CN1079372C - Process for preparing titanium-silicon molecular sieve - Google Patents
Process for preparing titanium-silicon molecular sieve Download PDFInfo
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- CN1079372C CN1079372C CN97106709A CN97106709A CN1079372C CN 1079372 C CN1079372 C CN 1079372C CN 97106709 A CN97106709 A CN 97106709A CN 97106709 A CN97106709 A CN 97106709A CN 1079372 C CN1079372 C CN 1079372C
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- molecular sieve
- titanium
- hts
- silicon
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Abstract
The present invention relates to a technology for preparing titanium-silicon molecular sieves. The titanium-silicon molecular sieve is synthesized by taking tetrabutyl titanate, or tetraethyl titanate, or trivalent inorganic titanium compounds, tetraethyl orthosilicate, or silica sol, recovered molecular sieve crystallized mother liquid and quaternary ammonium base or/and organic amine as raw materials by a hydrothermal method. The titanium-silicon molecular sieve synthesized by the method has the advantages of low cost of the molecular sieves, short synthesis period and high degree of crystallization, and the obtained titanium-silicon molecular sieve has very high catalytic activity and selectivity. At the same time, the environmental pollution of waste liquid (mother liquid) obtained after crystallized the molecular sieves is eliminated.
Description
The present invention relates to a kind of preparation technology of HTS.
HTS has very high catalytic activity and selectivity to the low-carbon (LC) oxidation operation: be oxygenant with the hydrogen peroxide, in temperature is under 40～100 ℃ of conditions, but the reactions such as ammonia oxidation of the hydroxylation of the partial oxidation of the epoxidation of catalyzed alkene, alkane, aromatic hydrocarbon and phenol and pimelinketone.The synthetic method of HTS generally has two kinds: a kind of is to be the titanium source with tetraethyl titanate or tetrabutyl titanate, and tetraethyl orthosilicate is the silicon source, is template with TPAOH TPAOH or TBAH TBAOH, utilizes hydrothermal method synthetic.Wherein the mol ratio of reaction mass is SiO
2/ TiO
2＞30; TPAOH or TBAOH/SiO
2=0.3～0.6.It is the method for the synthetic TS-1 HTS of template with TPAOH that U.S. Pat P04410501 has introduced.Utilize aforesaid method to synthesize its complicated operating process of TS-1, long reaction time (6～30 days), and be difficult to avoid the tetraethyl titanate hydrolysis and be polymerized to non-body phase anatase.Document BE1001038 (1989) has introduced a kind of method of synthetic TS-2 HTS, and it is to be the titanium source with the tetraethyl titanate, and tetraethyl orthosilicate is the silicon source, is template with the TBAH, utilizes hydrothermal method to synthesize the TS-2 HTS.There is following shortcoming equally in this synthetic method: complicated operating process, long reaction time needs 6～30 days, and is difficult to avoid the tetraethyl titanate hydrolysis and is polymerized to non-body phase anatase TiO
2Because the price of template is expensive, consumption is more in the process of synthesis of titanium silicon molecular sieve, had a strong impact on the preparation cost of HTS, in above-mentioned two documents through chemical analysis, the chemical reaction amount of the required template of synthesis of titanium silicon molecular sieve, far below the add-on of initiation reaction, therefore caused the increase of production cost.In addition, owing to the existence of itrogenous organic substance in the template, the reactive crystallization mother liquor can cause problem of environmental pollution in above-mentioned two documents.
The objective of the invention is in order to solve in the above-mentioned document template waste seriously, cause that production cost increases, and problem of environment pollution caused, a kind of new process for preparing titanium-silicon molecular sieve is provided, it is low that this technology has a production cost, and the reaction times is short, and the characteristics that environment is not polluted.
