CN101653715B - Process for improving chemical reaction conversion rate by utilizing FAU-type molecular sieve membrane - Google Patents
Process for improving chemical reaction conversion rate by utilizing FAU-type molecular sieve membrane Download PDFInfo
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- CN101653715B CN101653715B CN2008100128620A CN200810012862A CN101653715B CN 101653715 B CN101653715 B CN 101653715B CN 2008100128620 A CN2008100128620 A CN 2008100128620A CN 200810012862 A CN200810012862 A CN 200810012862A CN 101653715 B CN101653715 B CN 101653715B
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Abstract
The invention provides a process for improving chemical reaction conversion rate by utilizing an FAU-type molecular sieve membrane. A reaction device comprises a membrane component provided with the FAU-type molecular sieve membrane; when reaction raw materials are subjected to catalytic reaction in a reactor or during the interstage of multistage reaction, the FAU-type molecular sieve membrane selectively removes reaction products methanol or/and ethanol out of the reaction system so as to promote the reaction to be equilibrated and move to the positive reaction direction, and improve the reaction conversion rate; and the process has simple and convenient operation and no pollution to the environment, and meets the requirement of green chemistry.
Description
Technical field
The present invention relates to the application of molecular screen membrane, the technology of utilizing FAU type molecular screen membrane to improve chemical reaction conversion rate is provided.
Background technology
Zeolite molecular sieve film is one type of novel inorganic film that recent two decades grows up; Advantages such as it has that general inoranic membrane mechanical strength is high, high temperature resistant, chemical resistance of concrete and bioerosion; Have simultaneously the characteristic of zeolite molecular sieve again: the pore passage structure of rule possesses the molecule sieving capacity; Specific area is big, high adsorption capacity; But the parent/hydrophobicity of modulation etc.Therefore, zeolite molecular sieve film has good separating property, and the field replaces organic film gradually becomes new study subject at multinomial membrane technology (like infiltration evaporation, gas separation, film reaction etc.).Last century Mo, the BNRI company of Japan has taken the lead in realizing the commercial production and the commercial Application aspect ethanol dehydration thereof of LTA type molecular screen membrane.
FAU type molecular screen membrane is a kind of molecular screen membrane that has using value.FAU type molecular sieve is divided into X type (silica alumina ratio is 1～1.5) and Y type (silica alumina ratio is greater than 1.5) according to the difference of silica alumina ratio, has three-dimensional twelve-ring pore passage structure, and the aperture is about 0.74nm (greater than the aperture of LTA type and MFI type molecular sieve).FAU type molecular sieve has adsorptive selectivity to some compound, inorganic compound such as carbon dioxide, water, organic compound such as low-carbon alcohols, low-carbon (LC) unsaturated hydrocarbons etc.Because possess above characteristics, FAU type molecular screen membrane has separating power preferably for constant boiling point such as methyl alcohol/methyl ether, methyl alcohol/methyl esters, benzene/cyclohexane or nearly boiling point organic mixture except that can be used for organics dehydration.Chinese patent CN1453063A (open day on November 5th, 2003) discloses a kind of method of synthetic NaY type molecular screen membrane, and uses it for and separate dichloroethanes and nitrogen, and separation is 20～80.Chinese patent CN101112676A (open day on January 30th, 2008) discloses the method for the synthetic FAU type molecular screen membrane of a kind of two-step home-position hydro-thermal, and is used for steam permeability and separation methanol/isopropanol, methyl alcohol/isobutanol mixture.
Organic reaction belongs to reversible reaction mostly, receives Equilibrium limit, even if there is effective catalyst in reaction system, the conversion ratio of reaction also often rests on lower level.Constantly remove if can will react a certain product or the accessory substance that generate, just can impel molecular balance to move, thereby improve the conversion ratio of reaction to the positive reaction direction.Traditional industry takes methods such as absorption, rectifying, extraction to realize this process, complicated operation, and efficient is low, and energy consumption is high, also can produce a large amount of environmental contaminants.Increasingly mature along with molecular screen membrane technology separates film with catalytic reaction integrated, can effectively improve the conversion ratio of reaction, and meet the requirement of Green Chemistry.
