CN102309980B - Steam modifying method of titanium-silicon molecular sieve - Google Patents
Steam modifying method of titanium-silicon molecular sieve Download PDFInfo
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Abstract
The invention relates to a steam modifying method of a titanium-silicon molecular sieve. The method is characterized by comprising the following steps: mixing the titanium-silicon molecular sieve with organic aqueous alkali, treating the mixture in a sealed reaction kettle at the temperature of 80 to 200 DEG C for at least two hours; and taking the product at the normal temperature and normal pressure, drying and baking to obtain the modified product of the titanium-silicon molecular sieve, wherein the reaction kettle contains water which forms saturated steam under the reaction condition andthe weight ratio of the water to the titanium-silicon molecular sieve is less than 1.2; the treatment amount of the titanium-silicon molecular sieve is at least 10 grams per liter of the reaction kettle; and the mixing ratio of the titanium-silicon molecular sieve to organic alkali is 100g to (0.005-0.2) mol. The method has low cost, less three wastes and high efficiency; and the modified molecular sieve has excellent catalytic performance.
Description
Technical field
The present invention relates to a kind of method of modifying of HTS, will have HTS synthetic under the synthetic technology condition carries out modification under water vapour atmosphere method now more specifically to a kind of.
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 hydroxylating, cyclohexanone 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 molecular 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 oxidation reaction, can adopt free of contamination low concentration hydrogen peroxide as oxidant, oxidizing process complex process and problem of environment pollution caused have been avoided, have unrivaled energy-conservation, the economy of conventional oxidation system and advantages of environment protection, and have good reaction selectivity, therefore have great prospects for commercial application.
The synthetic 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 base (RN of containing earlier
+) and/or basic anhydride (Me
N/2O) reactant mixture, with this reactant mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 6～30 days, separate then, wash, dry, roasting and product.
People such as Thangaraj think enter skeleton in the TS-1 molecular sieve that the Taramasso method synthesizes effective Ti content seldom, so they disclose a kind of method (Zeolites that can effectively increase the synthetic TS-1 molecular sieve of Ti 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 silester (TEOS) solution, slowly adds the liquid mixture that the aqueous isopropanol of butyl titanate obtains clarifying then and (must slowly drip to prevent that tetrabutyl titanate hydrolysis is too fast and form white TiO under vigorous stirring
2Precipitation), stirs after 15 minutes, slowly add an amount of TPAOH aqueous solution again, then reactant mixture is transferred to after 3～6 hours in the autoclave in 170 ℃ of following hydrothermal crystallizings 3～6 days except alcohol in 75～80 ℃, get the TS-1 molecular sieve after the drying.
Effective Ti 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 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 ratio of (120～450) mixes, 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 earlier acid treatment among the CN1301599A, mix with organic base again, and mixture placed sealing autoclave, reaction is 1 hour to 8 days under 120～200 ℃ temperature and self-generated pressure, with products therefrom after filtration, washing, dry, roasting, the HTS that obtains having hollow-core construction, this molecular sieve extra-framework titanium is few, the catalytic oxidation activity height, good stability.CN1421389A discloses the method with the silicon modifying titanium-silicon molecular sieve, the HTS that this method has been synthesized with siliceous aqueous solution modification, mixture is formed: molecular sieve (gram): Si (mole): organic base (mole): water (mole)=(100～550): 1: (0.05～0.5): (150～350).After the modification molecular sieve catalytic oxidation activity and service life all obviously improve, accessory substance obviously reduces.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of cost low, the three wastes are few, the method for modifying of the HTS that efficient is high.
HTS water vapour method of modifying provided by the present invention, it is characterized in that HTS and organic base solution mixing back were handled 2 hours under 80～200 ℃ in closed reactor at least, take out the product drying at normal temperatures and pressures, roasting gets the modified product of HTS, wherein, contain in the reactor under reaction condition form saturated steam and with the weight ratio of HTS less than 1.2 the water yield, the treating capacity of HTS is at least 10 grams per liter reactors, the mixed proportion of HTS and organic base is 100: (0.005～0.2), HTS is in gram, and organic base is in mole.
Method of modifying provided by the invention has following advantage:
(1) because water vapour modification processing procedure does not have the mother liquor isolated by filtration, also there is not the washes discharging, can reduce the consumption of organic base simultaneously, significantly improved the environmental protection efficient of production process.
