CN102311128B - Method for treating titanium-silicon molecular sieve - Google Patents
Method for treating titanium-silicon molecular sieve Download PDFInfo
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Abstract
The invention relates to a method for treating a titanium-silicon molecular sieve. The method is characterized by modifying the titanium-silicon molecular sieve by a modifying solution in the presence of saturated steam, wherein the modifying solution is obtained by hydrolyzing a silicon source and a titanium source in a base solution. According to the method, mother liquor separation is not required, the filtration and washing procedures are omitted, pollution to environment is reduced greatly, the volume utilization efficiency of a high-pressure device is improved, the preparation cost is lowered, and the environmental protection and economic benefits of synthesis are improved.
Description
Technical field
The present invention relates to a kind of method of processing HTS, more specifically to processing the method for HTS under a kind of water vapour.
Background technology
HTS is the novel hetero-atom molecular-sieve that last century, early eighties started exploitation.The TS-1 that MFI type structure is arranged synthesized at present, the TS-2 of MEL type structure, and have than the Ti-MWW of macroporous structure etc.This molecular sieve analog is to many organic oxidizing reactions, epoxidation, aromatic hydrocarbons hydroxylation, pimelinketone oximate, the pure reactions such as oxidation such as alkene have good selective oxidation performance and higher catalytic activity, and they have a good application prospect as redox (red-ox) type molecular sieve catalyst.
The TS-1 molecular sieve is that the transition metal titanium is introduced to formed a kind of novel titanosilicate with good catalytic selectivity oxidation susceptibility in the framework of molecular sieve with ZSM-5 structure.TS-1 not only has the catalysed oxidn of titanium, but also has the shape effect selected and the good stability of ZSM-5 molecular sieve.Due to the TS-1 molecular sieve in organic oxidizing reaction, can adopt free of contamination lower concentration hydrogen peroxide as oxygenant, avoided the problem of oxidising process complex process and contaminate environment, there is unrivaled energy-conservation, the advantage such as economy and environment is friendly of conventional oxidation system, and there is good reaction preference, therefore there is great prospects for commercial application.
The synthetic method of TS-1 was disclosed (GB2071071A, USP4,410,501) first in 1981 by people such as gondola Marco Taramasso.The method is first to prepare a kind of ,Tai source, silicon source, organic bases (RN of containing
+) and/or basic oxide (Me
n/2o) reaction mixture, by this reaction mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 6～30 days, then separate, wash, dry, roasting and product.
The people such as Thangaraj think in the TS-1 molecular sieve that the Taramasso method synthesizes enter skeleton effective titanium content seldom, so they within 1992, disclose a kind of can effectively increase skeleton in the method (Zeolites of synthetic TS-1 molecular sieve of titanium content, 1992, Vol.12:943), it is reported can be by the Si/Ti of gained molecular sieve than from 39, dropping to 20.The method is that appropriate TPAOH (TPAOH) aqueous solution is joined to stirring and dissolving certain hour in tetraethyl silicate (TEOS) solution, and the liquid mixture that then under vigorous stirring, slowly adds the aqueous isopropanol of tetrabutyl titanate to obtain clarification (must slowly drip to prevent that tetrabutyl titanate hydrolysis is too fast and forms white TiO
2precipitation), after stirring 15 minutes, more slowly add the appropriate TPAOH aqueous solution, then reaction mixture be transferred to after 3～6 hours in autoclave in 170 ℃ of lower hydrothermal crystallizings 3～6 days except alcohol in 75～80 ℃, after drying the TS-1 molecular sieve.
