water-bath, forms somewhat lurid solution at last.This solution changed over to have in the teflon-lined stainless steel sealing crystallizing kettle, constant temperature is 3 days under 175 ℃ temperature and autogenous pressure, obtains the mixture of crystallization product; This mixture is filtered, is washed with water to neutrality, and in 110 ℃ of dryings 1 hour, and 600 ℃ of following air atmosphere roastings 6 hours, the TS-1 molecular sieve.Its XRD crystalline phase figure and Fig. 1 are similar, and stereoscan photograph and Fig. 4 and Fig. 5 are similar.
Embodiment 4
With embodiment 1 operation, wherein complexing agent methyl ethyl diketone is changed to diethanolamine, its quality is 0.62 gram, and the quality of other raw material is all constant, and crystallization condition is also constant.XRD crystalline phase figure and Fig. 1 of the sample that makes are similar.
Embodiment 5～7
With example 1 operation.The relative molar content of component is consistent with example 1 in the raw material, and last solution is divided into three parts, changes over to respectively to have in the teflon-lined stainless steel sealing crystallizing kettle, and wherein crystallization temperature is respectively 120 ℃, and 150 ℃, 200 ℃, crystallization time is 3 days.Its XRD crystalline phase figure is all similar with Fig. 1.
Embodiment 8～10
With example 1 operation.The relative molar content of raw material and component is consistent with example 1, and last solution is divided into three parts, changes over to respectively to have in the teflon-lined stainless steel sealing crystallizing kettle, and wherein crystallization temperature is 170 ℃, and crystallization time was respectively 1 day, 4 days and 7 days.Its XRD crystalline phase figure is all similar with Fig. 1.
Embodiment 11～12
With example 1 operation.Titanium source in the raw material changes titanous chloride and titanium tetrachloride respectively into, and the relative molar content of component and condition are all consistent with example 1.Its XRD crystalline phase figure is all similar with Fig. 1.
Embodiment 13～18
With example 1 operation.Change the alkali source in the raw material into methylamine, ethamine, Tri N-Propyl Amine, quadrol, diethylamine, hexanediamine respectively, the relative molar content of component and crystallization condition are all consistent with example 1.Its XRD crystalline phase figure is all similar with Fig. 1.
Claims (10)
1. the method with complexing agent raising titanium source stability synthesis of titanium silicon molecular sieve is characterized in that, comprises the steps:
(1) the titanium source is added the silicon source that contains template, reaction adds alkali source, and reaction obtains reaction-ure mixture solution;
Said titanium source is made up of titanium-containing compound, pure and mild complexing agent;
Said complexing agent is selected from methyl ethyl diketone or diethanolamine;
Said silicon source is a silicon sol;
Said template is a 4-propyl bromide;
(2) with the solution of step (1) crystallization 24～168 hours under airtight environment, obtain crystallization product, filter, washing, drying, roasting 4～8 hours in 500～650 ℃ of following air atmospheres then, molecular sieve of the present invention, general formula is as follows: xTiO
2(1-x) SiO
2, wherein x is a mol ratio, x=Ti/ (Si+Ti), x=0.003-0.05.
2. method according to claim 1 is characterized in that, the mole of each material consists of in the reaction-ure mixture: SiO
2/ TiO
2=5～300, TPABr/SiO
2=0.04～0.6, H
2O/SiO
2=20～100, OH
-/ SiO
2=0.05～3.0.
3. method according to claim 1 is characterized in that, said titanium-containing compound is selected from a kind of in positive tetraethyl titanate, tetrabutyl titanate, titanium tetrachloride or the titanous chloride.
4. method according to claim 1 is characterized in that said alkali source is selected from ammoniacal liquor or organic amine, and said organic amine is selected from methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, diethylamine or a kind of in the diamines.
5. method according to claim 1 is characterized in that, the SiO in template and the silicon sol
2Meter, mol ratio is: SiO
2: template=1: 0.04～0.6.
6. method according to claim 1, it is characterized in that the mole in titanium source consists of: titanium-containing compound: complexing agent: alcohol=1: 0.1～10: 0.01～5, after being to add moisture, the mol ratio of water and titanium complex compound does not produce white titanium dioxide (TiO between 0.01～10
2) precipitation.
7. method according to claim 1 is characterized in that said alcohol is selected from methyl alcohol, ethanol, Virahol or propyl carbinol.
8. method according to claim 1 is characterized in that, with the solution of step (1) crystallization under 120 ℃～200 ℃ temperature under the airtight environment and autogenous pressure.
9. adopt the HTS of each described method preparation of claim 1～8.
10. HTS according to claim 9 is characterized in that, grain-size is 1～10 μ m * 0.4～2 μ m * 0.1～2 μ m.
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