Summary of the invention
The purpose of this invention is to provide the technology of utilizing FAU type molecular screen membrane to improve chemical reaction conversion rate; This technology utilization FAU type molecular sieve film pervasion vaporization (steam infiltration) removes the methyl alcohol of reaction generation or/and ethanol; Thereby impel molecular balance to move, improve the conversion ratio of reaction to the positive reaction direction.
The invention provides the technology of utilizing FAU type molecular screen membrane to improve chemical reaction conversion rate; Reaction unit comprises the membrane module that FAU type molecular screen membrane is housed; Reaction raw materials takes place in the catalytic reaction in reactor or the inter-stage of reaction of high order, FAU type molecular screen membrane optionally with product methyl alcohol or/and ethanol shifts out reaction system.
The present invention is applicable to that product comprises methyl alcohol or/and the organic reaction of ethanol, the ester exchange reaction of participating in like methyl esters or ethyl ester compound, alcoholysis reaction, polycondensation reaction etc.
The technology of utilizing FAU type molecular screen membrane to improve chemical reaction conversion rate provided by the invention, said reaction raw materials comprises in methyl esters or the ethyl ester compound at least a; Said product comprises in methyl alcohol or the ethanol at least a.
The technology of utilizing FAU type molecular screen membrane to improve chemical reaction conversion rate provided by the invention, said reactor and membrane module can be the devices of two separations, and reactor places the upper reaches of membrane module, and reaction unit is made up of at least one bank of reactor and membrane module; Perhaps reactor combines with membrane module to constitute membrane reactor, catalytic reaction is separated simultaneously with film carry out, and reaction unit is made up of at least one membrane reactor.
The technology of utilizing FAU type molecular screen membrane to improve chemical reaction conversion rate provided by the invention, the used reaction unit of said this technology comprises the membrane module that FAU type molecular screen membrane is housed; Reaction raw materials fully mixes in blender; Get into the vaporizer vaporization through sampling pump; Steam after the vaporization gets into when in the fixed bed reactors catalytic reaction taking place or the inter-stage of reaction of high order, the membrane module of FAU type molecular screen membrane optionally with product methyl alcohol or/and ethanol shifts out reaction system.
The present invention is easy and simple to handle, and environmentally safe meets the requirement of Green Chemistry.
Description of drawings
The X-ray diffractogram of the FAU type molecular screen membrane of Fig. 1 embodiment 1;
The scanning electron microscope diagram that the FAU type molecular screen membrane of Fig. 2 embodiment 1 is positive;
The scanning electron microscope diagram of the FAU type molecular screen membrane side of Fig. 3 embodiment 1;
Several kinds of compounds of Fig. 4 embodiment 1 pass through amount and molecular dynamics diameter Relationship figure through the one-component steam of FAU type molecular screen membrane;
The experimental provision sketch map of Fig. 5 embodiment 2, wherein: 1 blender, 2 sampling pumps, 3 vaporizers, 4 Pressure gauges, 5 fixed bed reactors, 6 membrane modules, 7 condensers.
The specific embodiment
Following embodiment will further explain the present invention, but therefore not limit the present invention.
Embodiment 1: the separating property of the synthetic FAU type molecular screen membrane of microwave
Adopt original position aging-microwave heating method (synthetic method sees Chinese patent CN1778677A for details, open day on May 31st, 2006) is at porous α-Al
2O
3The X-ray diffractogram of the FAU type molecular screen membrane that support tube (porosity is about 30% for external diameter 12mm, internal diameter 9mm) outer surface is synthetic is as shown in Figure 1, has only FAU type molecular sieve and carrier α-Al among the figure
2O
3Diffraction maximum, do not have the diffraction maximum of other dephasigns.The sem photograph of FAU type molecular screen membrane (Fig. 2, Fig. 3) shows that carrier surface has covered a layer thickness and has been about 5 μ m, continuous fine and close molecular screen membrane.The molecular sieve crystal size is even, and adhesion is tight.Its silica alumina ratio is measured through energy-dispersion X-ray fluorescence spectrometer and is about 1.5.
