CN1212892C - Method of synthesizing titanium silicon molecular sieve - Google Patents

Method of synthesizing titanium silicon molecular sieve Download PDF

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CN1212892C
CN1212892C CN 02160124 CN02160124A CN1212892C CN 1212892 C CN1212892 C CN 1212892C CN 02160124 CN02160124 CN 02160124 CN 02160124 A CN02160124 A CN 02160124A CN 1212892 C CN1212892 C CN 1212892C
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accordance
molecular sieve
sio
template
alkyl
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CN1513760A (en
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张明森
柯丽
郝玉春
杨菁
冯静
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The present invention discloses a method for synthesizing a titanium-silicon molecular sieve. The present invention adopts a hydrothermal synthesis method, and alkoxyl quaternary ammonium compound whose general formula is R1 R2 R3 R4 N<+>OR is taken as a template agent, wherein the R1, the R2, the R3 and the R4 can be identical or different and represents alkyl or aralkyl with C1 to C20, and the R represents alkyl with C1 to C4. A TS-1 molecular sieve prepared by taking tetrapropyl isopropyl alcohol ammonium as a template agent and adopting the method of the present invention has the same structure as a TS-1 molecular sieve obtained by a classical method. The method of the present invention does not use high purity tetraalkyl ammonium hydroxide, so the present invention has the advantages of simple and convenient process, and little pollution.