The effective titanium content that the problem that the synthetic technology of above-mentioned TS-1 molecular sieve exists is to enter framework of molecular sieve is lower, and it is poor to be difficult for stably obtaining TS-1 molecular sieve, activity stability with good catalytic oxidation activity.CN1260241A discloses a kind of preparation method of HTS.It is by the hydrating solution of titanium and the TS-1 molecular sieve that synthesized according to molecular sieve (gram): Ti (mole): water (mole)=(200～1500): 1: the ratio of (120～450) mixes, and the gained mixture is reacted 1～8 day in sealing autoclave under 120～200 ℃.In CN1301599A, disclosed method is that the TS-1 molecular sieve is first used to acid treatment, with organic bases, mix again, and mixture is placed in to sealing autoclave, under the temperature of 120～200 ℃ and autogenous pressure, reaction is 1 hour to 8 days, by products therefrom after filtration, washing, dry, roasting, obtain having the HTS of hollow structure, this molecular sieve extra-framework titanium is few, catalytic oxidation activity is high, good stability.CN1421389A discloses the method with the silicon modifying titanium-silicon molecular sieve, siliceous aqueous solution modification synthetic HTS for the method, compositions of mixtures: molecular sieve (gram): Si (mole): organic bases (mole): water (mole)=(100～550): 1: (0.05～0.5): (150～350).After modification molecular sieve catalytic oxidation activity and work-ing life all obviously improve, by product obviously reduces.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method of processing HTS, the method is processed the former HTS activity of HTS specific activity obtained and is significantly improved.
The method of processing HTS provided by the invention, is characterized in that said modification liquid is that He Tai source, silicon source is hydrolyzed and obtains in organic bases solution with modification liquid modifying titanium-silicon molecular sieve under saturated steam.
More particularly, the method of processing HTS provided by the present invention comprises: the mixture of a kind of modification liquid and HTS is placed in closed reactor and processes at least 2 hours under 80～200 ℃, then at normal temperatures and pressures by the product drying, roasting obtains the HTS product of modification, wherein, contain under reaction conditions the water yield that forms saturated steam and be less than 1.2 with the weight ratio of HTS in reactor, said modification liquid mole consist of silicon: titanium: organic bases: water=1: (0～0.1): (0.05～5): (15～100), silicon is with SiO
2meter, titanium is with TiO
2meter, the weight ratio of HTS and modification liquid is 100: (10～150), the treatment capacity of HTS is at least 10 grams per liter reactors.
The method of processing HTS provided by the invention compared to existing technology, has following advantage:
1, the consumption consumption for the treatment of processes organic bases is low, without the mother liquor filtering separation, also without the washes discharge, has significantly improved the environmental protection efficiency of production process.
2, the high-tension apparatus capacity utilization improves, and has improved production efficiency, has reduced production cost.
Embodiment
Treatment process provided by the invention is applicable to various types of HTS, and common HTS has TS-1, TS-2, Ti-Beta, Ti-MWW molecular sieve etc., and the TS-1 molecular sieve of processing through the inventive method can effectively improve oxidation activity.
In treatment process provided by the invention, in mole composition of said modification liquid, silicon: titanium: organic bases: water=1: (0～0.1): (0.05～5.0): (15～100) (wherein silicon and titanium are with SiO
2and TiO
2meter), preferred mole of proportioning silicon: titanium: organic bases: water=1: (0.01～0.05): (0.3～3.0): (20～50) make through mixed hydrolysis under the condition that ,Tai source, silicon source is existed at alkaline organic.
In treatment process provided by the invention, said silicon source comprises silicon oxide, silica gel and organosilicon acid esters, and preferred silicon source is the organosilicon acid esters; Said its general formula of organosilicon acid esters is R
1 4siO
4, R wherein
1the alkyl that preferably has 1-4 carbon atom, preferred alkyl is ethyl.
In treatment process provided by the invention, said titanium source comprises inorganic titanium salt or organic titanate, and preferred titanium source is organic titanate; Said inorganic titanium salt can be TiCl
4, Ti (SO
4)
2perhaps TiOCl
2; Its general formula of said organic titanate is Ti (OR
2)
4, R wherein
2the alkyl that preferably has 1-6 carbon atom, preferred alkyl is ethyl, propyl group or butyl.
In treatment process provided by the invention, said organic bases can be selected from as organo-alkali compounds such as quaternary ammonium hydroxide compounds, fat amine compound and alcamine compounds.Said quaternary ammonium hydroxide compounds can be selected from TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH etc., said fat amine compound can be ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine or hexanediamine etc., and said alcamine compound can be monoethanolamine, diethanolamine or trolamine.Said organic bases also can be selected from TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine, one or more in trolamine, for example, the mixture of tetraethyl ammonium hydroxide and n-Butyl Amine 99, the mixture of tetraethyl ammonium hydroxide and n-Butyl Amine 99, the mixture of quadrol and TPAOH, the mixture of di-n-propylamine and TPAOH, the mixture of tetraethyl ammonium hydroxide and TPAOH, the mixture of hexanediamine and TPAOH all can be for the present invention.