(the effective film area is 24cm to measure FAU type molecular screen membrane
2) under normal pressure 393K condition the one-component vapour permeability can, the steam of water, methyl alcohol, ethanol, isopropyl alcohol, isobutanol and the benzene amount of passing through is as shown in Figure 4 with the relation of its kinetic diameter.Along with the increase of material molecule kinetic diameter, through the one-component steam amount decline rapidly thoroughly of FAU type molecular screen membrane.The amount of passing through of methyl alcohol and ethanol is bigger, and the molecular dynamics diameter is greater than isobutanol and the benzene of 0.5nm, and its amount of passing through is lower than 7 * 10
-10Mol/ (m
2SPa), than methyl alcohol and ethanol low more than two one magnitude.For 1,3,5-triisopropylbenzene (the molecular dynamics diameter is 0.84nm, greater than FAU type molecular sieve bore diameter), 4h is carried out in experiment is not had obvious gleanings.Above result shows, when the molecular dynamics diameter of compound greater than 0.5nm, its amount of passing through through FAU type molecular screen membrane is lower than 10
-9Mol/ (m
2SPa), differ bigger, thereby the mixture that their are formed is expected to utilize FAU type molecular screen membrane to realize separating with measuring thoroughly of methyl alcohol or ethanol.
Table 1 has specifically provided FAU type molecular screen membrane for several kinds of infiltration evaporation (steam infiltration) separating properties that contain the organic mixture of methyl alcohol or ethanol.When another component was fatty alcohol, the increase with the fatty alcohol carbon number increased film to the separation selectivity of methyl alcohol.For the mixture that methyl alcohol or ethanol and phenol, carbonic diester compounds etc. are formed, FAU type molecular screen membrane has higher separation selectivity.
Table 1FAU type molecular screen membrane is for infiltration evaporation (steam infiltration) separating property of organic mixture
Embodiment 2: the reaction of dimethyl carbonate and n-butanol
The ester exchange reaction of dimethyl carbonate and n-butanol is carried out in experimental provision as shown in Figure 5.0.1mol dimethyl carbonate and 0.4mol n-butanol after blender 1 fully mixes, get into vaporizer 3 vaporizations through sampling pump 2 with the flow of 1mL/min.Mixed vapour gets into the 2g nano-TiO is housed
2The fixed bed reactors 5 of catalyst react under 413K, 0.2MPa condition.Reaction back steam get into be equipped with FAU type molecular screen membrane (original position is aging-microwave heating method is synthetic, the effective film area is 22cm
2) membrane module 6 in, under 393K, 0.2MPa condition, realize to separate.The per-meate side of membrane module is found time through vavuum pump and is used liquid nitrogen condensation, and material liquid returns in the blender through condenser 7.After 4h is carried out in reaction, form with the gas chromatographic analysis reaction system, the conversion ratio of dimethyl carbonate is 82.6%, and the selectivity of dibutyl carbonate is 85.4%, and the productive rate of dibutyl carbonate is 70.5%.
Embodiment 3: the reaction of dimethyl carbonate and n-butanol
According to embodiment 2 identical operations; Just the FAU type molecular screen membrane in the membrane module adopts the two-step home-position hydro-thermal method synthetic (synthetic method sees Chinese patent CN101112676A for details; Open day on January 30th, 2008), its silica alumina ratio is determined as 1.2 through energy-dispersion X-ray fluorescence spectrometer.After reaction was carried out 4 hours, the conversion ratio of dimethyl carbonate was 81.5%, and the selectivity of dibutyl carbonate is 82.8%, and the productive rate of dibutyl carbonate is 67.5%.
Embodiment 4: the reaction of diethyl carbonate and n-butanol
According to embodiment 2 identical operations, just reactant is 10g diethyl carbonate and 40g n-butanol.After reaction was carried out 4 hours, the conversion ratio of diethyl carbonate was 52.4%, and the selectivity of dibutyl carbonate is 78.6%, and the productive rate of dibutyl carbonate is 41.2%.
Embodiment 5: the reaction of dimethyl carbonate and phenol
According to embodiment 2 similar operation, the 0.1mol dimethyl carbonate is with after 0.4mol phenol fully mixes, and gets into the vaporizer vaporization through sampling pump with the flow of 1mL/min.Mixed vapour gets into 2gTiO is housed
2/ SiO
2(TiO
2Load capacity is 12%) fixed bed reactors of catalyst, under 453K, condition of normal pressure, react.Reaction back steam get into be equipped with FAU type molecular screen membrane (original position is aging-microwave heating method is synthetic, the effective film area is 22cm
2) membrane module in, under 453K, condition of normal pressure, realize to separate.After 4h is carried out in reaction, form with the gas chromatographic analysis reaction system, the conversion ratio of dimethyl carbonate is 48.3%, and the selectivity of diphenyl carbonate is 64.6%, and the productive rate of diphenyl carbonate is 31.2%.