(2) because water vapour modification processing procedure Central Plains material usage reduces, and operation shortens, and product yield improves, the high-tension apparatus capacity utilization improves, and has improved production efficiency, greatly reduces production cost.
The specific embodiment
In the method for modifying provided by the invention, said HTS refers to HTS synthetic through hydro-thermal and that other existing methods are synthetic, comprises TS-1, TS-2, Ti-Beta, Ti-MWW molecular sieve, preferred TS-1 molecular sieve.
In the method for modifying provided by the invention, said organic base can be selected from and be organo-alkali compounds such as quaternary ammonium base compounds, fat amine compound and alcamine compound.Said quaternary ammonium base compounds can be selected from TPAOH, tetraethyl ammonium hydroxide, TMAH, TBAH etc., said fat amine compound can be ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine or hexamethylene diamine etc., and said alcamine compound can be MEA, diethanol amine or triethanolamine.Said organic base also can be selected from TPAOH, tetraethyl ammonium hydroxide, TMAH, TBAH, ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine, in the triethanolamine one or more, for example, the mixture of tetraethyl ammonium hydroxide and n-butylamine, the mixture of tetraethyl ammonium hydroxide and n-butylamine, the mixture of ethylenediamine and TPAOH, the mixture of di-n-propylamine and TPAOH, the mixture of tetraethyl ammonium hydroxide and TPAOH, the mixture of hexamethylene diamine and TPAOH all can be used for the present invention.
In the method for modifying provided by the invention, the mixed proportion of HTS and organic base is 100: (0.005～0.2), preferred 100: (0.01～0.15) HTS is in gram, and organic base is in mole.
In the method for modifying provided by the invention, carry out the exchange of goods and materials and energy by the mode that gas phase shifts.Contain in the reactor under reaction condition form saturated steam and with the weight ratio of HTS less than 1.2 the water yield, the treating capacity of HTS is at least 10 grams per liter reactors.The said water yield is provided by mixture contained humidity in the closed reactor, or realizes through adding outside steam.In the method for modifying provided by the invention, particularly in reactor, contain under reaction condition form saturated steam and with the weight ratio of HTS less than also can requirement of the present invention under 0.9 the situation.
In the method for modifying provided by the invention, said processing, its condition be in the closed reactor 135～180 ℃ carried out 6～72 hours.
In the method for modifying provided by the invention, when through after the steam treatment, with reaction system cooling, pressure release, reclaim product under the normal temperature and pressure, said recovery need not to filter and washing, directly takes out the product drying, calcination process obtains modified product.Said dry run and roasting process are familiar with by those skilled in the art, at this and have no special requirements, dry can carrying out under the temperature between the room temperature to 200 ℃ for example, said roasting can be between 300 ℃ to 800 ℃ carry out in air atmosphere in 2～12 hours.
Be further described below by the present invention of embodiment, but therefore do not 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 distilled 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 the solution of being formed by 1.1 gram butyl titanates and 5.0 gram anhydrous isopropyl alcohols lentamente, 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, 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 got TS-1 molecular sieve DB-1.
Comparative Examples 2
This Comparative Examples is with the effect that molecular sieve DB-1 reference literature CN1421389A handles molecular sieve that obtains 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 base (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 wash with water 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
Get the above-mentioned TS-1 molecular sieve that obtains of 10 grams, 4.8 grams, 28% tetraethyl ammonium hydroxide solution mixes.With pack into 50ml polytetrafluoroethyllining lining and place the 100ml polytetrafluoroethyllining lining to add in the support of said mixture, under supporting, add water 2ml simultaneously, then in sealing autoclave in 145 ℃ of reactions 12 hours.
With gained through the molecular sieve of steam treatment modification in 100 ℃ of oven dry 180 minutes, then 650 ℃ of roasting temperatures 3 hours, obtain the TS-1 molecular sieve-4 A of water vapour modification.
Embodiment 2
Get the above-mentioned TS-1 molecular sieve that obtains of 12 grams, restrain 16.3% TPAOH solution and mix with 1 gram triethanolamine and 5.With pack into 50ml polytetrafluoroethyllining lining and place the 100ml polytetrafluoroethyllining lining to add in the support of said mixture, under supporting, add water 3ml simultaneously, then in sealing autoclave in 160 ℃ of reactions 56 hours.