Description

A kind of method of synthesis of titanium silicon molecular sieve
Technical field
The present invention relates to a kind of method of synthesis of molecular sieve.
Background technology
HTS is the novel hetero-atom molecular-sieve that begins to develop the early 1980s, the TS-1 type molecular sieve that MFI type structure is arranged that has synthesized at present, the TS-2 type molecular sieve of MEL type structure etc.Since coming out, because its good selective oxidation performance, and be widely used in the selective oxidation field.In reactions such as benzene oxidation system phenol, phenol hydrogen peroxide hydroxylation preparing benzenediol, oxidation of alkanes system ketone and alcohol, ammoxidation of cyclohexanone preparing cyclohexanone oxime, olefin oxidation system epoxide, HTS shows good catalytic activity and selective oxidation as catalyzer.
The synthetic method of HTS roughly has two kinds at present, and a kind of is that classical synthetic method is that hydrothermal synthesis method prepares HTS; Another kind is a secondary synthetic method, and promptly isomorphous substitution method prepares HTS.But the performance of the molecular sieve of latter's preparation is poor than the former.
The TS-1 molecular sieve is that the transition metal titanium is introduced formed a kind of new titanium-silicone molecular sieve with good selective paraffin oxidation catalytic performance in the framework of molecular sieve with ZSM-5 structure.Because the TS-1 molecular sieve has been avoided oxidising process complex process and problem of environment pollution caused in the application in selective oxidation field, have unrivaled energy-conservation, economy of conventional oxidation system and advantages of environment protection, be considered to the milestone of the zeolite catalysis eighties.Over nearly 20 years, the preparation of HTS and applied research become a focus in zeolite catalysis field.
US4410501 discloses the synthetic method of TS-1 molecular sieve first, and this method adopts hydrothermal synthesis method, earlier a kind of silicon of preparation source, titanium source, organic bases (RN +) and/or the reaction mixture of basic oxide, and do not contain basic metal and alkaline-earth metal ions in this mixture, with this reaction mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 6～30 days, separate then, wash, dry, roasting and product.Silicon source wherein can be tetraalkyl silicon ester, colloidal state SiO 2Or alkalimetal silicate, the titanium source can be hydrolyzable titanium compound, the template of using is TPAOH.
Document Applied Catalysis, 58 (1990) L1-L4 use conventional methods, and are the silicon source with the tetraethyl orthosilicate promptly, are that template is synthesized the TS-2 molecular sieve with the TBAH.The synthetic method of the disclosed TS-2 molecular sieve of CN1268401 also is to be template with the TBAH.
In the prior art, when preparation TS-1 and TS-2 HTS, all need highly purified TPAOH and TBAH as template.But owing to costing an arm and a leg of this template, consumption is more in the process of synthesis of titanium silicon molecular sieve, makes the preparation cost of HTS increase; And because the preparation process complexity of template, seriously polluted exists problem of environmental pollution.Therefore, above-mentioned factor has become one of major reason of restriction HTS industrial application.
Summary of the invention
The objective of the invention is to seek a kind of material and replace the used template tetra-alkyl ammonium hydroxide of prior art, the HTS that processability is good solves environmental pollution and the cost problem of higher of using existing template to bring.
The inventor finds by number of research projects, uses general formula to be R 1R 2R 3R 4N +RO -Alkoxy quaternary ammonium compounds do template, can prepare HTS with good catalytic performance.
The method of synthesis of titanium silicon molecular sieve of the present invention comprises: adopt hydrothermal synthesis method, use general formula to be R 1R 2R 3R 4N +RO -Alkoxy quaternary ammonium compounds make template, R wherein 1, R 2, R 3, R 4Can be identical or different, represent C 1-C 20Alkyl or aralkyl, R is C 1-C 4Alkyl;
Preferred described R 1, R 2, R 3, R 4Identical, represent C 1-C 5Alkyl, a kind of as in methyl, ethyl, propyl group, sec.-propyl, the butyl;
A kind of in preferred R represent methylidene, ethyl, propyl group, sec.-propyl, the butyl.
Preferred described template is tetrapropyl Virahol ammonium, tetrabutyl Virahol ammonium.
The method of preferred synthesis of titanium silicon molecular sieve of the present invention may further comprise the steps:
(1) with a certain amount of silicic acid tetraalkyl ester, be dissolved in template in the solvent and hydrolyzable titanium compound mixes, add proper amount of deionized water then, stir, after heating removes solvent, add proper amount of deionized water again, wherein the mol ratio of each initial reagent is: SiO 2/ TiO 2Be 5-200, be preferably 40-70, template R 1R 2R 3R 4N +RO -/ SiO 2Be 0.1-1.0, be preferably 0.2-0.6, H 2O/SiO 2Be 10-100, be preferably 15-55;
(2) solution of step (1) gained is transferred to carried out hydrothermal treatment consists in the autoclave, temperature is 140-200 ℃, and is aging after 18-72 hour, obtains crystal and mother liquor;
(3) described crystal is separated with mother liquor,, obtain purpose product HTS through washing, dry, roasting.
Wherein preferred described silicic acid tetraalkyl ester is selected from quanmethyl silicate, tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters.
Solvent described in the preferred steps (1) can be selected from low-carbon alcohol R 5OH and lower carbon number hydrocarbons R 6At least a among the H, wherein R 5, R 6Be C 1-C 6Alkyl.
Be 1: 1～3: 1 with the weight ratio of the deionized water that adds for the second time the first time in the preferred steps (1).
Preferred described titanium compound is selected from TiCl 4, TiOCl 2Or tetralkyl titanate; More preferably described titanium compound is selected from tetraethyl titanate, metatitanic acid orthocarbonate, tetrabutyl titanate.
General formula is R 1R 2R 3R 4N +RO -Alkoxy quaternary ammonium compounds can adopt the preparation of the precipitator method and ion exchange method.Application number is that disclosed content is introduced the present invention as a reference in full in 01134711.2 and 01143458.9 the patent application.
The described precipitator method are exactly with general formula R 1R 2R 3R 4N +X -Shown quaternary ammonium salt is dissolved in the organic solvent, with a certain amount of general formula be that the metal-alcoholates of ROM (wherein M is a basic metal) reacts, obtain containing the solution of solids, filter, the filtrate that obtains is for containing R 1R 2R 3R 4N +RO -The solution of alkoxy quaternary ammonium compounds, contain the alkalimetal ion of trace in this solution.The mol ratio of described metal-alcoholates and quaternary ammonium salt is 0.75-1.25, is preferably 0.85-0.95.This method is easy to operate, and cost is low, does not almost have the three wastes.