Embodiment 6: the reaction of dimethyl carbonate and phenol
According to embodiment 5 similar operation, just get into three groups of fixed bed reactors and membrane module successively after the reactant mixture vaporization, return blender again.After 4h was carried out in reaction, the conversion ratio of dimethyl carbonate was 71.2%, and the selectivity of diphenyl carbonate is 84.5%, and the productive rate of diphenyl carbonate is 60.2%.
Comparative example 1: the reaction of dimethyl carbonate and n-butanol
Comparative example 2: the reaction of dimethyl carbonate and phenol
Claims (5)
1. utilize FAU type molecular screen membrane to improve the technology of chemical reaction conversion rate, it is characterized in that: the used reaction unit of this technology comprises the membrane module that FAU type molecular screen membrane is housed; Reaction raw materials takes place in the catalytic reaction in reactor or the inter-stage of reaction of high order, FAU type molecular screen membrane optionally with product methyl alcohol or/and ethanol shifts out reaction system; Said reaction comprises ester exchange reaction or the alcoholysis reaction or the polycondensation reaction of at least a participation in methyl esters or the ethyl ester compound; The used reaction unit of this technology comprises the membrane module that FAU type molecular screen membrane is housed; Reaction raw materials fully mixes in blender; Get into the vaporizer vaporization through sampling pump; Steam after the vaporization gets into when in the reactor catalytic reaction taking place or the inter-stage of reaction of high order, the membrane module of FAU type molecular screen membrane optionally with product methyl alcohol or/and ethanol shifts out reaction system.
2. according to the said technology of utilizing FAU type molecular screen membrane to improve chemical reaction conversion rate of claim 1, it is characterized in that: said reaction raw materials comprises in methyl esters or the ethyl ester compound at least a.
3. according to the said technology of utilizing FAU type molecular screen membrane to improve chemical reaction conversion rate of claim 1, it is characterized in that: said product comprises in methyl alcohol or the ethanol at least a.
4. according to the said technology of utilizing FAU type molecular screen membrane to improve chemical reaction conversion rate of claim 1, it is characterized in that: said reactor and membrane module are the devices of two separations, and reactor places the upper reaches of membrane module.
5. according to the said technology of utilizing FAU type molecular screen membrane to improve chemical reaction conversion rate of claim 1, it is characterized in that: said reactor combines to constitute membrane reactor with membrane module.
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| CN104801340B (en) * | 2015-04-03 | 2017-04-19 | 太原理工大学 | Catalytic membrane reaction preparation technology for diphenyl carbonate |
| CN115572215B (en) * | 2022-10-24 | 2024-04-30 | 浙江汇甬新材料有限公司 | Separation method of methanol and dimethyl carbonate azeotrope through coupling and rectification of membrane separation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083822C (en) * | 1996-01-25 | 2002-05-01 | 埃克森美孚化学专利公司 | Process for conversion of ethylbenzene |
| CN2622190Y (en) * | 2003-05-13 | 2004-06-30 | 南京工业大学 | Biological reactor with inorganical film |
| CN1195578C (en) * | 2003-05-15 | 2005-04-06 | 大连理工大学 | Application of zeolite molecular sieve film in the separation of ethylidene dichloride-nitrogen mixture |
-
2008
- 2008-08-20 CN CN2008100128620A patent/CN101653715B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083822C (en) * | 1996-01-25 | 2002-05-01 | 埃克森美孚化学专利公司 | Process for conversion of ethylbenzene |
| CN2622190Y (en) * | 2003-05-13 | 2004-06-30 | 南京工业大学 | Biological reactor with inorganical film |
| CN1195578C (en) * | 2003-05-15 | 2005-04-06 | 大连理工大学 | Application of zeolite molecular sieve film in the separation of ethylidene dichloride-nitrogen mixture |
Non-Patent Citations (1)
| Title |
|---|
| 沈永德.NaY型分子筛膜的制备.《中国优秀硕士学位论文全文数据库》.2007,(第5期), * |
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