The objective of the invention is to realize by following technical scheme: a kind of process for preparing titanium-silicon molecular sieve, HTS have following general formula: xTiO
2(l-x) SiO
2, x=0.0005～0.04, wherein x is a mol ratio, x=Ti/ (Si+Ti); It is with titanium compound: tetrabutyl titanate or tetraethyl titanate or trivalent inorganic titanium are the titanium source, tetraethyl orthosilicate or silicon sol are the silicon source, quaternary ammonium hydroxide or quaternary ammonium salt are or/and organic amine is template RN, wherein part or all of template is from the HTS crystalline mother solution, and the mol ratio of each material is in the molecular sieve precursor: SiO
2/ TiO
2=20～200, OH/SiO
2=0.03～0.6, RN/SiO
2=0.1～1.0, H
2O/SiO
2=60～100, above-mentioned reaction mixture carries out crystallization, 120～200 ℃ of crystallization temperatures, crystallization time 5～120 hours after stirring 1～5 hour under 50～90 ℃; Fractional crystallization product and reclaim mother liquor then, crystallized product gets HTS through washing, dry, roasting.
In the technique scheme, in the HTS preparation process, the HTS crystalline mother solution of recovery can be recycled, and contains a kind of quaternary ammonium hydroxide or quaternary ammonium salt at least in the crystallization of molecular sieves mother liquor of recovery.Quaternary ammonium hydroxide is TPAOH, tetraethyl ammonium hydroxide or TBAH; Quaternary ammonium salt is tetrapropyl ammonium halide, tetraethyl-ammonium halide or tetrabutyl ammonium halide; Organic amine is hexanediamine, diethylamine, quadrol, triethylamine or butylamine.The mol ratio preferable range in silicon source is in template in the HTS crystalline mother solution that reclaims and the HTS precursor: 0.1～0.8, and its preferred range is 0.1～0.5.The x preferable range is 0.005～0.025 in the synthetic HTS; The trivalent inorganic titanium is titanous chloride or titanium tribromide.In preparation HTS process, add before the titanium-containing compound, make silicon compound partial hydrolysis in advance.
Main points of the present invention are to utilize in the crystalline mother solution unreacted template that the reaction of crystallization of molecular sieves mother liquor is used, and reach on the one hand and save the HTS preparation cost, eliminate in the crystalline mother solution itrogenous organic substance on the other hand to the pollution problem of environment.
The present invention carries out the synthetic of HTS by reclaiming, utilize the mother liquor after the molecular sieve crystallization, has reduced the cost of catalyzer, has improved the degree of crystallinity of molecular sieve, has shortened generated time, has eliminated in the crystallization mother liquor nitrogenous organic liquid waste to the pollution of environment.The HTS of gained also has higher catalytic activity simultaneously, has obtained effect preferably.
The present invention is further elaborated below by embodiment.[embodiment 1]
The mixing solutions that the positive tetraethyl orthosilicate of 50.0g, 14.6g TPAOH (TPAOH), 1.8g tetrabutyl titanate and suitable quantity of water are formed is added in the container of band whipping appts.After at room temperature stirring 1 hour, slowly be heated to 80-95 ℃, and kept 5 hours.Change over to again in the stainless autoclave that is lined with PTFE and carry out crystallization, crystallizing kettle is airtight, be warming up to 175 ℃, constant temperature 48 hours in 2 hours.The crystalline mother solution of the solid product of cooling, filtering for crystallizing, and recovery then.Above-mentioned solid crystallized product after 120 ℃ of dryings, 550 ℃ of roastings, gets the TS-1 HTS then again through washing, and its crystallization yields is about 92%.The relative molar content of each component: SiO in the precursor wherein
2/ TiO
2=45, TPAOH/SiO
2=0.30, H
2O/SiO
2=45[embodiment 2]
The mixing solutions that the positive tetraethyl orthosilicate of 50.0g, 5.0g TPAOH (TPAOH), 1.6g tetrabutyl titanate, 250g HTS crystalline mother solution (the content 3-5wt.% of organic amine and ammonium, below each example identical) and suitable quantity of water are formed is added in the container of band whipping appts.After at room temperature stirring 1 hour, slowly be heated to 80-95 ℃, and kept 5 hours.Change over to again in the stainless autoclave that is lined with PTFE and carry out crystallization, crystallizing kettle is airtight, be warming up to 170 ℃, constant temperature 48 hours in 2 hours.The crystalline mother solution of the solid product of cooling, filtering for crystallizing, and recovery then.Above-mentioned solid crystallized product after 120 ℃ of dryings, 550 ℃ of roastings, gets the TS-1 HTS then again through washing, and crystallization yields is greater than 97%.The relative charging capacity (mole) of each component: SiO wherein