Described ion exchange method is exactly the general formula R that will be dissolved in the organic solvent 1R 2R 3R 4N +X -Shown quaternary ammonium salt is used RO -The strongly basic anion exchange resin of ionic is handled, and obtains general formula R 1R 2R 3R 4N +RO -Shown silane alcohol base quaternary ammonium compound solution; This method can be carried out in ion exchange column continuously, also can carry out in container interchanger discontinuous.The purity of the silane alcohol base quaternary ammonium compound solution that this method obtains is higher, does not contain alkalimetal ion substantially.
General formula is R 1R 2R 3R 4N +RO -The preparation of alkoxy quaternary ammonium compounds with respect to the preparation of tetra-alkyl ammonium hydroxide, process is simple and convenient, pollution-free, is eco-friendly technology.
Method of the present invention has avoided using highly purified tetra-alkyl ammonium hydroxide when the preparation HTS, process is simple, convenient, pollutes few.
Description of drawings
Fig. 1 is the infrared spectrum of the molecular sieve of embodiment 2 preparations.
Fig. 2 is the infrared spectrum of the molecular sieve of embodiment 4 preparations.
Fig. 3 is the infrared spectrum of the molecular sieve of comparative example 1 preparation.
Embodiment
Describe the process of using method of the present invention to prepare the TS-1 molecular sieve below in detail.
Take by weighing a certain amount of tetraethyl orthosilicate; join in the four-hole bottle that stirring is housed; open and stir; under nitrogen protection; drip an amount of tetrapropyl Virahol ammonium/aqueous isopropanol; drip the tetrabutyl titanate in the Virahol of being dissolved in of aequum afterwards, drip part tetrapropyl Virahol ammonium/aqueous isopropanol again, drip a certain amount of deionized water at last; continue to stir; heat to certain temperature, remove solvent, treat that solvent removal is clean after; add a certain amount of deionized water in the solution again; then solution is transferred in the autoclave, under stirring at a slow speed, be warmed up to certain temperature, stop to stir; behind the insulation certain hour; cooling; discharging; filter; washing, oven dry; roasting promptly obtains the TS-1 molecular sieve.
With embodiment the present invention is described below, but the present invention is not limited only to present embodiment.
Embodiment 1 usefulness ion exchange method prepares tetrapropyl Virahol ammonium/aqueous isopropanol
With 100gRO -Type anionite-exchange resin (R is a sec.-propyl), with the 4-propyl bromide aqueous isopropanol 135g soaking and stirring of 20Wt%, preparation tetrapropyl Virahol ammonium solution.Sampling analysis after 1 hour, [RO in the solution -]/[Br -]=0.9671, [RO -]=0.2588mmol/g, [Br -]=0.2676mmol/g.Repeat above-mentioned steps, gained solution is mixed, concentrate, obtain [RO -The tetrapropyl Virahol ammonium solution of]=1.03mmol/g.
Embodiment 2
The 32.5g tetraethyl orthosilicate is joined 500ml to be equipped with in the four-hole bottle of stirring; open and stir; under nitrogen protection, in four-hole bottle, drip the tetrapropyl Virahol ammonium/aqueous isopropanol 30g of embodiment 1 preparation; afterwards; dropwise adding tetrabutyl titanate/aqueous isopropanol 11g (the 1g tetrabutyl titanate is dissolved in the 10g Virahol); drip the above-mentioned tetrapropyl Virahol of 12.5g ammonium/aqueous isopropanol again, drip the 100g deionized water at last, this moment, solution was clear solution.Be warmed up to 78-82 ℃, be incubated 1-3 hour, to guarantee that solvent removal is clean.After treating that solvent removal is clean, add the 50g deionized water, solution is transferred to autoclave.
Stir at a slow speed down that autoclave is warmed up to 170 ℃, stop to stir, and be incubated 24 hours, cooling, discharging, filtration, washing, to neutral, in baking oven after the oven dry, 550 ℃ of roastings are 6 hours in the retort furnace, promptly obtain HTS with solution washing.
By examination of infrared spectrum figure shown in Figure 1 as can be seen, this molecular sieve is 960cm at the characteristic peak of TS-1 molecular sieve -1The absorption peak at place is obvious, illustrates that titanium atom has entered into SiO 2In the lattice, the molecular sieve that promptly adopts this method to obtain is the TS-1 molecular sieve.Again because 960cm -1The peak height of the absorption peak at place is bigger, illustrates to enter into SiO 2Titanium atom in the lattice is more, can illustrate that the catalytic performance of the TS-1 molecular sieve that makes is better.
The embodiment 3 usefulness precipitator method prepare tetrapropyl Virahol ammonium/aqueous isopropanol
5.0g (0.13mol) potassium metal is dissolved in the 50ml Virahol, the preparation potassium isopropoxide; 40g (0.15mol) 4-propyl bromide is dissolved in joins in the 100ml Virahol in the above-mentioned potassium isopropoxide, stirred 1 hour, left standstill 30 minutes, solution is filtered, obtain tetrapropyl Virahol ammonium/aqueous isopropanol, sampling analysis, [RO in the solution -]/[Br -]=2.425, [K +]/[RO -]=0.07, [RO -]=0.97mmol/g, [Br -]=0.4mmol/g, [K +]=0.069mmol/g.
Embodiment 4
Except that the tetrapropyl Virahol ammonium/aqueous isopropanol 81.4g with embodiment 3 preparations replaces the tetrapropyl Virahol ammonium/aqueous isopropanol 42.5g of embodiment 1 preparation, other step is identical with embodiment 2.
By examination of infrared spectrum figure shown in Figure 2 as can be seen, there is the characteristic peak of TS-1 molecular sieve in resulting molecular sieve, illustrates that titanium atom has entered into SiO 2In the lattice, promptly adopt the tetrapropyl Virahol ammonium/aqueous isopropanol that contains micro-potassium ion to make template, also can obtain the TS-1 molecular sieve.
Comparative example 1
Adopt classical hydrothermal synthesis method to prepare the TS-1 molecular sieve.
The 32.5g tetraethyl orthosilicate is joined 500ml to be equipped with in the four-hole bottle of stirring; open and stir; under nitrogen protection, in four-hole bottle, drip weight percent concentration and be 17% TPAOH aqueous solution 75g; afterwards; dropwise adding tetrabutyl titanate/aqueous isopropanol 11g (the 1g tetrabutyl titanate is dissolved in the 10g Virahol); drip the above-mentioned TPAOH aqueous solution of 25g again, this moment, solution was clear solution.Be warmed up to 78-82 ℃, be incubated 1-3 hour, to guarantee that solvent removal is clean.After treating that solvent removal is clean, add the 50g deionized water, solution is transferred to autoclave.
Stir at a slow speed down that autoclave is warmed up to 170 ℃, stop to stir, and be incubated 24 hours, cooling, discharging, filtration, washing, to neutral, in baking oven after the oven dry, 550 ℃ of roastings are 6 hours in the retort furnace, promptly obtain the TS-1 molecular sieve with solution washing.
Figure 3 shows that the infrared spectrum of standard TS-1 molecular sieve, at 960cm -1The absorption peak at place is obvious.
Embodiment 2 and 4 is obtained the infrared spectrum of molecular sieve and infrared spectrum that comparative example 1 obtains molecular sieve relatively, observe the size of characteristic peak, the TS-1 molecular sieve that adopts method of the present invention to obtain as can be known has identical structure with the TS-1 molecular sieve that classical approach obtains.

