CN1107027C - Process for preparation of titanium-silicon molecular sieve - Google Patents
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Abstract
The present invention discloses a preparation method of titanium-silicon molecular sieve TS-1 with an MFI structure. Reaction mixtures of silicon resources, titanium sources, alkali sources and template agents, which can be used for synthesizing the TS-1 molecular sieve, are placed in an autoclave, and generated steam is released at the temperature from 100 to 200 DEG C and in the crystallization time from 15 hours to 4 days to make the volume of steam condensate is 60% to 85% of the total volume of water in charging materials. The method has the advantages of little environment pollution, high yield of molecular sieve and shortened crystallization time.
Description
The invention relates to the method for hydrothermal crystallizing synthesis of titanium silicon molecular sieve, specifically about the hydrothermal crystallizing synthetic method of HTS (TS-1) with MFI structure.
HTS is the hetero-atom molecular-sieve of early eighties exploitation, developed the TS-1 of MFI structure so far, the TS-2 of MEL structure, the Ti-β of β zeolite topological framework etc., this makes the application of molecular sieve enter the catalyzed oxidation field from fractionation by adsorption and acid catalyzed reaction.TS-1/H particularly
2O
2Catalytic oxidation system, can be applicable to the oxidation of stable hydrocarbon, the reactions such as oxidation, alkene epoxidation, aromatic hydrocarbon hydroxylation, ammoxidation of cyclohexanone of alcohol, traditional relatively oxidizing process, the application of HTS, can make the reaction conditions gentleness, technology is simple and safe, and is environmentally friendly, and transformation efficiency is high and selectivity is good.
The synthetic method of HTS is a hydrothermal crystallization method, and the titanium source, silicon source, organic bases and the water that are about to definite composition mix, and carry out crystallization under certain temperature and pressure, and obtains through preparation processes such as separation, washing, dryings.
USP4410501 has at first disclosed the preparation method of the titanium-silicon molecular sieve TS-1 with MFI structure, this method is after by certain reaction thing proportioning silicon source, titanium source, organic bases and water being mixed, above-mentioned reaction mixture is put into autoclave, at 130-200 ℃ of hydrothermal crystallizing 6-30 days; Perhaps above-mentioned reaction mixture is at room temperature left standstill some hrs, be warming up to 80 ℃ stir some hrs after, in 175 ℃ of hydrothermal crystallizings 10 days, separate then, wash, dry and must product.Wherein the silicon source can be the tetraalkyl silicon ester, silica colloidal or alkalimetal silicate, and the titanium source is hydrolyzable titanium compound, preferred tetraethyl-titanic acid ester, the preferred TPAOH of organic bases (TPAOH).Wherein the mole compositing range of reaction mixture is:
The general range preferable range
SiO
2/TiO
2 5～200 35～65
OH
-/SiO
2 0.1～1.0 0.03～0.6
H
2O/SiO
2 20～200 60～100
Me/SiO
2 0～0.5 0
RN
+/SiO
2 0.1～2.0 0.4～1.0
Zeolites, Vol12, p943, reported the method for synthetic TS-1 molecular sieve in 1992, can make the framework of molecular sieve titanium content higher, this method is to substitute the tetraethyl-titanic acid ester with the slower tetrabutyl titanate ester of hydrolysis rate, with anhydrous isopropyl alcohol is cosolvent, adopted two kinds of approach to synthesize TS-1, a kind of approach is with the hydrolysis in an amount of TPAOH (TPAOH) aqueous solution of tetraethyl orthosilicate ester, adds the aqueous isopropanol of tetrabutyl titanate ester then under violent stirring, stirred 1 hour down at 60 ℃, form clear soln, add an amount of distilled water again, in reactor 160 ℃ of following crystallization 1～2 day; Another kind of approach is earlier with tetraethyl silicane acid esters dilute acid hydrolysis, form settled solution, order adds the aqueous isopropanol and TPAOH (TPAOH) aqueous solution of tetrabutyl titanate ester again, form transparent titanium silicon gel, 60 ℃ were stirred 1 hour down, form the solution of slight haze, add an amount of distilled water again, in reactor 160 ℃ of following crystallization 1～2 day.The yield of two kinds of approach synthetic TS-1 is respectively 70～85% and 70～90%.
