CN101538187A - Application of nanometer ZSM-5 molecular sieve in reaction for preparing methanol by dimethyl ether catalysis and hydrolyzation - Google Patents

Application of nanometer ZSM-5 molecular sieve in reaction for preparing methanol by dimethyl ether catalysis and hydrolyzation Download PDF

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CN101538187A
CN101538187A CN200910050262A CN200910050262A CN101538187A CN 101538187 A CN101538187 A CN 101538187A CN 200910050262 A CN200910050262 A CN 200910050262A CN 200910050262 A CN200910050262 A CN 200910050262A CN 101538187 A CN101538187 A CN 101538187A
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molecular sieve
zsm
dme
methyl alcohol
nano
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李平
熊刚华
朱贻安
赵茜
陈春波
周兴贵
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

The invention discloses the application of nanometer ZSM-5 molecular sieve in the reaction for preparing methanol by dimethyl ether catalysis and hydrolyzation, relating to a method for preparing the methanol by gas-solid phase catalysis, namely, the dimethyl ether, water vapour and the ZSM-5 molecular sieve are mixed to obtain the methanol. The invention also discloses the novel application of the nanometer ZSM-5 molecular sieve.

Description

The application of nano-ZSM-5 molecular sieve in reaction for preparing methanol by dimethyl ether catalysis and hydrolyzation
Technical field
The present invention relates to the preparation of methyl alcohol, relate in particular to a kind of gas and solid phase catalyzing preparation method of methyl alcohol.
Background technology
Dme (DME) is a kind of colourless gas or compressed liquid, has slight ether fragrance.Dme has inertia under the normal temperature, is difficult for autoxidation, and no burn into non-carcinogenesis is a kind of industrial chemical of environmental protection.Dme has easy compression, condensation, gasification, and with characteristics such as many polarity or non-polar solvent dissolve each other, be widely used in aerosol goods propellant, freonll-11 alternative refrigerant, solvent etc. at present, also be used for the synthetic of other chemical, purposes is very extensive.Dme still is the ideal fuels of motor car engine, compares with methanol fuel automobile, does not have problems such as cold-starting automobile.Dme developing direction in the future is that market outlook are very wide as the substitute of vehicle fuel, oil liquefied gas etc.
Dme is met water and is generated methyl alcohol, therefore, and alternative deleterious methyl alcohol generation chemical reaction, as carry out vapor reforming hydrogen production etc., suit very much in environment such as household, automobile, to use.Yet under the situation that does not have catalyzer to exist, the speed of reaction of dme hydrolysis is very slow, can't satisfy actual needs.After adding an acidic catalyst, the hydrolysis rate of dme is significantly accelerated.Sulfuric acid is the liquid acid catalyst of using always, and is active high, but sulfuric acid corrosion resistance is strong, and toxicity is very big, easily environment is polluted.Some solid acid catalysts such as γ-Al 2O 3, ZSM-5, mordenite, β zeolite, Y zeolite, SiO 2-Al 2O 3And SO 4 2-/ ZrO 2Deng the dme hydrolysis is also had activity (document [1]: Wang Xiaolei etc., the gas chemical industry, 2008,33 (3): 65-70), molecular sieve catalysts active higher under low temperature (being lower than 300 ℃) wherein, and γ-Al 2O 3Etc. oxide-based catalyzer active better (document [2]: Feng Dongmei etc., the Chinese science and technology paper is online, 2007,1-6, http://www.paper.edu.cn) when temperature of reaction is higher than 300 ℃.Because the solid acid catalyst stable performance, be easy to separate, and free from environmental pollution with product, so the investigator use more, most popular (document [3]: Wang Wenjin etc., gas chemical industry, 2008,33 (1): 6-13) of molecular sieve catalysts particularly.
But everybody molecular sieve catalysts that adopts is conventional micron particles at present, exists problems such as active low and poor stability in the catalyzer use.
Therefore, this area presses for provides a kind of activity and all high molecular sieve catalyst of stability to be applied in the process of dme hydrolysis system methyl alcohol.
Summary of the invention
The present invention aims to provide a kind of gas and solid phase catalyzing preparation method of methyl alcohol.
Another object of the present invention provides the purposes of nano-ZSM-5 molecular sieve.
In a first aspect of the present invention, a kind of gas and solid phase catalyzing preparation method of methyl alcohol is provided, described method is that dme, water vapor and nano-ZSM-5 molecular sieve are mixed, and obtains methyl alcohol.
In another preference, the particle sphere diameter of described nano-ZSM-5 molecular sieve is 50-500nm; More preferably, the particle sphere diameter of described nano-ZSM-5 molecular sieve is 80-450nm.
In another preference, the silica alumina ratio of described nano-ZSM-5 molecular sieve is 15-150: 1; More preferably, the silica alumina ratio of described nano-ZSM-5 molecular sieve is 20-140: 1.
In another preference, the mol ratio of dme and water vapor is 1: 0.5-5; More preferably, the mol ratio of dme and water vapor is 1: 0.8-4.
In another preference, the blended air speed is 500-25000ml/ (gcath); More preferably, the blended air speed is 800-22000ml/ (gcath).