In treatment process provided by the invention, the weight ratio of HTS and modification liquid is 100: (10～150), the weight ratio of preferred HTS and modification liquid is 100: (30～120).In mole composition of said modification liquid, silicon: titanium: organic bases=1: (0～0.1): (0.05～5), said modification liquid refers to that the Water Under solution existed at organic bases by He Tai source, silicon source forms, and in hydrolytic process, controls silicon (with SiO
2meter) be preferably 1 with the molar ratio of water: (20～50).
In treatment process provided by the invention, contain under reaction conditions the water yield that forms saturated steam and be less than 1.2 with the weight ratio of the HTS of inactivation in reactor, the water yield of said formation saturated steam can be provided by reaction kettle for reaction thing material, also can realize through adding outside water vapour.
In treatment process provided by the invention, reaction mixture treatment temp in closed reactor is 80～200 ℃, is preferably 150～180 ℃, and the treatment time is 2～72 hours, is preferably 6～72 hours.
In treatment process provided by the invention, after temperature and pressure returns under normal temperature and pressure in reactor, reclaim product in reactor, without after filtration and washing step, drying process and roasting process get final product.Said drying process can be carried out at the temperature between room temperature to 200 ℃, and said roasting can be carried out in 2～12 hours in air atmosphere between 300 ℃ to 800 ℃, and these processes are familiar with by those skilled in the art, at this and have no special requirements.
Below by embodiment, the present invention is further described, but does not therefore limit content of the present invention.
In embodiment, all to reagent be commercially available chemically pure reagent.
Comparative Examples 1
This Comparative Examples is to prepare the process of TS-1 sieve sample by the method described in " Zeolites, 1992, Vol.12:943-950 ".
22.5 gram tetraethyl orthosilicates are mixed with 7.0 gram TPAOH, and add 59.8 gram distilled water, hydrolysis 1.0 hours under normal pressure and 60 ℃ after mixing, obtain the hydrating solution of tetraethyl orthosilicate, add lentamente the solution formed by 1.1 gram tetrabutyl titanates and 5.0 gram anhydrous isopropyl alcohols under vigorous stirring, the gained mixture is stirred 3 hours under 75 ℃, obtain the clear colloid.This colloid is put into to the stainless steel sealed reactor, and at the temperature of 170 ℃, constant temperature is placed 3 days, obtains the mixture of crystallization product; This mixture is filtered, washes with water, and, in 110 ℃ of dryings 60 minutes, obtain the former powder of TS-1.The former powder of this TS-1, in 550 ℃ of roasting temperatures 3 hours, is obtained to TS-1 molecular sieve DB-1.
Comparative Examples 2
This Comparative Examples is by the effect that molecular sieve DB-1 reference literature CN1421389A processes molecular sieve that obtains in Comparative Examples 1.
To be hydrolyzed solution and mix with molecular sieve, it consists of: molecular sieve (gram): Si (mole): organic bases (mole): water (mole)=100: 0.33: 0.18: 100.This mixture is put into to the stainless steel sealed reactor, and at the temperature of 170 ℃, constant temperature is placed and then mixture to be filtered, to wash with water in 3 days, and in 110 ℃ of dryings 60 minutes, then by it in 550 ℃ of roasting temperatures 3 hours, obtain sieve sample, be designated as DB-2.
Embodiment 1
The tetraethyl orthosilicate of metering is mixed with tetraethyl ammonium hydroxide, and add distilled water, after mixing in stirring at normal temperature 1.0 hours, stir under 75 ℃ and within 3 hours, obtain modification liquid again, its consist of silicon (mole): titanium (mole): organic bases (mole): water (mole)=1: 0: 0.85: 20 (wherein silicon and titanium are with SiO
2and TiO
2meter)).Getting 12 gram TS-1 molecular sieve obtained above mixes with 10 gram modification liquids.By pack into 50ml polytetrafluoroethyllining lining be placed on the 100ml polytetrafluoroethyllining lining of said mixture, then in sealing autoclave in 175 ℃ of reactions 12 hours.
Products therefrom is dried 120 minutes in 150 ℃, then, 580 ℃ of roasting temperatures 5 hours, obtain modification TS-1 molecular sieve-4 A.