CN1167082A has proposed the preparation method of a kind of HTS (TS-1), be that the titanium source is dissolved in TPAOH (TPAOH) aqueous solution, and mix with the solid silicone bead and to obtain reaction mixture, with this reaction mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 1～6 day, filter according to a conventional method then, washing drying and roasting, wherein the mole of said reaction mixture consists of:
Scope is preferred
SiO
2/TiO
2 5～220 10～150
TPAOH/SiO
2 0.03～0.5 0.05～0.4
H
2O/SiO
2 0.6～40 1～30
This method is with SiO
2Bead is the silicon source, and the water that adds in synthetic is the least possible, and the concentration of organic bases is improved, and crystallization occurs in the solid-liquid interface place, and the silicon ball is crystallization successively.But show that by experiment reactant is difficult for uniform mixing in this method.
The method of a kind of synthesis of titanium silicon molecular sieve (TS-1) has been reported in Zeolite Vol16:p108～117,1996, is to be organic bases with the hexanediamine, and 4-propyl bromide is a template, and tetrabutyl titanate and tetraethyl orthosilicate are respectively titanium source and silicon source.This method is that hexanediamine is dissolved in the distilled water, and under agitation order adds the tetraethyl silicane acid esters, the aqueous isopropanol of tetrabutyl titanate ester, the aqueous solution of 4-propyl bromide forms gel, catches up with alcohol 3 hours in 80 ℃, in the autoclave of packing into 180 ℃ of crystallization 5 days.
Zeolites, the method of the synthetic TS-1 molecular sieve of Vol19:246 1997 reports is to be the titanium source with the titanium tetrachloride, is the silicon source with positive tetraethyl orthosilicate or silicon tetrachloride, 4-propyl bromide is a template, methylamine be organic bases and in the presence of mineralizer hydrothermal crystallizing 120 hours.
The HTS of existing hydrothermal crystallization method preparation is a synthetic in the higher system of liquid hold-up, and the relative concentration of template is low, and efficient is not high.Liquid hold-up is bigger in the reaction product system, crystallization product and mother liquor disengaging time are increased, and a large amount of distilled water wash, make a lot of expensive raw materials in the washings, as TPAOH (TPAOH), be mixed in the water and run off and cause certain environmental pollution, but if reclaim, again can be very low because of the relative concentration of various raw materials, make very difficulty of recycling.Product behind the hydrothermal crystallizing is through the multistep aftertreatment, as separating with mother liquor (as filtering or centrifugal), and washing, drying and other steps, inevitable material loss makes the molecular sieve yield low, and the yield of molecular sieve is generally below 90%.
The purpose of this invention is to provide a kind of pollution less, the short hydrothermal crystallizing of yield height, crystallization time prepares the method for TS-1 molecular sieve.
Method provided by the invention is that the reaction mixture of silicon source, titanium source, alkali source and the template that can synthesize the TS-1 molecular sieve places autoclave, under 100～200 ℃ of temperature, in 15 hours～4 days the crystallization time, the steam that discharge to produce, the volume that makes steam condensate be water in feeding intake cumulative volume 60%～85%.
The reaction mixture of the silicon source of the said TS-1 of synthesizing, titanium source, alkali source and template can be prepared according to the method for prior art in the synthetic method of TS-1 molecular sieve provided by the present invention, the method that discloses among for example foregoing USP4410501, Zeolites, Vol12, p943,1992 and ZeolitesVol 16:p108～117,1996 in reported method, and institute's reported method in other documents.
Said silicon source is selected from silica gel, silicon sol or tetraalkyl silicon ester, preferred tetraalkyl silicon ester, more preferably tetraethyl silicane acid esters.
Said titanium source is the compound of hydrolyzable titanium, as TiCl
4, TiOCl
2And tetraalkyl titanate, preferred tetraalkyl titanate, more preferably tetraethyl-titanic acid ester or tetrabutyl titanate ester.
Said alkali source is an organic bases, is selected from fat amine compound, alcamine compound, quaternary amine alkali compounds or two or more mixture among them, preferred quaternary amine alkali compounds.Said quaternary amine alkali compounds is the alkyl quaternary amine bases compound that contains 1～4 carbon atom, wherein preferred TPAOH.
Said template is TPAOH or 4-propyl bromide.
In the method provided by the invention, preferred 130～180 ℃ of the temperature of reaction mixture in autoclave.The steam that produces is by the valve sustained release, and the steam of release reclaims by condensation, when the volume of phlegma reach feed intake in water cumulative volume 60%～85%,, stop discharged steam at preferred 65%～80% o'clock.The average release rate of steam is determined by the phlegma volume and the crystallization time of the steam that need discharge.The discharging modes of steam can be intermittently, i.e. certain interval of time discharging also can be a successive once, the initial discharged steam time, can be in the crystallization initial stage, also can carry out after for some time, be preferably in crystallization and begin after inductive phase to carry out in crystallization.