With gained through the molecular sieve of steam treatment modification in 150 ℃ of oven dry 120 minutes, then 540 ℃ of roasting temperatures 6 hours, obtain the TS-1 molecular sieve B of water vapour modification.
Embodiment 3
Get the above-mentioned TS-1 molecular sieve that obtains of 12 grams, mix with 0.5 gram n-propylamine and 7.5 grams, 16.3% TPAOH solution.With the said mixture 50ml polytetrafluoroethyllining lining of packing into, be placed on the 100ml polytetrafluoroethyllining lining again and add in the support, then in sealing autoclave in 175 ℃ of reactions 48 hours.
With gained through the molecular sieve of steam treatment modification in 90 ℃ of oven dry 240 minutes, 700 ℃ of roasting temperatures 2 hours, obtain water vapour modification TS-1 molecular sieve C then.
Embodiment 4
Get the above-mentioned TS-1 molecular sieve that obtains of 12 grams, mix with TMAH and 3.5 grams, the 16.3% TPAOH solution of 3 grams 12%, said mixture is placed in the 100ml polytetrafluoroethyllining lining, in sealing autoclave, reacted 36 hours in 150 ℃ then.
With gained through the molecular sieve of steam treatment modification in 150 ℃ of oven dry 180 minutes, 530 ℃ of roasting temperatures 5 hours, obtain water vapour modification TS-1 molecular sieve D then.
Embodiment 5
Get the above-mentioned TS-1 molecular sieve that obtains of 14 grams, mix with 0.5 gram di-n-propylamine and 6.5 grams, 28% tetramethyl ammonium hydroxide solution.With pack into 50ml polytetrafluoroethyllining lining and place the 100ml polytetrafluoroethyllining lining to add in the support of said mixture, at it under, add water 2ml simultaneously, in sealing autoclave, reacted 56 hours in 150 ℃ then.
With gained through the molecular sieve of steam treatment modification in 150 ℃ of oven dry 180 minutes, 550 ℃ of roasting temperatures 3 hours, obtain water vapour modification TS-1 molecular sieve E then.
Embodiment 6
Get 10 grams and treat modification TS-1 molecular sieve, mix with 2.5 gram triethanolamines and 3 gram water, with pack into 50ml polytetrafluoroethyllining lining and place the 100ml polytetrafluoroethylene (PTFE) to add in the support of said mixture, at it under, add water 3ml simultaneously, in sealing autoclave, reacted 24 hours in 135 ℃ then.
With gained through the molecular sieve of steam treatment modification in 160 ℃ of oven dry 120 minutes, 650 ℃ of roasting temperatures 4 hours, obtain water vapour modification TS-1 molecular sieve F then.
Embodiment 7
Get 10 grams and treat modification TS-1 molecular sieve, mix with 0.5 gram ethylenediamine and 4.0 grams, 16.3% TPAOH solution.With the said mixture 50ml polytetrafluoroethyllining lining of packing into, be placed on the 100ml polytetrafluoroethyllining lining again and add in the support, at it under, add water 5ml simultaneously, in sealing autoclave, reacted 54 hours in 160 ℃ then.
With gained through the molecular sieve of steam treatment modification in 140 ℃ of oven dry 120 minutes, 600 ℃ of roasting temperatures 6 hours, obtain water vapour modification TS-1 molecular sieve G then.
Embodiment 8
Get 15 grams and treat modification TS-1 molecular sieve, mix with 0.4 gram n-butylamine and 4.8 grams, 27% tetraethyl ammonium hydroxide solution.With pack into 50ml polytetrafluoroethyllining lining and be placed on the 100ml polytetrafluoroethyllining lining and add in the support of said mixture, at it under, add water 8ml simultaneously, in sealing autoclave, reacted 16 hours in 180 ℃ then.
With gained through the molecular sieve of steam treatment modification in 130 ℃ of oven dry 120 minutes, 570 ℃ of roasting temperatures 3 hours, obtain water vapour modification TS-1 molecular sieve H then.
Embodiment 9
Get 12 grams and treat modification TS-1 molecular sieve, mix with 0.5 restrain oneself diamines and 6.5 grams 18% and TPAOH solution.Again mixture is placed in the 100ml polytetrafluoroethyllining lining and the vial of dress water 3ml in is placed on it, then in sealing autoclave in 165 ℃ of reactions 18 hours.