In another preference, in 0.5-2.5atm and 180-350 ℃ of mixing.
In another preference, described being blended in the fixed-bed reactor carried out.
In a second aspect of the present invention, a kind of purposes of nano-ZSM-5 molecular sieve is provided, described nano-ZSM-5 molecular sieve is used for the gas and solid phase catalyzing preparation of methyl alcohol.
In another preference, the particle sphere diameter of described nano-ZSM-5 molecular sieve is 50-500nm.
In another preference, the silica alumina ratio of described nano-ZSM-5 molecular sieve is 15-150: 1.
In view of the above, the invention provides method in a kind of process that active and all high molecular sieve catalyst of stability is applied to dme hydrolysis system methyl alcohol.
Description of drawings
Fig. 1 has shown that silica alumina ratio is X-ray diffraction crystal phase structure (XRD) collection of illustrative plates of 60: 1 nano-ZSM-5 molecular sieve.
Fig. 2 has shown that silica alumina ratio is X-ray diffraction crystal phase structure (XRD) collection of illustrative plates of 50: 1 commodity ZSM-5 molecular sieve.
Fig. 3 has shown that silica alumina ratio is scanning electron microscope (SEM) picture of 60: 1 nano-ZSM-5 molecular sieve.
Fig. 4 has shown that silica alumina ratio is scanning electron microscope (SEM) picture of 50: 1 commodity ZSM-5 molecular sieve.
Embodiment
The contriver is surprised to find that through extensive and deep research nano-ZSM-5 molecular sieve is used for dme hydrolysis system methanol process, reactive behavior height, and good stability as catalyzer.
Particularly, nano-ZSM-5 molecular sieve catalyzer of the present invention is a kind of Si-Al molecular sieve of the MFI of having structure, identical with the crystal phase structure of commodity ZSM-5 molecular sieve (providing) as the Tianjin Catalyst Factory, Nankai Univ, but it is spherical that particle is approximately, diameter is 50-500nm, is significantly less than the commodity ZSM-5 molecular sieve of main particle scale more than 1 μ m.
As used herein, " atm " is meant standard atmospheric pressure, 1atm=0.101325MPa
As used herein, " ZSM-5 molecular sieve " is meant a kind of micropore five-element circular type zeolite (molecular sieve) with three-D pore structure of synthetic, is a kind of Powdered porous silicoaluminate crystalline material.Have the MFI topological structure, belong to rhombic system, spacer is Pnma, and structure cell is formed can be expressed as Na nAl nSi 96-nO 19216H 2O, n is the atomicity of aluminium in the structure cell in the formula, n can from 0 to 27 variation in theory.Have two kinds of cross one another ten-ring pore canal system in its structure, one is for being parallel to the axial ten-ring straight hole of b road, the duct ovalize, and another is for being parallel to the ten-ring duct of a axial " Z " font.
As used herein, " nano-ZSM-5 molecular sieve " is meant that particle diameter is nano level ZSM-5 molecular sieve.
Nano-ZSM-5 molecular sieve of the present invention can prepare by method well known in the art, prepares such as but not limited to hydrothermal synthesis method.Can adopt document disclosed method (document [4]: Van Griekenet al.Microporous and Mesoporous Materials.2000,39 (1-2): 135-147), in one embodiment of the invention, adopt the preparation of Chinese patent CN1313207C disclosed method, preparation process is as follows:
(1) takes by weighing the 0.002mol aluminum isopropylate and put into beaker, add the TPAOH solution (weight concentration is 20%) of 0.0214mol, mix, add 11.7g water then;
(2) add 10g water again through behind the 30min, continue to be stirred to the solution clarification;
(3) add the 0.06mol tetraethoxy, continue to stir 1h;
(4) place step (3) gained solution 85 ℃ water-bath to heat, alcohol and water is removed in evaporation, and the time is 2-8h;
(5) step (4) gained solution is put into crystallizing kettle, under 170 ℃ of conditions, be incubated 48h;
(6) after the cooling solution is filtered, to filter cake wash, drying, at 550 ℃ of calcining 6h, promptly get nano-ZSM-5 molecular sieve then.
The silica alumina ratio of nano-ZSM-5 molecular sieve of the present invention is 15: 1-150: 1.
As used herein, " the gas and solid phase catalyzing preparation method of methyl alcohol " and " dme hydrolysis system methyl alcohol " can exchange use, all is meant the catalysis synthesis process of methyl alcohol, i.e. the mixed gas of dme and water vapor, through with the process that obtains methyl alcohol after catalyzer contacts.
In a preference of the present invention, the gas and solid phase catalyzing preparation method of methyl alcohol carries out in fixed-bed reactor, dme is a gas, water is after 250 ℃ of heating vaporizations, be mixed into the nano-ZSM-5 molecular sieve beds with dme, the mol ratio of dme and water vapor is 1: 0.5-1: 5, at normal pressure 0.5-2.5atm and temperature of reaction is 180-350 ℃, air speed (referring to the volume number that every gram catalyzer per hour flows through) is reacted under the condition of 500-25000ml/ (gcath), reactor outlet gas separates through cooling off laggard promoting the circulation of qi liquid, collect liquid phase substance, be methanol aqueous solution.