Method provided by the invention has following advantage:
1, major part is outside the water vapour in the steam of Pai Chuing, and also having small portion is that template tetrapropyl oxyammonia (TPAOH) part is decomposed Tri-n-Propylamine and the propyl alcohol that forms, and they can and reclaim by the fractionation plant condensate fractionation, have reduced the pollution to environment.
2, the crystallization system is concentrated gradually, and liquid hold-up is little, makes aftertreatment relatively easy, can avoid the loss of material in the post-processing step, improves the yield of molecular sieve, and its actual recovery reaches more than 90% of theoretical yield.
3, because the crystallization system is concentrated, and the reactant relative concentration increases gradually, the utilising efficiency of template improves, and can shorten crystallization time.
Fig. 1 is " Microporous Materials ", Vol22, p637, the standard x optical diffraction spectrogram of the HTS with MFI structure of record on 1998.
Following embodiment will the present invention is further illustrated, but protection scope of the present invention is not subjected to the restriction of these embodiment.
In each of the embodiments described below, used TPAOH and 4-propyl bromide are Japanese Fluka company product, and wherein TPAOH is the aqueous solution of 20 (weight) %; The tetraethyl silicane acid esters is a chemical pure, SiO
2〉=28%, Tianjin chemical reagent factory product; Tetraethyl-titanic acid ester and tetrabutyl titanate ester are chemical pure, Great Wall, Beijing chemical reagent factory product.
Comparative Examples 1
This Comparative Examples prepares TS-1 for the method that provides according to embodiment among the USP4410501 1.
Get the 20ml TPAOH and be dissolved in the 40ml bi-distilled water, under 0～5 ℃, slowly splash in the 23ml tetraethyl silicane acid esters, drip off the back and stir 20min, splash into 0.68ml tetraethyl-titanic acid ester, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, stirring heating 5 hours adds the 50ml bi-distilled water.Above-mentioned reaction mixture is moved into band teflon-lined autoclave, be warmed up to 175 ℃, crystallization time is 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying, 540 ℃ of following roastings got product in 6 hours, and its x-ray diffraction spectra conforms to Fig. 1.The yield of products obtained therefrom is 84%.
Example 1～3
The effect of method enforcement of the present invention is adopted in these example explanations according to the reaction mixture of USP4410501 method preparation.
Get the 20ml TPAOH and be dissolved in the 40ml bi-distilled water, under 0～5 ℃, slowly splash in the 23ml tetraethyl silicane acid esters, drip off the back and stir 20min, splash into 0.68ml tetraethyl-titanic acid ester, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, stirring heating 5 hours adds the 50ml bi-distilled water.Above-mentioned reaction mixture is moved into band teflon-lined autoclave, be warmed up to 130 ℃.By the valve released vapour, vapor condensation reclaims to calculate the volume of phlegma, the speed of sustained release steam.After crystallization is finished, reactant is taken out filtration, washing, drying, 540 ℃ of following roastings 6 hours.The x-ray diffraction spectra of sample conforms to Fig. 1.Reaction conditions and product yield see Table 1.
Table 1
| Embodiment | The average release rate (ml/h) of steam | Crystallization time (h) | The percentage ratio of the cumulative volume of water during the phlegma volume accounts for and feeds intake | Product yield (%) |
| 1 | 4.6 | 15 | 65％ | 94 |
| 2 | 3.3 | 24 | 75％ | 96 |
| 3 | 1.7 | 48 | 80％ | 96 |
Comparative Examples 2
This Comparative Examples is according to Zeolites, Vol12, and p943, the method for record prepares TS-1 on 1992.
Get 20ml TPAOH (TPAOH) and be dissolved in the 40ml bi-distilled water, under 5～10 ℃ condition, slowly splash in the 35ml tetraethyl silicane acid esters, drip off back stirring 20min and stir into uniform sol shape liquid; Get 1.4ml tetrabutyl titanate ester again, be dissolved in the 5ml Virahol, under 5～10 ℃ of stirrings, slowly splash into the mixing solutions of 10ml TPAOH and 40ml water, drip off the back and stir hydrolysis 10min, obtain the mixed solution of homogeneous transparent, it is splashed in the colloidal sol shape liquid that makes previously, dropwise the back and continue to stir 30min.Slowly be warming up to 80 ℃, stirring heating 3 hours is removed the alcohols that hydrolysis produces, and adds the 40ml bi-distilled water and replenishes moisture evaporated, the consisting of of prepared reaction mixture: SiO
2: 0.03TiO
2: 0.15TPAOH:50H
2O.Above-mentioned reaction mixture is moved into band teflon-lined autoclave, be warmed up to 170 ℃.Crystallization 48 hours after crystallization is finished, is taken out reactant, filtration, washing, drying, and 540 ℃ of following roastings 6 hours, its x-ray diffraction spectra conforms to Fig. 1.The yield of products obtained therefrom is 80%.
