CN102311128A - Method for treating titanium-silicon molecular sieve - Google Patents
Method for treating titanium-silicon molecular sieve Download PDFInfo
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- CN102311128A CN102311128A CN2010102136012A CN201010213601A CN102311128A CN 102311128 A CN102311128 A CN 102311128A CN 2010102136012 A CN2010102136012 A CN 2010102136012A CN 201010213601 A CN201010213601 A CN 201010213601A CN 102311128 A CN102311128 A CN 102311128A
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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 handling HTS, handle the method for HTS more specifically to a kind of water vapour down.
Background technology
HTS is the novel hetero-atom molecular-sieve that last century, early eighties began to develop.The TS-1 that MFI type structure is arranged that has 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; For example the reactions such as oxidation of the epoxidation of alkene, aromatic hydrocarbons hydroxylation, pimelinketone oximate, alcohol have good selective oxidation performance and advantages of high catalytic activity, and they have a good application prospect as redox (red-ox) type sieve catalyst.
The TS-1 molecular sieve is that the transition metal titanium is introduced formed a kind of new titanium-silicone molecular sieve 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 advantages of excellent stability of ZSM-5 molecular sieve.Because the TS-1 molecular sieve is in organic oxidizing reaction; Can adopt free of contamination lower concentration hydrogen peroxide as oxygenant; Oxidising process complex process and problem of environment pollution caused have been avoided; Have unrivaled energy-conservation, economy of conventional oxidation system and advantages of environment protection, and have good reaction preference, therefore have great prospects for commercial application.
The compound method of TS-1 disclosed (GB2071071A, USP4,410,501) first by people such as gondola Marco Taramasso in 1981.This method is to prepare a kind of silicon source, titanium source, organic bases (RN of containing earlier
+) and/or basic oxide (Me
N/2O) reaction mixture, with this reaction mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 6～30 days, separate then, wash, dry, roasting and product.
People such as Thangaraj think get into skeleton in the TS-1 molecular sieve that the Taramasso method synthesizes effective titanium content seldom; So they disclose a kind of method (Zeolites that can effectively increase the synthetic TS-1 molecular sieve of titanium content in the skeleton in 1992; 1992; Vol.12:943), it is reported can be with the Si/Ti of gained molecular sieve than dropping to 20 from 39.This method is that an amount of TPAOH (TPAOH) aqueous solution is joined stirring and dissolving certain hour in tetraethyl silicate (TEOS) solution, and the aqueous isopropanol that under vigorous stirring, slowly adds tetrabutyl titanate then obtains clarifying liquid mixture and (must slowly drip to prevent that tetrabutyl titanate hydrolysis is too fast and form white TiO
2Deposition), stirs after 15 minutes, slowly add an amount of TPAOH aqueous solution again, then reaction mixture is removed alcohol in 75～80 ℃ and be transferred to after 3～6 hours in the autoclave, get the TS-1 molecular sieve after the drying in 170 ℃ of following hydrothermal crystallizings 3～6 days.
Effective titanium content that the problem that the synthetic technology of above-mentioned TS-1 molecular sieve exists is to get into framework of molecular sieve is lower, and it is relatively poor to be difficult for stably obtaining having TS-1 molecular sieve, the activity stability of good catalytic oxidation activity.CN1260241A discloses a kind of preparation method of HTS.It is with 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 mixed of (120～450) is even, with the gained mixture in sealing autoclave in 120～200 ℃ of reactions 1～8 day down.Disclosed method is that the TS-1 molecular sieve is used s.t. earlier among the CN1301599A, mixes with organic bases, and mixture is placed sealing autoclave; Reaction is 1 hour to 8 days under 120～200 ℃ temperature and autogenous pressure; With products therefrom through filter, washing, dry, roasting, the HTS that obtains having 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; This method is with siliceous aqueous solution modification synthetic HTS, and mixture is formed: molecular sieve (gram): Si (mole): organic bases (mole): water (mole)=(100～550): 1: (0.05～0.5): (150～350).After the 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 handling HTS, this method is handled the former HTS activity of HTS specific activity that obtains and is significantly improved.
The method of processing HTS provided by the invention is characterized in that with modification liquid modifying titanium-silicon molecular sieve under moist steam said modification liquid is that the hydrolysis in organic bases solution of silicon source and titanium source is obtained.
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 the closed reactor in 80～200 ℃ of following processing at least 2 hours; At normal temperatures and pressures product is obtained the HTS product of modification then through drying, roasting; Wherein, Contain in the reaction kettle under reaction conditions form moist steam and with the weight ratio of HTS less than 1.2 the water yield, the mole of said modification liquid consists 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 reaction kettles.