2/ TiO
2=51, TPAOH/SiO
2=0.1, H
2O/SiO
2=60[embodiment 3]
The mixing solutions that the positive tetraethyl orthosilicate of 50.0g, 5.0g TPAOH (TPAOH), 2.Og tetrabutyl titanate, the HTS crystalline mother solution 250g that reaches recovery and suitable quantity of water are formed is added in the container of band whipping appts.After at room temperature stirring 1 hour, slowly be heated to 80-95 ℃, and kept 5 hours.Change over to again in the stainless autoclave that is lined with PTFE and carry out crystallization, crystallizing kettle is airtight, be warming up to 175 ℃, constant temperature 60 hours in 2 hours.The crystalline mother solution of the solid product of cooling, filtering for crystallizing, and recovery then.Through washing, after 120 ℃ of dryings, 550 ℃ of roastings, the crystallization yields of gained TS-1 HTS is greater than 98% then again for above-mentioned solid crystallized product.The relative charging capacity (mole) of each component: SiO wherein
2/ TiO
2=41, TPAOH/SiO
2=0.1, H
2O/SiO
2=60[embodiment 4]
The mixing solutions that the positive tetraethyl orthosilicate of 50.0g, 2.5g TPAOH (TPAOH), 1.5g quadrol, 1.6g tetrabutyl titanate, HTS crystalline mother solution and suitable quantity of water are formed is added in the container of band whipping appts.After at room temperature stirring 1 hour, slowly be heated to 80-95 ℃, and kept 5 hours.Change over to again in the stainless autoclave that is lined with PTFE and carry out crystallization, crystallizing kettle is airtight, be warming up to 170 ℃, constant temperature 48 hours in 2 hours.The crystalline mother solution of the solid product of cooling, filtering for crystallizing, and recovery then.Through washing, after 120 ℃ of dryings, 550 ℃ of roastings 5 hours, the crystallization yields of gained TS-1 HTS was greater than 93% then again for above-mentioned solid crystallized product.The relative charging capacity (mole) of each component: SiO wherein
2/ TiO
2=51, TPAOH/SiO
2=O.05, quadrol/SiO
2=O.1, H
2O/SiO
2=60[embodiment 5]
The mixing solutions that the positive tetraethyl orthosilicate of 50.0g, 2.0g TPAOH (TPAOH), 3.0g tetraethyl ammonium hydroxide (TEAOH), 1.6g tetrabutyl titanate, HTS crystalline mother solution and suitable quantity of water are formed is added in the container of band whipping appts.After at room temperature stirring 1 hour, slowly be heated to 80-95 ℃, and kept 5 hours.Change over to again in the stainless autoclave that is lined with PTFE and carry out crystallization, crystallizing kettle is airtight, be warming up to 170 ℃, constant temperature 48 hours in 2 hours.The crystalline mother solution of the solid product of cooling, filtering for crystallizing, and recovery then.Through washing, after 120 ℃ of dryings, 550 ℃ of roastings 10 hours, the crystallization yields of gained TS-1 molecular sieve was greater than 97% then again for above-mentioned solid crystallized product.The relative charging capacity (mole) of each component: SiO wherein
2/ TiO
2=51, TPAOH/SiO
2=0.04, TEAOH/SiO
2=0.08, H
2O/SiO
2=60[embodiment 6]
According to each step of embodiment 3, just the add-on of tetrabutyl titanate is 2.5g.The relative charging capacity (mole) of each component: SiO wherein
2/ TiO
2=32.6, TPAOH/SiO
2=0.1, H
2O/SiO
2=60, the crystallization yields of final TS-1 molecular sieve is greater than 97%[embodiment 7]
The HTS crystalline mother solution 250g and the suitable quantity of water that add 7.5gTPAOH, recovery in the positive tetraethyl orthosilicate of 50.0g under agitation, add 4.0g 17%TiCl
3The aqueous solution.Afterwards, slowly be heated to 80-90 ℃, and under nitrogen protection, kept 2-5 hour.Change over to again in the stainless autoclave that is lined with PTFE and carry out crystallization, crystallization temperature 150-190 ℃, crystallization time 1-5 days.After crystallization finished, water cooled off fast, and isolates crystallized product; After 120 ℃ of dryings, 550 ℃ of calcinations 6 hours.Then get titanium-silicon molecular sieve TS-1.The relative molar content of each component in the precursor wherein:
SiO
2/ TiO
2=54, TPAOH/SiO
2=0.15, H
2O/SiO
2=25-45[embodiment 8]
TS-1 HTS with embodiment 1 preparation is made catalyzer, carries out the reaction of ammoxidation of cyclohexanone preparing cyclohexanone oxime, and specific implementation process and result are as follows.