Claims (10)

1, a kind of method of synthesis of titanium silicon molecular sieve is characterized in that this method adopts hydrothermal synthesis method, uses general formula to be R 1R 2R 3R 4N +RO -Alkoxy quaternary ammonium compounds make template, R wherein 1, R 2, R 3, R 4Can be identical or different, represent C 1-C 20Alkyl or aralkyl, R is C 1-C 4Alkyl.
2, in accordance with the method for claim 1, it is characterized in that described R 1, R 2, R 3, R 4Identical, represent C 1-C 5Alkyl.
3, in accordance with the method for claim 1, it is characterized in that described R 1, R 2, R 3, R 4Identical, a kind of in represent methylidene, ethyl, propyl group, sec.-propyl and the butyl; A kind of in R represent methylidene, ethyl, propyl group, sec.-propyl, the butyl.
4, in accordance with the method for claim 1, it is characterized in that described template is a tetrapropyl Virahol ammonium.
5, in accordance with the method for claim 1, it is characterized in that described hydrothermal synthesis method may further comprise the steps:
(1) with a certain amount of silicic acid tetraalkyl ester, be dissolved in template in the solvent and hydrolyzable titanium compound mixes, add proper amount of deionized water then, stir, after heating removes solvent, add proper amount of deionized water again, wherein the mol ratio of each initial reagent is: SiO 2/ TiO 2Be 5-200, template R 1R 2R 3R 4N +RO -/ SiO 2Be 0.1-1.0, H 2O/SiO 2Be 10-100;
(2) solution of step (1) gained is transferred to carried out hydrothermal treatment consists in the autoclave, temperature is 140-200 ℃, and is aging after 18-72 hour, obtains crystal and mother liquor;
(3) described crystal is separated with mother liquor,, obtain purpose product HTS through washing, dry, roasting.
6, in accordance with the method for claim 5, it is characterized in that described silicic acid tetraalkyl ester is selected from quanmethyl silicate, tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters.
7, in accordance with the method for claim 5, it is characterized in that described solvent can be selected from low-carbon alcohol R 5OH and lower carbon number hydrocarbons R 6At least a among the H, wherein R 5, R 6Be C 1-C 6Alkyl.
8, in accordance with the method for claim 5, the mol ratio that it is characterized in that each initial reagent is: SiO 2/ TiO 2Be 40-70, template R 1R 2R 3R 4N +RO -/ SiO 2Be 0.2-0.6, H 2O/SiO 2Be 15-55.
9, in accordance with the method for claim 5, it is characterized in that described titanium compound is selected from TiCl 4, TiOCl 2Or tetralkyl titanate.
10, in accordance with the method for claim 9, it is characterized in that described titanium compound is selected from tetraethyl titanate, metatitanic acid orthocarbonate, tetrabutyl titanate.
CN 02160124 2002-12-31 2002-12-31 Method of synthesizing titanium silicon molecular sieve Expired - Lifetime CN1212892C (en)

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CN100430318C (en) * 2004-09-24 2008-11-05 中国石油化工股份有限公司 Method of synthesizing titanium containing porous material
CN101428814B (en) * 2007-11-07 2011-04-27 中国石油化工股份有限公司 Synthesis of titanium-silicon molecular sieve TS-1
CN102344150A (en) * 2010-07-29 2012-02-08 中国石油化工股份有限公司 Synthetic method for mesopore titanium-silicon molecular sieve
CN102502690A (en) 2011-10-31 2012-06-20 大连理工大学 Method for modifying TS (Titanium silicalite)-1 based on mixed liquor of quaternary ammonium salt and inorganic base

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