CN1115297C - Process for synthesizing titanium-silicon molecular sieve in microwave radiation field - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000005855 radiation Effects 0.000 title claims abstract description 11
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000002425 crystallisation Methods 0.000 claims abstract description 27
- 230000008025 crystallization Effects 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011541 reaction mixture Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 19
- -1 alcohol amine compounds Chemical class 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims 1
- 229910003074 TiCl4 Inorganic materials 0.000 claims 1
- 229910010270 TiOCl2 Inorganic materials 0.000 claims 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 150000001412 amines Chemical group 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000012690 zeolite precursor Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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Abstract
The present invention discloses a method for preparing a TS-1 molecular sieve. Reaction mixtures of silicon resources, titanium sources and alkali sources, which can be used for synthesizing an MFI structure titanium silicon molecular sieve, are placed in an autoclave and generated steam is released in microwave radiation field from 600 to 50000MHz, under pressure from 0.4 to 1.0MPa and in crystallization time from 15 hours to 3 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, and small grain size and high yield of prepared molecular sieves.
Description
Present method is the preparation method about HTS, has the method for MFI structure titanium silicon molecular sieve (TS-1) about preparation in the microwave radiation field specifically.
The Application Areas of molecular sieve has greatly been opened up in the appearance of HTS, and exploitation has synthesized the TS-1 with MFI structure, the TS-2 of MEL structure and the HTS of β zeolite topological framework at present to people through years of researches.Make 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 five-ring titanium-silicon molecular sieve TS-1 with MFI structure, this method is after by certain reaction thing proportioning silicon source, titanium source, organic bases 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
RN
+/SiO
2 0.1～2.0 0.4～1.0
Zeolites, Vol 12, 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, and 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%.
Product behind the HTS hydrothermal crystallizing also will pass through the multistep aftertreatment, and as separate (as filtration or centrifugal) with mother liquor, washing, drying and other steps just can obtain solid-state crystallization product, and step is numerous and diverse.Need to use a large amount of distilled water washs in such last handling process, the raw material that a lot of costlinesses are usually arranged in the washings, as template TPAOH (TPAOH), be mixed in the water and run off, will not cause environmental pollution if do not recycle, but if reclaim, again can be very low because of the relative concentration of various raw materials, make very difficulty of recycling.
General TS-1 molecular sieve crystallization under hydrothermal condition obtains, generally, use the heating of electrically heated or water vapor mostly, promptly in heat conducting mode, by reactor wall heat is passed to reaction mixture, just inevitably there is a temperature gradient explained in this, makes reaction mixture can not get even heating and influences the performance of product.
USP4778666 has disclosed the method that in microwave radiation field hydrothermal crystallizing prepares aluminosilicate molecular sieves.This method comprises (a) but zeolite precursor that contains crystallization and the thermal conduction solvent that can respond to microwave energy is provided; (b) mixture of above-mentioned zeolite precursor and thermal conduction solvent is positioned over crystallization in the microwave radiation field of certain frequency.
The purpose of this invention is to provide that a kind of zeolite crystal size is little, yield is high, and the few method for preparing the TS-1 molecular sieve of preparation process environmental pollution.
Method provided by the invention is, can synthesize silicon source, the titanium source of TS-1, the reaction mixture of alkali source, be positioned in the autoclave, in the microwave radiation field of 600～50000MHz frequency, keep under reaction system 0.4～1MPa pressure, in 15 hours～3 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 said synthetic TS-1 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, 1992, Vol 12, reported method among the p943, 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.
In the method provided by the invention, in order to reduce the loss of microwave energy as far as possible, said autoclave can be glass, pottery or macromolecule engineering material preferably by the material manufacturing that does not absorb or seldom absorb microwave energy, preferred macromolecule engineering material, more preferably polyether-ether-ketone.
Preferred 900～the 4500MHz of the microwave frequency of said microwave radiation field.
In method provided by the invention, the vapor pressure that is produced should remain 0.4～1.0MPa, discharges excessive steam by valve, and by condensation it is reclaimed.The discharging modes of steam can be intermittently, be that certain interval of time discharges once, it also can be successive, the opportunity of discharged steam and time length and no requirement (NR), can be in the crystallization initial stage, also can carry out after for some time in crystallization, be preferably in crystallization and begin after inductive phase to carry out, the volume that makes steam condensate be feed intake in water cumulative volume 60%～85%, preferred 65%～80% o'clock, stop discharged steam, the average release rate of steam is to be determined by the phlegma volume of need released vapour and crystallization time.
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, because the microwave heating energy distribution is even, avoided the problem of the heating inequality that thermograde causes in the conventional hydrothermal crystallization method, thereby the gained molecular sieve crystallinity is good, grain-size is less, the synthetic product has littler particle size, for example adopting the crystal size of the TS-1 molecular sieve of ordinary method preparation is 0.30～0.40 μ m, is 0.10～0.25 μ m and adopt the crystal size of the TS-1 molecular sieve of present method preparation.
3, the liquid phase in the reaction system is evaporated discharge, solid-to-liquid ratio was very little when crystallization was finished, thereby it is easier that mother liquor separation and template are reclaimed, and avoided the loss of material in the post-processing step, improved the yield of molecular sieve, its actual recovery reaches more than 90% of theoretical yield.