In one 500 milliliters reactor, add 5.0 gram catalyzer, 40 gram pimelinketone, 60 milliliters of strong aquas, 55 ml waters, 55 milliliters of trimethyl carbinols, under agitation, be warming up to 82 ℃ after, add 40.5 milliliter 30% H
2O
2Begin reaction, 1.5 hours reaction times.With pimelinketone and cyclohexanone-oxime in the gas Chromatographic Determination reaction mixture, the result was as follows after reaction finished:
The transformation efficiency 97.9% of pimelinketone, the selectivity 91.2% of cyclohexanone-oxime.[embodiment 9]
TS-1 HTS with embodiment 3 preparations is made catalyzer, carries out the reaction of ammoxidation of cyclohexanone preparing cyclohexanone oxime, and specific implementation process is with embodiment 7, and the result is as follows.
The transformation efficiency 98.6% of pimelinketone, the selectivity 95.2% of cyclohexanone-oxime.
With the foregoing description 3 synthetic TS-1 molecular sieves, show that through X-ray powder diffraction and infrared spectrum characterization this HTS has the MFI topological framework of feature and has typical infrared spectra 960cm
-1Absorption band.
Claims (10)
1, a kind of process for preparing titanium-silicon molecular sieve, HTS has following general formula: xTiO
2(1-x) SiO
2, x=0.0005～0.04, wherein x is a mol ratio, x=Ti/ (Si+Ti); It is with titanium compound: tetrabutyl titanate or tetraethyl titanate or trivalent inorganic titanium are the titanium source, and tetraethyl orthosilicate or silicon sol are the silicon source, and quaternary ammonium hydroxide or quaternary ammonium salt are or/and organic amine is template RN, and wherein the mol ratio of each material is in the molecular sieve precursor: SiO
2/ TiO
2=20～200, OH
-/ SiO
2=0.03～0.6, RN/SiO
2=0.1～1.0, H
2O/SiO
2=60～100, above-mentioned reaction mixture carries out crystallization after stirring 1～5 hour under 50～90 ℃, and crystallization temperature is 120～200 ℃, and crystallization time is 5～120 hours; Fractional crystallization product and reclaim mother liquor then, crystallized product makes HTS through washing, dry, roasting, and part or all that it is characterized in that template is from the HTS crystalline mother solution.
2, process for preparing titanium-silicon molecular sieve according to claim 1 is characterized in that recycling the HTS crystalline mother solution synthesis of titanium silicon molecular sieve of recovery.
3, process for preparing titanium-silicon molecular sieve according to claim 1 contains a kind of quaternary ammonium hydroxide or quaternary ammonium salt in the HTS crystalline mother solution that it is characterized in that reclaiming at least.
4, process for preparing titanium-silicon molecular sieve according to claim 1 is characterized in that quaternary ammonium hydroxide is TPAOH, tetraethyl ammonium hydroxide or TBAH; Quaternary ammonium salt is tetrapropyl ammonium halide, tetraethyl-ammonium halide or tetrabutyl ammonium halide.
5, process for preparing titanium-silicon molecular sieve according to claim 1 is characterized in that organic amine is hexanediamine, diethylamine, quadrol, triethylamine or butylamine.
6, process for preparing titanium-silicon molecular sieve according to claim 1, the mol ratio in silicon source is in template in the HTS crystalline mother solution that it is characterized in that reclaiming and the HTS precursor: 0.1～0.8.