Example 4～6
These example explanations are according to Zeolites, and Vol 12, p943, the effect that the reaction mixture of 1992 methods preparation adopts method of the present invention to implement.
Get 20ml TPAOH (TPAOH) and be dissolved in the 40ml bi-distilled water, under 5～10 ℃ condition, slowly splash in the 35ml tetraethyl silicane acid esters, drip off back stirring 20min and stir into uniform sol shape liquid; Get 1.4ml tetrabutyl titanate ester again, be dissolved in the 5ml Virahol, under 5～10 ℃ of stirrings, slowly splash into the mixing solutions of 10ml TPAOH and 40ml water, drip off the back and stir hydrolysis 10min, obtain the mixed solution of homogeneous transparent, it is splashed in the colloidal sol shape liquid that makes previously, dropwise the back and continue to stir 30min.Slowly be warming up to 80 ℃, stirring heating 3 hours is removed the alcohols that hydrolysis produces, and adds the 40ml bi-distilled water and replenishes moisture evaporated, the consisting of of prepared reaction mixture: SiO
2: 0.03TiO
2: 0.15TPAOH:50H
2O.Above-mentioned reaction mixture is moved into band teflon-lined autoclave, be warmed up to 160 ℃.By the valve released vapour, vapor condensation reclaims to calculate the volume of phlegma, the speed of sustained release steam.After crystallization is finished, reactant is taken out, filtration, washing, drying, 540 ℃ of following roastings 6 hours, the x-ray diffraction spectra of sample conforms to Fig. 1.Reaction conditions and product yield see Table 2.
Table 2
| Embodiment | The average release rate (ml/h) of steam | Crystallization time (h) | The percentage ratio of the cumulative volume of water during the phlegma volume accounts for and feeds intake | Product yield (%) |
| 4 | 4.8 | 15 | 70％ | 94 |
| 5 | 3.3 | 24 | 75％ | 96 |
| 6 | 1.4 | 48 | 65％ | 96 |
Comparative Examples 3～5
These Comparative Examples are to prepare TS-1 according to the method for putting down in writing on Zeolites Vol16:p108～117,1996.
Get 3.5g hexanediamine (C
6DN) be dissolved in the 80ml distilled water, be as cold as 5～10 ℃, stir down and slowly splash into 23ml tetraethyl silicane acid esters, drip off the continuation stirring and obtained uniform sol liquid in 30 minutes; Get 0.34ml tetrabutyl titanate ester, be dissolved in the 20ml Virahol, it is slowly splashed in the sol liquid that makes previously, drip off and continue to stir 30 minutes, the 50ml aqueous solution toward wherein adding 2.7g 4-propyl bromide (TPABr) stirs evenly, and the homogeneous reaction mixture that obtains slowly is warming up to 80 ℃, heated and stirred was removed Virahol in 3 hours, the consisting of of prepared reaction mixture: SiO
2: 0.01TiO
2: 0.3C
6DN:0.1TPABr:50H
2O.Above-mentioned reaction mixture is moved into band teflon-lined autoclave, be warmed up to 180 ℃, reaction conditions such as following table 4 after after a while, are taken out reactant, filtration, washing, drying, 540 ℃ of following roastings 6 hours.Reaction conditions and product yield see Table 3.As can be seen from the table, crystallization time is in the time of 72 hours, and products obtained therefrom is an amorphous article, and crystallization time is that 96 and 120 hours product yield is respectively 70% and 84%.Table 3
| Comparative example | Crystallization time (h) | Product yield (%) |
| 3 | 72 | Product is unformed |
| 4 | 96 | 70 |
| 5 | 120 | 84 |
Example 7～9
These example explanations are adopted the effect of method enforcement of the present invention according to the Zeolites Vol16:p108～reaction mixture of 117,1996 methods preparation.