In an embodiment of the present invention, adopt vapor-phase chromatography (sky, Hong Kong U.S. chromatographic apparatus GC7890F of company gas chromatograph) to analyze methanol concentration in the aqueous solution, chromatographic column is the PEG-20M capillary column, column temperature is 10 ℃/min of 80-190 ℃ of temperature programming, carrier gas is an Ar gas, use the marker method analysis, internal standard substance is 1, the 2-propylene glycol.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can arbitrary combination.All features that this case specification sheets is disclosed can with any composition forms and usefulness, each feature that is disclosed in the specification sheets can anyly provide the alternative characteristics of identical, impartial or similar purpose to replace.Therefore removing has special instruction, and the feature that is disclosed only is the general example of equalization or similar features.
Major advantage of the present invention is:
1, catalyst reaction is active high, good stability, and no liquid phase by product can be used for on-site preparation methyl alcohol, also can be used for the reaction that is coupled and needs methyl alcohol to participate in.
2, dme can generate methyl alcohol by catalytic hydrolysis under normal pressure and lesser temps.
3, reaction raw materials is nontoxic, inexpensive, and reaction unit is simple.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to the normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise all percentage ratio, ratio, ratio or umber by weight.
Unit in the percent weight in volume among the present invention is well-known to those skilled in the art, for example is meant the weight of solute in 100 milliliters solution.
Unless otherwise defined, the same meaning that employed all specialties and scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The usefulness that preferable implementation method described in the literary composition and material only present a demonstration.
Embodiment 1
Dme hydrolysis system methyl alcohol I
The employing silica alumina ratio is 15: 1 a nano-ZSM-5 molecular sieve, and average diameter of particles is 400nm.The mol ratio of dme and water vapor is 1: 0.5, in normal pressure (2.5atm) and temperature of reaction is that 180 ℃, air speed are to react under the condition of 1000ml/ (gcath), record that the methyl alcohol weight concentration is 26.6% in the product water solution, no liquid phase by product, calculating the dimethyl ether conversion rate is 13.8%, near equilibrium conversion, react that the dimethyl ether conversion rate is 12.5% after 50 hours.
Embodiment 2
Dme hydrolysis system methyl alcohol II
The employing silica alumina ratio is 130: 1 a nano-ZSM-5 molecular sieve, and average diameter of particles is 100nm.The mol ratio of dme and water vapor is 1: 5, in normal pressure (1.5atm) and temperature of reaction is that 220 ℃, air speed are to react under the condition of 2000ml/ (gcath), record that the methyl alcohol weight concentration is 13.8% in the product water solution, no liquid phase by product, calculating the dimethyl ether conversion rate is 20.9%, react that the dimethyl ether conversion rate is 18.6% after 500 hours, visible good stability.
Embodiment 3
Dme hydrolysis system methyl alcohol III
The employing silica alumina ratio is 60: 1 a nano-ZSM-5 molecular sieve, and average diameter of particles is 200nm.The mol ratio of dme and water vapor is 1: 3, in normal pressure (1.0atm) and temperature of reaction is that 290 ℃, air speed are to react under the condition of 20000ml/ (gcath), record that the methyl alcohol weight concentration is 18.1% in the product water solution, calculating the dimethyl ether conversion rate is 23.6%, reacts that the dimethyl ether conversion rate is 14.7% after 50 hours.
Embodiment 4
Dme hydrolysis system methyl alcohol IV
The employing silica alumina ratio is 100: 1 a nano-ZSM-5 molecular sieve, and average diameter of particles is 300nm.The mol ratio of dme and water vapor is 1: 1, in normal pressure (0.5atm) and temperature of reaction is that 350 ℃, air speed are to react under the condition of 10000ml/ (gcath), record that the methyl alcohol weight concentration is 26.9% in the product water solution, calculating the dimethyl ether conversion rate is 31.7%, react that the dimethyl ether conversion rate is 15.3% after 20 hours, visible less stable.
Comparative Examples 1
The employing silica alumina ratio is 50: 1 a commodity ZSM-5 molecular sieve, and average diameter of particles is 1 μ m.The mol ratio of dme and water vapor is 1: 3, in normal pressure (1.0atm) and temperature of reaction is that 290 ℃, air speed are to react under the condition of 20000ml/ (gcath), record that the methyl alcohol weight concentration is 11.5% in the product water solution, calculating the dimethyl ether conversion rate is 10.6%, reacts that the dimethyl ether conversion rate is 5.1% after 50 hours.
Comparative Examples 2
Employing is all the nanometer HTS (TS-1) of MFI structure, and average diameter of particles is 200nm.The mol ratio of dme and water vapor is 1: 3, in normal pressure (1.0atm) and temperature of reaction is that 290 ℃, air speed are to react under the condition of 20000ml/ (gcath), not detecting methyl alcohol in the product water solution exists, the dimethyl ether conversion rate is zero, react that the dimethyl ether conversion rate still is zero after 2 hours.
The above only is preferred embodiment of the present invention, be not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people finish, if it is defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.