7, process for preparing titanium-silicon molecular sieve according to claim 6, the mol ratio in silicon source is in template in the HTS crystalline mother solution that it is characterized in that reclaiming and the HTS precursor: 0.1～0.5.
8, process for preparing titanium-silicon molecular sieve according to claim 1 is characterized in that x=0.005～0.025.
9, process for preparing titanium-silicon molecular sieve according to claim 1 is characterized in that the trivalent inorganic titanium is titanous chloride or titanium tribromide.
10, process for preparing titanium-silicon molecular sieve according to claim 1 is characterized in that adding before the titanium-containing compound, makes silicon compound partial hydrolysis in advance.
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|---|---|---|---|
| CN97106709A CN1079372C (en) | 1997-11-13 | 1997-11-13 | Process for preparing titanium-silicon molecular sieve |
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|---|---|---|---|
| CN97106709A CN1079372C (en) | 1997-11-13 | 1997-11-13 | Process for preparing titanium-silicon molecular sieve |
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| CN1217232A CN1217232A (en) | 1999-05-26 |
| CN1079372C true CN1079372C (en) | 2002-02-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103917492A (en) * | 2011-09-09 | 2014-07-09 | 巴斯夫欧洲公司 | Process for the organotemplate-free synthetic production of a zeolitic material using recycled mother liquor |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457622C (en) * | 2001-12-28 | 2009-02-04 | 大连理工大学 | Prepn. of small-grain Ti-Si molecular sieve in cheap hydrothermal system and its application |
| DE102006017701A1 (en) * | 2006-04-15 | 2007-10-25 | Degussa Gmbh | Silicon-titanium mixed oxide powder, dispersion thereof and titanium-containing zeolite produced therefrom |
| CN101439863B (en) * | 2007-11-20 | 2011-05-25 | 石大卓越科技股份有限公司 | Preparation of Beta molecular sieve |
| CN102502690A (en) | 2011-10-31 | 2012-06-20 | 大连理工大学 | Method for modifying TS (Titanium silicalite)-1 based on mixed liquor of quaternary ammonium salt and inorganic base |
| CN104528761B (en) * | 2014-12-25 | 2016-08-24 | 中国天辰工程有限公司 | A kind of synthetic method of high skeleton Ti content HTS |
| CN106006665B (en) * | 2016-05-13 | 2018-08-21 | 浙江师范大学 | A kind of preparation method of titanium-silicon molecular sieve TS-1 |
| CN108793183B (en) * | 2017-12-15 | 2021-04-13 | 中国科学院大连化学物理研究所 | Method for separating mother liquor of titanium-silicon molecular sieve |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| US4828812A (en) * | 1987-12-29 | 1989-05-09 | Mobil Oil Corporation | Titanosilicates of enhanced ion exchange capacity and their preparation |
| US5082641A (en) * | 1987-05-22 | 1992-01-21 | Rhone-Poulenc Chimie | Silicon/titanium oxide mfi zeolites |
| CN1129067A (en) * | 1995-02-09 | 1996-08-21 | 吕向东 | Technology for production of hollow noodles and cutting tool thereof |
-
1997
- 1997-11-13 CN CN97106709A patent/CN1079372C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| US5082641A (en) * | 1987-05-22 | 1992-01-21 | Rhone-Poulenc Chimie | Silicon/titanium oxide mfi zeolites |
| US4828812A (en) * | 1987-12-29 | 1989-05-09 | Mobil Oil Corporation | Titanosilicates of enhanced ion exchange capacity and their preparation |
| CN1129067A (en) * | 1995-02-09 | 1996-08-21 | 吕向东 | Technology for production of hollow noodles and cutting tool thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103917492A (en) * | 2011-09-09 | 2014-07-09 | 巴斯夫欧洲公司 | Process for the organotemplate-free synthetic production of a zeolitic material using recycled mother liquor |
| CN103917492B (en) * | 2011-09-09 | 2016-08-17 | 巴斯夫欧洲公司 | Use the method without the synthetically prepared zeolitic material of organic formwork of recirculation mother solution |
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| CN1217232A (en) | 1999-05-26 |
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