Embodiment 2
The amorphous silica gel of metering is mixed with TPAOH, and add distilled water, after mixing in stirring at normal temperature 1.5 hours, add again tetrabutyl titanate to stir 0.5 hour, then under 70 ℃, stir and within 3 hours, obtain modification liquid, its consist of silicon (mole): titanium (mole): organic bases (mole): water (mole)=1: 0.02: 0.75: 25 (wherein silicon and titanium are with SiO
2and TiO
2meter)).Getting 10 gram TS-1 molecular sieve obtained above mixes with in 8.5 gram modification liquids.By the mixture 50ml polytetrafluoroethyllining lining of packing into, then be placed on the 100ml polytetrafluoroethyllining lining, then in sealing autoclave in 180 ℃ of reactions 24 hours.
Products therefrom is dried 120 minutes in 150 ℃, then, 650 ℃ of roasting temperatures 2 hours, obtain modification TS-1 molecular sieve B.
Embodiment 3
Tetraethyl orthosilicate, the tetraethyl titanate of metering are mixed with TPAOH, and add distilled water, after mixing in stirring at normal temperature 1.0 hours, stir under 80 ℃ and within 3 hours, obtain modification liquid again, its consist of silicon (mole): titanium (mole): organic bases (mole): water (mole)=1: 0.02: 0.75: 35 (wherein silicon and titanium are with SiO
2and TiO
2meter)).Getting 15 gram TS-1 molecular sieve obtained above mixes with 13 gram modification liquids.By pack into 50ml polytetrafluoroethyllining lining be placed on the 100ml polytetrafluoroethyllining lining of mixture, then in sealing autoclave in 160 ℃ of reactions 62 hours.
Products therefrom is dried 240 minutes in 135 ℃, then, 560 ℃ of roasting temperatures 3 hours, obtain modification TS-1 molecular sieve C.
Embodiment 4
The tetraethyl orthosilicate of metering, tetraethyl titanate, trolamine and 4-propyl bromide are mixed, and add distilled water, after mixing in stirring at normal temperature 1.0 hours, stir under 75 ℃ and within 3 hours, obtain modification liquid again, its consist of silicon (mole): titanium (mole): trolamine (mole): 4-propyl bromide (mole): water (mole)=1: 0.015: 0.35: within 0.3: 20, (wherein silicon and titanium are with SiO
2and TiO
2meter)).Getting 12 gram TS-1 molecular sieve obtained above mixes with 9.5 gram modification liquids.By the mixture 50ml polytetrafluoroethyllining lining of packing into, then be placed on the 100ml polytetrafluoroethyllining lining, then in sealing autoclave in 165 ℃ of reactions 48 hours.
Products therefrom is dried 360 minutes in 100 ℃, then, 540 ℃ of roasting temperatures 6 hours, obtain modification TS-1 molecular sieve D.
Embodiment 5
The silicon-dioxide of metering is mixed with 4-propyl bromide, n-Butyl Amine 99, and add distilled water, in stirring at normal temperature 2.0 hours, add again tetrabutyl titanate to stir 0.5 hour, then under 75 ℃, stir and within 3 hours, obtain modification liquid, its consist of silicon (mole): titanium (mole): 4-propyl bromide (mole): n-Butyl Amine 99 (mole): water (mole)=1: 0.025: 0.85: within 1: 20, (wherein silicon and titanium are with SiO
2and TiO
2meter)).Getting 12 gram TS-1 molecular sieve obtained above mixes with 5 gram modification liquids.By pack into 50ml polytetrafluoroethyllining lining be placed on the 100ml polytetrafluoroethyllining lining and add and support of mixture, and add water 5ml under it, then in sealing autoclave in 155 ℃ of reactions 36 hours.
Products therefrom is dried 180 minutes in 175 ℃, then, 500 ℃ of roasting temperatures 5 hours, obtain modification TS-1 molecular sieve E.