Claims (10)

1. the gas and solid phase catalyzing preparation method of a methyl alcohol is characterized in that, dme, water vapor and nano-ZSM-5 molecular sieve are mixed, and obtains methyl alcohol.
2. preparation method as claimed in claim 1 is characterized in that, the particle sphere diameter of described nano-ZSM-5 molecular sieve is 50-500nm; Preferably, the particle sphere diameter of described nano-ZSM-5 molecular sieve is 80-450nm.
3. preparation method as claimed in claim 1 is characterized in that, the silica alumina ratio of described nano-ZSM-5 molecular sieve is 15-150: 1; Preferably, the silica alumina ratio of described nano-ZSM-5 molecular sieve is 20-140: 1.
4. preparation method as claimed in claim 1 is characterized in that, the mol ratio of dme and water vapor is 1: 0.5-5; Preferably, the mol ratio of dme and water vapor is 1: 0.8-4.
5. preparation method as claimed in claim 1 is characterized in that, the blended air speed is 500-25000ml/ (gcath); Preferably, the blended air speed is 800-22000ml/ (gcath).
6. preparation method as claimed in claim 1 is characterized in that, in 0.5-2.5atm and 180-350 ℃ of mixing.
7. preparation method as claimed in claim 1 is characterized in that, described being blended in the fixed-bed reactor carried out.
8. the purposes of a nano-ZSM-5 molecular sieve is characterized in that, is used for the gas and solid phase catalyzing preparation of methyl alcohol.
9. purposes as claimed in claim 8 is characterized in that, the particle sphere diameter of described nano-ZSM-5 molecular sieve is 50-500nm.
10. purposes as claimed in claim 8 is characterized in that, the silica alumina ratio of described nano-ZSM-5 molecular sieve is 15-150: 1.
CN200910050262A 2009-04-29 2009-04-29 Application of nanometer ZSM-5 molecular sieve in reaction for preparing methanol by dimethyl ether catalysis and hydrolyzation Pending CN101538187A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103007983A (en) * 2012-10-08 2013-04-03 太原理工大学 HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof
CN110240177A (en) * 2019-07-02 2019-09-17 华东理工大学 A kind of laminated structure MFI type zeolite molecular sieve and preparation method thereof
CN113443965A (en) * 2021-05-20 2021-09-28 华东师范大学 Method for generating aryl phenol compound by hydrolyzing diaryl ether compound
CN114853592A (en) * 2021-02-03 2022-08-05 中国科学院大连化学物理研究所 Method for preparing glycollic acid by hydrolyzing alkoxy acetate

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103007983A (en) * 2012-10-08 2013-04-03 太原理工大学 HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof
CN103007983B (en) * 2012-10-08 2015-07-08 太原理工大学 HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof
CN110240177A (en) * 2019-07-02 2019-09-17 华东理工大学 A kind of laminated structure MFI type zeolite molecular sieve and preparation method thereof
CN110240177B (en) * 2019-07-02 2022-11-11 华东理工大学 MFI type zeolite molecular sieve with sheet structure and preparation method thereof
CN114853592A (en) * 2021-02-03 2022-08-05 中国科学院大连化学物理研究所 Method for preparing glycollic acid by hydrolyzing alkoxy acetate
CN114853592B (en) * 2021-02-03 2024-03-19 中国科学院大连化学物理研究所 Method for preparing glycollic acid by hydrolyzing alkoxy acetate
CN113443965A (en) * 2021-05-20 2021-09-28 华东师范大学 Method for generating aryl phenol compound by hydrolyzing diaryl ether compound

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Application publication date: 20090923