The method of processing HTS provided by the invention is compared prior art, has following advantage:
1, the consumption consumption of treating processes organic bases is low, and no mother liquor filtering separation does not have the washes discharging yet, has significantly improved the environmental protection efficient 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 HTSs, and common HTS has TS-1, TS-2, Ti-Beta, Ti-MWW molecular sieve or the like, and the TS-1 molecular sieve of handling through the inventive method can effectively improve oxidation activity.
In the treatment process provided by the invention, during the mole of said modification liquid was formed, silicon: titanium: organic bases: water=1: (0～0.1): (0.05～5.0): (15～100) (wherein silicon and titanium were with SiO
2And TiO
2Meter), preferred mole proportioning silicon: titanium: organic bases: water=1: (0.01～0.05): (0.3～3.0): (20～50) make silicon source, titanium source under the condition that alkaline organic exists through mixed hydrolysis.
In the 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 an ethyl.
In the treatment process provided by the invention, said titanium source comprises inorganic titanium salt or organic titanate, and preferred titanium source is an organic titanate; Said inorganic titanium salt can be TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2Its 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 the treatment process provided by the invention, said organic bases can be selected from and be organo-alkali compounds such as quaternary ammonium hydroxide compounds, fat amine compound and alcamine compound.Said quaternary ammonium hydroxide compounds can be selected from TPAOH, tetraethyl ammonium hydroxide, TMAH, TBAH etc.; Said fat amine compound can be ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, tetramethylenediamine or hexanediamine etc., and said alcamine compound can be monoethanolamine, diethylolamine or trolamine.Said organic bases also can be selected from one or more in TPAOH, tetraethyl ammonium hydroxide, TMAH, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, tetramethylenediamine, hexanediamine, monoethanolamine, diethylolamine, the 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 used for the present invention.
In the 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).During the mole of said modification liquid was formed, silicon: titanium: organic bases=1: (0～0.1): (0.05～5), said modification liquid were meant by the hydrolysis under the condition that organic bases exists of silicon source and titanium source and form that in hydrolytic process, control silicon is (with SiO
2Meter) molar ratio with water is preferably 1: (20～50).
In the treatment process provided by the invention; Contain in the reaction kettle under reaction conditions form moist steam and with the weight ratio of the HTS of inactivation less than 1.2 the water yield; The water yield of said formation moist steam can be provided by reaction kettle for reaction thing material, also can realize through adding the external water steam.
In the 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 the treatment process provided by the invention, after temperature and pressure in the reaction kettle returns under the normal temperature and pressure, reclaim product in the reaction kettle, need not to get final product through drying process and roasting process through filtering and washing step.Said drying process can be carried out under the temperature between the room temperature to 200 ℃, and said roasting can be between 300 ℃ to 800 ℃ be carried out in air atmosphere in 2～12 hours, 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.
Among the embodiment, all to reagent be commercially available chemically pure reagent.
Comparative Examples 1
This Comparative Examples is for preparing the process of TS-1 sieve sample by the method described in " Zeolites, 1992, Vol.12:943-950 ".
The positive tetraethyl orthosilicate of 22.5 grams is mixed with 7.0 gram TPAOHs; And add 59.8 the gram zero(ppm) water; Mix the back in normal pressure and 60 ℃ of following hydrolysis 1.0 hours, obtain the hydrating solution of positive tetraethyl orthosilicate, under vigorous stirring, add lentamente by 1.1 gram tetrabutyl titanates and restrain the solution that anhydrous isopropyl alcohols are formed with 5.0; The gained mixture was stirred 3 hours down at 75 ℃, obtain the clear colloid.This colloid is put into the stainless steel sealed reactor, and constant temperature was placed 3 days under 170 ℃ temperature, obtained the mixture of crystallization product; This mixture is filtered, uses water washing, and, obtain the former powder of TS-1 in 110 ℃ of dryings 60 minutes.With the former powder of this TS-1 in 550 ℃ of roasting temperatures 3 hours, TS-1 molecular sieve DB-1.
Comparative Examples 2
This Comparative Examples is with the effect that obtains molecular sieve DB-1 reference literature CN1421389A handling of molecular sieve in the Comparative Examples 1.
The intact solution of hydrolysis is mixed with molecular sieve, and it consists of: molecular sieve (gram): Si (mole): organic bases (mole): water (mole)=100: 0.33: 0.18: 100.This mixture is put into the stainless steel sealed reactor, and constant temperature is placed and then mixture to be filtered, to use water washing in 3 days under 170 ℃ temperature, and in 110 ℃ of dryings 60 minutes, again with it in 550 ℃ of roasting temperatures 3 hours, obtain sieve sample, be designated as DB-2.