Get 3.5g hexanediamine (C
6DN) be dissolved in the 80ml distilled water, be as cold as 5～10 ℃, stir down and slowly splash into 23ml tetraethyl silicane acid esters, drip off the continuation stirring and obtained uniform sol liquid in 30 minutes; Get 0.34ml tetrabutyl titanate ester, be dissolved in the 20ml Virahol, it is slowly splashed in the sol liquid that makes previously, drip off and continue to stir 30 minutes, the 50ml aqueous solution toward wherein adding 2.7g 4-propyl bromide (TPABr) stirs evenly, and the homogeneous reaction mixture that obtains slowly is warming up to 80 ℃, heated and stirred was removed Virahol in 3 hours, the consisting of of prepared reaction mixture: SiO
2: 0.01TiO
2: 0.3C
6DN:0.1TPABr:50H
2O.Above-mentioned reaction mixture is moved into band teflon-lined autoclave, be warmed up to 180 ℃.By the valve released vapour, vapor condensation reclaims to calculate the volume of phlegma, the speed of sustained release steam.After crystallization is finished, reactant is taken out filtration, washing, drying, 540 ℃ of following roastings 6 hours.The x-ray diffraction spectra of sample conforms to Fig. 1.Reaction conditions and product yield see Table 4.As can be seen from Table 4, product yield is apparently higher than Comparative Examples.Table 4
| Embodiment | The average release rate (ml/h) of steam | Crystallization time (h) | The percentage ratio of the cumulative volume of water during the phlegma volume accounts for and feeds intake | Product yield (%) |
| 7 | 1.9 | 48 | 70％ | 90 |
| 8 | 1.4 | 72 | 75％ | 94 |
| 9 | 1.1 | 96 | 80％ | 98 |
Claims (14)
1, a kind of preparation method with titanium-silicon molecular sieve TS-1 of MFI structure, be that reaction mixture with silicon source, titanium source, alkali source and template places autoclave to carry out crystallization, it is characterized in that this reaction is 100～200 ℃ of following crystallization 15 hours～4 days, and the steam that in the crystallization process, discharge to produce, the volume that makes steam condensate be water in feeding intake cumulative volume 60%～85%.
2, in accordance with the method for claim 1, wherein said temperature is 130～180 ℃.
3, in accordance with the method for claim 1, wherein the volume of said steam condensate be feed intake in water cumulative volume 65%～80%.
4, in accordance with the method for claim 1, wherein said silicon source is selected from silica gel, silicon sol or tetraalkyl silicon ester.
5, in accordance with the method for claim 4, wherein said silicon source is the tetraalkyl silicon ester.
6, in accordance with the method for claim 5, wherein said silicon source is the tetraethyl silicane acid esters.
7, in accordance with the method for claim 1, wherein said titanium source is selected from TiCl
4, TiOCl
2Or tetraalkyl titanate.
8, in accordance with the method for claim 7, wherein said titanium source is a tetraalkyl titanate.
9, in accordance with the method for claim 8, wherein said titanium source is tetraethyl-titanic acid ester or tetrabutyl titanate ester.
10, in accordance with the method for claim 1, wherein said alkali source is selected from fat amine compound, alcamine compound, quaternary amine alkali compounds or two or more mixture among them.
11, in accordance with the method for claim 10, wherein said alkali source is the quaternary amine alkali compounds.
12, in accordance with the method for claim 11, wherein said quaternary amine alkali compounds is the alkyl quaternary amine bases compound that contains 1～4 carbon atom.
13, in accordance with the method for claim 12, wherein said alkali source is a TPAOH.
14, in accordance with the method for claim 1, wherein said template is TPAOH or 4-propyl bromide.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134575B (en) * | 2006-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing TS-1 molecular sieve |
| CN102464331A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Melt flow index (MFI) structure titanium silicalite molecular sieve with small crystal particle and preparation method thereof |
| CN102060307B (en) * | 2010-11-18 | 2012-09-05 | 西北工业大学 | Method for preparing titanium-silicon 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 |
| CN109721064B (en) * | 2017-10-31 | 2020-10-27 | 中国石油化工股份有限公司 | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method |
| CN109721069B (en) * | 2017-10-31 | 2021-02-09 | 中国石油化工股份有限公司 | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method |
| CN109721065B (en) * | 2017-10-31 | 2020-10-27 | 中国石油化工股份有限公司 | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method |
| CN112978748B (en) * | 2019-12-13 | 2022-10-04 | 中国科学院大连化学物理研究所 | TS-1 molecular sieve with macroporous-microporous composite pore channel structure, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1167082A (en) * | 1915-07-03 | 1916-01-04 | George W Kinnard | Bow holder or clamp for vehicle-tops. |
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| US4778666A (en) * | 1986-12-04 | 1988-10-18 | Mobil Oil Corporation | Crystallization method employing microwave radiation |
-
1999
- 1999-05-28 CN CN99107789A patent/CN1107027C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1167082A (en) * | 1915-07-03 | 1916-01-04 | George W Kinnard | Bow holder or clamp for vehicle-tops. |
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| US4778666A (en) * | 1986-12-04 | 1988-10-18 | Mobil Oil Corporation | Crystallization method employing microwave radiation |
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