4, the direct provocative reaction mixture of the microwave in microwave radiation field molecule has increased internal energy of molecular, thereby has accelerated the molecular sieve crystallization rate; Because the crystallization system is concentrated, the reactant relative concentration increases gradually, has improved the utilising efficiency of template, has shortened crystallization time simultaneously.
The granularity of TS-1 sample is measured by the JEM-2000FX-II transmission electron microscope (TEM) of NEC company.
Fig. 1 is the standard x optical diffraction spectrogram of the HTS with MFI structure of the last record of Microporous Materials Vol 22 (1998) p637.
Transmission electron microscope (TEM) photo of the TS-1 of the method that provides according to embodiment among the USP4410501 1 and method provided by the invention preparation is provided for Fig. 2 a and 2b.
Fig. 3 a and 3b are respectively according to Zeolites, and Vol 12, p943, transmission electron microscope (TEM) photo of the TS-1 of the method for record and method provided by the invention preparation on 1992.
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 is the aqueous solution of 20 (weight) %, is Japanese Fluka company product; 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.With above-mentioned reaction mixture 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 6 hours.The yield of products obtained therefrom is 84%.
The x-ray diffraction spectra of product conforms to Fig. 1.
Transmission electron microscope photo is seen Fig. 2 a, and from Fig. 2 a as can be known, the granularity of prepared TS-1 is about 0.30～0.40 μ m.
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.But above-mentioned reaction mixture is put in the autoclave by the polyether-ether-ketone preparation of microwave heating system (SH9402, Research Institute of Petro-Chemical Engineering make) of automatic voltage measurement and pressure control function, set certain microwave frequency and 0.8MPa system pressure.By the valve released vapour, vapor condensation reclaims to calculate the volume of phlegma, the V-bar of sustained release steam.After crystallization is finished, reactant is taken out, filtration, washing, drying, 540 ℃ of following roastings got sample in 6 hours.Reaction conditions and product yield see Table 1.
The x-ray diffraction spectra of product conforms to Fig. 1.
Wherein the transmission electron microscope photo of the TS-1 of example 3 preparations is seen Fig. 2 b, and from Fig. 2 b as can be known, its granularity is about 0.10～0.25 μ m, less than 0.30～0.40 μ m of conventional method preparation.
Table 1
| Embodiment | Microwave frequency (MHz) | 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 | 2450 | 4.6 | 15 | 65％ | 94 |
| 2 | 2450 | 3.3 | 24 | 75％ | 96 |
| 3 | 910 | 1.7 | 48 | 80％ | 96 |
Comparative Examples 2
This Comparative Examples is according to Zeolites, and Vol 12, p943, and 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, 540 ℃ of following roastings 6 hours.The yield of product be 80%.Transmission electron microscope photo is seen Fig. 3 a, and from Fig. 3 a as can be known, the granularity of prepared TS-1 is about 0.30～0.40 μ m.
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 the 20ml 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.But in the autoclave of making by polyether-ether-ketone in the microwave heating system (SH9402, Research Institute of Petro-Chemical Engineering makes) of above-mentioned reaction mixture immigration automatic voltage measurement and pressure control, set certain microwave frequency and 0.8MPa system pressure.By the valve released vapour, according to the phlegma volume that vapor condensation reclaims, control the speed of different released vapours, after crystallization is finished, with the reactant taking-up, filtration, washing, drying, 540 ℃ of following roastings 6 hours.
The x-ray diffraction spectra of product conforms to Fig. 1.
Wherein the transmission electron microscope photo of the TS-1 of example 5 preparations is seen Fig. 3 b, and from Fig. 3 b as can be known, its granularity is about 0.10～0.25 μ m, less than 0.30～0.40 μ m of conventional method preparation.
Table 2
| Embodiment | Microwave frequency (MHz) | 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 | 910 | 7.6 | 15 | 65％ | 94 |
| 5 | 2450 | 4.9 | 24 | 75％ | 95 |
| 6 | 2450 | 2.5 | 48 | 80％ | 96 |
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|---|---|---|---|---|
| US6387349B1 (en) * | 2001-03-26 | 2002-05-14 | Council Of Scientific And Industrial Research | Process for the microwave induced preparation of crystalline microporous titanium silicalite |
| 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 | Production method of titanium-silicon molecular sieve, titanium-silicon molecular sieve produced by the method and ammoximation reaction method |
| CN115650249B (en) * | 2022-09-19 | 2024-01-05 | 中建安装集团有限公司 | Method for preparing high-performance TS-1 titanium silicalite molecular sieve at low cost |
Citations (2)
| 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 |
| US4778666A (en) * | 1986-12-04 | 1988-10-18 | Mobil Oil Corporation | Crystallization method employing microwave radiation |
-
1999
- 1999-05-28 CN CN99107790A patent/CN1115297C/en not_active Expired - Fee Related
Patent Citations (2)
| 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 |
| US4778666A (en) * | 1986-12-04 | 1988-10-18 | Mobil Oil Corporation | Crystallization method employing microwave radiation |
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