Embodiment 1
The positive tetraethyl orthosilicate of metering is mixed with tetraethyl ammonium hydroxide; And adding zero(ppm) water; Mix the back in stirring at normal temperature 1.0 hours; Stir down at 75 ℃ and obtained modification liquid in 3 hours, it consists 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 the above-mentioned TS-1 molecular sieves that obtain of 12 grams and 10 restrains the modification liquid and mixes.With pack into 50ml polytetrafluoroethyllining lining and be placed on the 100ml polytetrafluoroethyllining lining of said mixture, then in sealing autoclave in 175 ℃ of reactions 12 hours.
Products therefrom in 150 ℃ of oven dry 120 minutes, then 580 ℃ of roasting temperatures 5 hours, is obtained modification TS-1 molecular sieve-4 A.
Embodiment 2
The amorphous silica gel of metering is mixed with TPAOH; And adding zero(ppm) water; Mix the back in stirring at normal temperature 1.5 hours; Add tetrabutyl titanate again and stirred 0.5 hour, then stir down at 70 ℃ and obtained modification liquid in 3 hours, it consists 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)).Get in 10 above-mentioned TS-1 molecular sieves that obtain of gram and the 8.5 gram modification liquid and mix.With the mixture 50ml polytetrafluoroethyllining lining of packing into, be placed on the 100ml polytetrafluoroethyllining lining again, then in sealing autoclave in 180 ℃ of reactions 24 hours.
Products therefrom in 150 ℃ of oven dry 120 minutes, then 650 ℃ of roasting temperatures 2 hours, is obtained modification TS-1 molecular sieve B.
Embodiment 3
Positive tetraethyl orthosilicate, the tetraethyl titanate of metering are mixed with TPAOH; And adding zero(ppm) water; Mix the back in stirring at normal temperature 1.0 hours; Stir down at 80 ℃ and obtained modification liquid in 3 hours, it consists 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 the above-mentioned TS-1 molecular sieves that obtain of 15 grams and 13 restrains the modification liquid and mixes.With pack into 50ml polytetrafluoroethyllining lining and be placed on the 100ml polytetrafluoroethyllining lining of mixture, then in sealing autoclave in 160 ℃ of reactions 62 hours.
Products therefrom in 135 ℃ of oven dry 240 minutes, then 560 ℃ of roasting temperatures 3 hours, is obtained modification TS-1 molecular sieve C.
Embodiment 4
Positive tetraethyl orthosilicate, tetraethyl titanate, trolamine and the 4-propyl bromide of metering are mixed; And adding zero(ppm) water; Mix the back in stirring at normal temperature 1.0 hours; Stir down at 75 ℃ and obtained modification liquid in 3 hours, it consists of silicon (mole): titanium (mole): trolamine (mole): 4-propyl bromide (mole): water (mole)=1: 0.015: 0.35: (wherein silicon and titanium were with SiO in 0.3: 20
2And TiO
2Meter)).Getting the above-mentioned TS-1 molecular sieves that obtain of 12 grams and 9.5 restrains the modification liquid and mixes.With the mixture 50ml polytetrafluoroethyllining lining of packing into, be placed on the 100ml polytetrafluoroethyllining lining again, then in sealing autoclave in 165 ℃ of reactions 48 hours.
Products therefrom in 100 ℃ of oven dry 360 minutes, then 540 ℃ of roasting temperatures 6 hours, is obtained modification TS-1 molecular sieve D.
Embodiment 5
The silicon-dioxide of metering is mixed with 4-propyl bromide, n-Butyl Amine 99; And adding zero(ppm) water; In stirring at normal temperature 2.0 hours; Add tetrabutyl titanate again and stirred 0.5 hour, then stir down at 75 ℃ and obtained modification liquid in 3 hours, it consists of silicon (mole): titanium (mole): 4-propyl bromide (mole): n-Butyl Amine 99 (mole): water (mole)=1: 0.025: 0.85: (wherein silicon and titanium were with SiO in 1: 20
2And TiO
2Meter)).Getting the above-mentioned TS-1 molecular sieve that obtains of 12 grams mixes with 5 gram modification liquid.With pack into 50ml polytetrafluoroethyllining lining and be placed on the 100ml polytetrafluoroethyllining lining and add in the support of mixture, and under it, add water 5ml, then in sealing autoclave in 155 ℃ of reactions 36 hours.
Products therefrom in 175 ℃ of oven dry 180 minutes, then 500 ℃ of roasting temperatures 5 hours, is obtained modification TS-1 molecular sieve E.