Embodiment 6
The silica gel of metering, di-n-propylamine and TPAOH are mixed, and add distilled water, after mixing in stirring at normal temperature 1.5 hours, add again tetraethyl titanate to stir 0.5 hour, then under 65 ℃, stir and within 5 hours, obtain modification liquid, its consist of silicon (mole): titanium (mole): di-n-propylamine (mole): TPAOH (mole): water (mole)=1: 0.025: 0.35: within 1.2: 30, (wherein silicon and titanium are with SiO
2and TiO
2meter)).Getting 10 gram TS-1 molecular sieve obtained above mixes with 5 gram modification liquids.By the mixture 100ml polytetrafluoroethyllining lining of packing into, then in sealing autoclave, in 150 ℃, process 65 hours.
Products therefrom is dried 120 minutes in 160 ℃, then, 700 ℃ of roasting temperatures 3 hours, obtain modification TS-1 molecular sieve F.
Embodiment 7
The Z-type silica gel of metering, n-Butyl Amine 99,4-propyl bromide are mixed, and add distilled water, in stirring at normal temperature 1.5 hours, then add tetraethyl titanate, stir under 75 ℃ and within 3 hours, obtain modification liquid again, its consist of silicon (mole): titanium (mole): n-Butyl Amine 99 (mole): 4-propyl bromide (mole): water (mole)=1: 0.02: 0.95: within 0.8: 45, (wherein silicon and titanium are with SiO
2and TiO
2meter)).Getting 12 gram TS-1 molecular sieve obtained above mixes with 6 gram modification liquids.Said mixture is packed into, and also it is placed in the 100ml polytetrafluoroethyllining lining to the 50ml polytetrafluoroethyllining lining, then in sealing autoclave, in 180 ℃, reacts 18 hours.
Products therefrom is dried 270 minutes in 130 ℃, then, 550 ℃ of roasting temperatures 3 hours, obtain modification TS-1 molecular sieve G.
Embodiment 8
The silicic acid orthocarbonate of metering, butyl (tetra) titanate, Tri N-Propyl Amine and TPAOH are mixed, and add distilled water, after mixing in stirring at normal temperature 1.0 hours, stir under 75 ℃ and within 3 hours, obtain modification liquid again, its consist of silicon (mole): titanium (mole): Tri N-Propyl Amine (mole): TPAOH (mole): water (mole)=1: 0.02: 0.3: within 1.5: 20, (wherein silicon and titanium are with SiO
2and TiO
2meter)).Getting 9 gram TS-1 molecular sieve obtained above mixes with 4 gram modification liquids.By pack into 50ml polytetrafluoroethyllining lining be placed on the 100ml polytetrafluoroethyllining lining of said mixture, then in sealing autoclave in 160 ℃ of reactions 55 hours.
Products therefrom is dried 300 minutes in 135 ℃, then, 670 ℃ of roasting temperatures 4 hours, obtain modification TS-1 molecular sieve H.
Embodiment 9
The amorphous silica gel of metering, trolamine and TPAOH are mixed, and add distilled water, after mixing in stirring at normal temperature 1.5 hours, add tetraethyl titanate, then stir under 70 ℃ and within 4 hours, obtain modification liquid, its consist of silicon (mole): titanium (mole): trolamine (mole): TPAOH (mole): water (mole)=1: 0.02: 0.2: within 1: 22, (wherein silicon and titanium are with SiO
2and TiO
2meter)).Getting 12 gram TS-1 molecular sieve obtained above mixes with 4.5 gram modification liquids.By pack into 100ml polytetrafluoroethyllining lining the vial of in-built 3ml water is placed on mixture of mixture, then in sealing autoclave in 160 ℃ of reactions 56 hours.
Gained is dried 180 minutes in product in 180 ℃, then, 780 ℃ of roasting temperatures 2 hours, obtain modification TS-1 molecular sieve I.
Embodiment 10
The tetraethyl orthosilicate of metering, tetraethyl titanate, TBAH and 4-propyl bromide are mixed, and add distilled water, after mixing in stirring at normal temperature 1.0 hours, stir under 65 ℃ and within 5 hours, obtain modification liquid again, its consist of silicon (mole): titanium (mole): 4-propyl bromide (mole): TBAH (mole): water (mole)=1: 0.02: 0.8: within 0.85: 25, (wherein silicon and titanium are with SiO
2and TiO
2meter)).Get 12 gram TS-1 molecular sieve obtained above, join 5 gram modification liquids and mix.By the mixture 100ml polytetrafluoroethyllining lining of packing into, then in sealing autoclave in 165 ℃ of reactions 56 hours.