With gained through the molecular sieve of steam treatment modification in 135 ℃ of oven dry 360 minutes, 650 ℃ of roasting temperatures 5 hours, obtain water vapour modification TS-1 molecular sieve I then.
Embodiment 10
Get 10 grams and treat modification TS-1 molecular sieve, with 0.5 gram ethylenediamine and 6.0 grams, 25% TBAH solution, mix.The 50ml polytetrafluoroethyllining lining of then said mixture being packed into is placed on the 100ml polytetrafluoroethyllining lining again, then in sealing autoclave in 175 ℃ of reactions 24 hours.
With gained through the molecular sieve of steam treatment modification in 110 ℃ of oven dry 120 minutes, 580 ℃ of roasting temperatures 7 hours, obtain water vapour modification TS-1 molecular sieve J then.
Embodiment 11
The method gained TS-1 molecular sieve of present embodiment explanation the present invention and contrast is used for the effect of the catalytic oxidation of phenol hydroxylation.
The TS-1 molecular sieve that above-described embodiment 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 condenser pipe, be warming up to 80 ℃, then under stirring 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 at 6890N type chromatograph, and (30m * 0.25mm) measure phenol conversion the results are shown in Table 1.
Table 1
| The sample name | Phenol conversion |
| DB-1 | 20.01 |
| DB-2 | 26.47 |
| A | 26.18 |
| B | 26.70 |
| C | 26.22 |
| D | 26.30 |
| E | 23.22 |
| F | 22.06 |
| G | 26.05 |
| H | 23.25 |
| I | 26.56 |
| J | 22.78 |
From table 1 data as can be seen, to compare catalytic performance more superior for method of modifying gained molecular sieve of the present invention and Comparative Examples gained molecular sieve DB-1.Simultaneously, compare with other method of modifying and not only to have kept the superiority on the performance, can also reduce production cost, alleviate environmental pollution.
Claims (8)
1. the steam method of modifying of a HTS, it is characterized in that HTS and organic base solution mixing back were handled 2 hours under 80～200 ℃ in closed reactor at least, take out the product drying at normal temperatures and pressures, roasting gets the modified product of HTS, wherein, contain in the reactor under reaction condition form saturated steam and with the weight ratio of HTS less than 1.2 the water yield, the treating capacity of HTS is at least 10 grams per liter reactors, the mixed proportion of HTS and organic base is 100: (0.005～0.2), HTS is in gram, and organic base is in mole.
2. according to the process of claim 1 wherein, said HTS is selected from TS-1, TS-2, Ti-Beta, Ti-MWW molecular sieve.
3. according to the process of claim 1 wherein, said organic base is selected from quaternary ammonium base compounds, fat amine compound or alcamine compound.
4. according to the method for claim 1, wherein, said organic base is selected from one or more in TPAOH, tetraethyl ammonium hydroxide, TMAH, TBAH, ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine and the triethanolamine.
5. according to the process of claim 1 wherein, the mixed proportion of HTS and organic base is 100: (0.01～0.15), HTS are in gram, and organic base is in mole.
6. according to the process of claim 1 wherein, the said water yield is provided by mixture contained humidity in the closed reactor, or realizes through adding outside steam.
7. according to the process of claim 1 wherein, said processing, its condition be in the closed reactor 135～180 ℃ carried out 6～72 hours.
8. according to the process of claim 1 wherein, contain in the reactor under reaction condition, form saturated steam and with the weight ratio of HTS less than 0.9 the water yield.
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| CN103962177B (en) * | 2013-01-31 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of preparation method of the catalyst containing molecular sieve |
| 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 |
| CN104016338B (en) * | 2014-06-17 | 2015-12-09 | 中国科学院青海盐湖研究所 | A kind of method improving gentle thermal drivers graphene oxide phase change efficiency |
| CN105983437B (en) * | 2015-01-29 | 2019-02-01 | 中国石油化工股份有限公司 | A kind of catalyst of the structure molecular screen containing MWW, preparation method and applications |
| CN105984879B (en) * | 2015-01-29 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of MWW structure molecular screen and preparation method thereof |
| CN106145149B (en) * | 2015-03-31 | 2019-02-01 | 中国石油化工股份有限公司 | A method of preparing multi-stage porous Titanium Sieve Molecular Sieve |
| CN113880101A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | TS-1 molecular sieve and preparation method and application thereof |
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