Embodiment 6
Silica gel, di-n-propylamine and the TPAOH of metering are mixed; And adding zero(ppm) water; Mix the back in stirring at normal temperature 1.5 hours; Add tetraethyl titanate again and stirred 0.5 hour, then stir down at 65 ℃ and obtained modification liquid in 5 hours, it consists of silicon (mole): titanium (mole): di-n-propylamine (mole): TPAOH (mole): water (mole)=1: 0.025: 0.35: (wherein silicon and titanium were with SiO in 1.2: 30
2And TiO
2Meter)).Getting the above-mentioned TS-1 molecular sieves that obtain of 10 grams and 5 restrains the modification liquid and mixes.With the mixture 100ml polytetrafluoroethyllining lining of packing into, in sealing autoclave, handled 65 hours then in 150 ℃.
Products therefrom in 160 ℃ of oven dry 120 minutes, then 700 ℃ of roasting temperatures 3 hours, is obtained modification TS-1 molecular sieve F.
Embodiment 7
Z type silica gel, n-Butyl Amine 99, the 4-propyl bromide of metering are mixed; And adding zero(ppm) water; In stirring at normal temperature 1.5 hours; Add tetraethyl titanate then, stir down at 75 ℃ and obtained modification liquid in 3 hours, it consists of silicon (mole): titanium (mole): n-Butyl Amine 99 (mole): 4-propyl bromide (mole): water (mole)=1: 0.02: 0.95: (wherein silicon and titanium were with SiO in 0.8: 45
2And TiO
2Meter)).Getting the above-mentioned TS-1 molecular sieves that obtain of 12 grams and 6 restrains the modification liquid and mixes.Pack into 50ml polytetrafluoroethyllining lining and its of said mixture placed the 100ml polytetrafluoroethyllining lining, then in sealing autoclave in 180 ℃ of reactions 18 hours.
Products therefrom in 130 ℃ of oven dry 270 minutes, then 550 ℃ of roasting temperatures 3 hours, is obtained modification TS-1 molecular sieve G.
Embodiment 8
Silicic acid orthocarbonate, butyl(tetra)titanate, Tri N-Propyl Amine and the TPAOH of metering are mixed; And adding zero(ppm) water; Mix the back in stirring at normal temperature 1.0 hours; Stir down at 75 ℃ and obtained modification liquid in 3 hours, it consists of silicon (mole): titanium (mole): Tri N-Propyl Amine (mole): TPAOH (mole): water (mole)=1: 0.02: 0.3: (wherein silicon and titanium were with SiO in 1.5: 20
2And TiO
2Meter)).Getting the above-mentioned TS-1 molecular sieves that obtain of 9 grams and 4 restrains the modification liquid and mixes.With pack into 50ml polytetrafluoroethyllining lining and be placed on the 100ml polytetrafluoroethyllining lining of said mixture, then in sealing autoclave in 160 ℃ of reactions 55 hours.
Products therefrom in 135 ℃ of oven dry 300 minutes, then 670 ℃ of roasting temperatures 4 hours, is obtained modification TS-1 molecular sieve H.
Embodiment 9
Amorphous silica gel, trolamine and the TPAOH of metering are mixed; And adding zero(ppm) water; Mix the back in stirring at normal temperature 1.5 hours; Add tetraethyl titanate, stir down at 70 ℃ then and obtained modification liquid in 4 hours, it consists of silicon (mole): titanium (mole): trolamine (mole): TPAOH (mole): water (mole)=1: 0.02: 0.2: (wherein silicon and titanium were with SiO in 1: 22
2And TiO
2Meter)).Getting the above-mentioned TS-1 molecular sieves that obtain of 12 grams and 4.5 restrains the modification liquid and mixes.With pack into 100ml polytetrafluoroethyllining lining and the vial of interior dress 3ml water placed on the mixture of mixture, then in sealing autoclave in 160 ℃ of reactions 56 hours.
With gained in product in 180 ℃ of oven dry 180 minutes, then 780 ℃ of roasting temperatures 2 hours, obtain modification TS-1 molecular sieve I.
Embodiment 10
Positive tetraethyl orthosilicate, tetraethyl titanate, TBAH and the 4-propyl bromide of metering are mixed; And adding zero(ppm) water; Mix the back in stirring at normal temperature 1.0 hours; Stir down at 65 ℃ and obtained modification liquid in 5 hours, it consists of silicon (mole): titanium (mole): 4-propyl bromide (mole): TBAH (mole): water (mole)=1: 0.02: 0.8: (wherein silicon and titanium were with SiO in 0.85: 25
2And TiO
2Meter)).Get the above-mentioned TS-1 molecular sieve that obtains of 12 grams, join 5 gram modification liquid and mix.With the mixture 100ml polytetrafluoroethyllining lining of packing into, then in sealing autoclave in 165 ℃ of reactions 56 hours.