Products therefrom is dried 150 minutes in 120 ℃, then, 570 ℃ of roasting temperatures 6 hours, obtain modification TS-1 molecular sieve J.
Embodiment 11
The method gained TS-1 molecular sieve of the present embodiment explanation the present invention and contrast is for the effect of the catalytic oxidation of phenol hydroxylation.
By above-described embodiment and the prepared TS-1 molecular sieve of Comparative Examples according to TS-1: phenol: the weight ratio of acetone=1: 20: 16 mixes in a there-necked flask with prolong, be warming up to 80 ℃, then under whipped state according to phenol: the weight ratio of hydrogen peroxide=1: 0.39 adds the hydrogen peroxide that concentration is 30wt%, at this temperature, reaction is 4 hours, products therefrom is used HP-5 capillary column (30m * 0.25mm) to measure phenol conversion on 6890N type chromatographic instrument, the results are shown in Table 1.
Table 1
| The sample name | Phenol conversion % |
| DB-1 | 20.01 |
| DB-2 | 26.47 |
| A | 26.02 |
| B | 26.68 |
| C | 26.22 |
| D | 26.31 |
| E | 26.12 |
| F | 26.04 |
| G | 27.18 |
| H | 26.53 |
| I | 27.13 |
| J | 26.88 |
As can be seen from Table 1, to compare catalytic performance more superior for treatment process gained molecular sieve of the present invention and Comparative Examples gained molecular sieve DB-1.Simultaneously, with other method of modifying, compare and not only kept the superiority on the performance, can also reduce production cost, alleviate environmental pollution.
Claims (10)
1. a method of processing HTS, it is characterized in that the mixture of a kind of modification liquid and HTS is placed in closed reactor and processes at least 2 hours under 80～200 ℃, then at normal temperatures and pressures by the product drying, roasting obtains the HTS product of modification, wherein, contain under reaction conditions the water yield that forms saturated steam and be less than 1.2 with the weight ratio of HTS in reactor, said modification liquid is that He Tai source, silicon source is hydrolyzed and obtains in organic bases solution, in its mole of composition, silicon: titanium: organic bases: water=1: (0～0.1): (0.05～5): (15～100), silicon is with SiO
2meter, titanium is with TiO
2meter, the weight ratio of HTS and modification liquid is 100: (10～150), the treatment capacity of HTS is at least 10 grams per liter reactors.
2. according to the method for claim 1, the weight ratio of HTS and modification liquid is 100: (30～120).
3. according to the process of claim 1 wherein, in mole composition of said modification liquid, silicon: titanium: organic bases: water=1: (0.01～0.05): (0.3～3.0): (20～50).
4. according to the process of claim 1 wherein, said HTS is TS-1, TS-2, Ti-Beta, Ti-MWW molecular sieve.
5. according to the process of claim 1 wherein, the said water yield is provided by mixture contained humidity in closed reactor, or through adding outside water vapour to realize.
6. according to the process of claim 1 wherein, said organic bases is selected from quaternary ammonium hydroxide compounds, fat amine compound or alcamine compound.
7. according to the method for claim 1, wherein, said organic bases is selected from one or more in TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine, monoethanolamine, diethanolamine and trolamine.
8. according to the process of claim 1 wherein, it is R that said silicon source is selected from silicon oxide, silica gel or general formula
1 4siO
4the organosilicon acid esters, R
1be selected from the alkyl of 1～4 carbon atom.
9. according to the process of claim 1 wherein, said titanium source is selected from TiCl
4, Ti (SO
4)
2perhaps TiOCl
2, or general formula is Ti (OR
2)
4organic titanate, R
2be selected from the alkyl of 2～4 carbon atoms.
10. according to the process of claim 1 wherein, its condition of said processing for to carry out 6～72 hours in 135～180 ℃ of closed reactors.
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| CN104028300B (en) * | 2014-06-06 | 2017-05-03 | 郑州大学 | Modified TS-1 molecular sieve as well as preparation method and application thereof |
| CN106145145B (en) * | 2015-04-17 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of hetero-atom molecular-sieve and its synthetic method |
| CN106238094B (en) * | 2016-08-04 | 2018-10-19 | 大连理工大学 | A kind of method that extruded moulding Titanium Sieve Molecular Sieve is modified |
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