Products therefrom in 120 ℃ of oven dry 150 minutes, then 570 ℃ of roasting temperatures 6 hours, is obtained modification TS-1 molecular sieve J.
Embodiment 11
Present embodiment explanation the present invention and correlated method gained TS-1 molecular sieve are used for the effect of the catalytic oxidation of phenol hydroxylation.
The TS-1 molecular sieve that the foregoing description and Comparative Examples is prepared is according to TS-1: phenol: the weight ratio of acetone=1: 20: 16 mixes in the there-necked flask of a band prolong; Be warming up to 80 ℃; Then under whipped state according to phenol: it is the hydrogen peroxide of 30wt% that the weight ratio of hydrogen peroxide=1: 0.39 adds concentration; Reaction is 4 hours under this temperature; Products therefrom uses the HP-5 capillary column on 6890N type chromatographic instrument (30m * 0.25mm) measure phenol conversion, the result sees 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 |
Can find out that from table 1 data it is more superior that treatment process gained molecular sieve of the present invention and Comparative Examples gained molecular sieve DB-1 compare catalytic performance.Simultaneously, compare with other method of modifying and not only to have kept the meliority on the performance, can also reduce production cost, alleviate environmental pollution.
Claims (11)
1. a method of handling HTS is characterized in that with modification liquid modifying titanium-silicon molecular sieve under moist steam, and said modification liquid is that the hydrolysis in organic bases solution of silicon source and titanium source is obtained.
2. according to the method for claim 1; It is characterized in that the mixture of a kind of modification liquid and HTS is placed in the closed reactor in 80～200 ℃ of following processing at least 2 hours; At normal temperatures and pressures product is obtained the HTS product of modification then through drying, roasting; Wherein, contain in the reaction kettle under reaction conditions form moist steam and with the weight ratio of HTS less than 1.2 the water yield, during the mole of said modification liquid is formed; 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 reaction kettles.
3. according to the method for claim 1, the weight ratio of HTS and modification liquid is 100: (30～120).
4. according to the method for claim 2, wherein, during the mole of said modification liquid is formed, silicon: titanium: organic bases: water=1: (0.01～0.05): (0.3～3.0): (20～50).
5. according to the process of claim 1 wherein, said HTS is TS-1, TS-2, Ti-Beta, Ti-MWW molecular sieve.
6. according to the method for claim 7, wherein, the said water yield is provided by mixture contained humidity in the closed reactor, or realizes through adding the external water steam.
7. according to the process of claim 1 wherein, said organic bases is selected from quaternary ammonium hydroxide compounds, fat amine compound or alcamine compound.
8. according to the method for claim 1; Wherein, said organic bases is selected from one or more in TPAOH, tetraethyl ammonium hydroxide, TMAH, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, tetramethylenediamine, hexanediamine, monoethanolamine, diethylolamine and the trolamine.
9. 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.
10. 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.
11. according to the process of claim 1 wherein, its condition of said processing is for to carry out 6～72 hours in 135～180 ℃ of closed reactors.
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| CN104028300A (en) * | 2014-06-06 | 2014-09-10 | 郑州大学 | Modified TS-1 molecular sieve as well as preparation method and application thereof |
| CN104556111A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Ti-Si molecular sieve and synthesis method thereof |
| CN106145145A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hetero-atom molecular-sieve and synthetic method thereof |
| CN106238094A (en) * | 2016-08-04 | 2016-12-21 | 大连理工大学 | A kind of method that extruded moulding HTS is modified |
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| CN1421389A (en) * | 2001-11-29 | 2003-06-04 | 中国石油化工股份有限公司 | Ti-Si molecular sieve modifying method |
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|---|---|---|---|---|
| CN104556111A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Ti-Si molecular sieve and synthesis method thereof |
| CN104556111B (en) * | 2013-10-29 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of Titanium Sieve Molecular Sieve and its synthetic method |
| CN104028300A (en) * | 2014-06-06 | 2014-09-10 | 郑州大学 | Modified TS-1 molecular sieve as well as preparation method and application thereof |
| CN106145145A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hetero-atom molecular-sieve and synthetic method 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 |
| CN106238094A (en) * | 2016-08-04 | 2016-12-21 | 大连理工大学 | A kind of method that extruded moulding HTS is modified |
| 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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