CN114558466A - Modified zeolite membrane, preparation method and application thereof, and system for separating methanol from crude alcohol - Google Patents
Modified zeolite membrane, preparation method and application thereof, and system for separating methanol from crude alcohol Download PDFInfo
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Abstract
The invention relates to the technical field of membrane separation, and discloses a modified zeolite membrane, a preparation method and application thereof, and a system for separating methanol from crude alcohol, wherein a hydrophobic organic matter is adsorbed on hydroxyl of the modified zeolite membrane, and the adsorption rate of the hydroxyl is 40-60%; the preparation method of the modified zeolite membrane comprises the following steps: and (3) reacting the zeolite membrane with hydrophobic organic steam at the temperature of 300-400 ℃ for 20-120min to obtain the modified zeolite membrane. Through the technical scheme, the zeolite membrane is treated by hydrophobic organic steam, so that hydrophobic organic matters cover the positions of hydroxyl groups in the zeolite membrane to obtain the zeolite membrane with high selectivity for methanol adsorption and desorption, thereby obtaining superior alcohol through zeolite membrane separation.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a modified zeolite membrane, a preparation method and application thereof, and a system for separating methanol from crude alcohol.
Background
Pectin consists of long chains of methyl galacturonic acid linkages containing a plurality of methoxy-OCH groups3Under the action of heat and enzyme, methoxy group is hydrolyzed and dissociated, and methanol is easily reduced and generated.
[RCOOCH3]n+11H2O———→[RCOOH]n+11CH3OH
Edible alcohol is based on grains, many of which contain pectins, such as corn pericarp, dried potato, bran, rice hulls, and the like. In conventional alcohol production processes, the main production of methanol is caused by three aspects: firstly, the raw material is generated by thermal decomposition; secondly, in the saccharification process, the pectic substance is decomposed under the action of pectinase to generate methoxyl, and methanol is formed after reduction; thirdly, during distillation, the remaining pectin substance generates methanol under the conditions of acid and heating. The formation of methanol is therefore accompanied by the entire process of refining the alcohol production by conventional methods.
Methanol is a highly toxic substance to human bodies, and for adult men, 7g of the methanol is taken to cause poisoning and visual impairment, and 70ml of the methanol is taken to cause death, so that the content of methanol in alcohol is strictly controlled in many countries. The general method for reducing the methanol impurity in the edible alcohol in the industrial production is a multi-tower rectification method, a zeolite adsorption method and a chemical reaction method, but the method has great difficulty and high cost when the methanol alcohol is not used. Wherein, the multi-tower rectification method usually needs 5 to 9 separation towers, has high cost and complex equipment, increases carbon emission, causes energy waste, and in addition, the methanol content in the head rectification liquid and the tail rectification liquid is higher and is usually abandoned, thereby causing the waste of raw materials; the zeolite adsorption method requires a large amount of zeolite, high-temperature activation is required for better zeolite adsorption effect, intermittent regeneration is required after zeolite adsorption saturation, and finally the cost is increased; the chemical method for removing the methanol needs to add soda lime, potassium permanganate, calcium chloride, magnesium chloride and other substances, the removal rate of the methanol is less than 10 percent, the edible alcohol can be polluted, and the method has no practical value.
Therefore, the prior art lacks a method for efficiently separating methanol from alcohol on the premise of low energy consumption, less pollution and convenient operation.
Disclosure of Invention
The invention aims to solve the problems of high energy consumption, large pollution and inconvenient operation of a method for separating methanol from alcohol in the prior art, and provides a modified zeolite membrane, a preparation method and application thereof, and a system for separating methanol from crude alcohol.
In order to achieve the above object, one aspect of the present invention provides a modified zeolite membrane having a hydroxyl group to which a hydrophobic organic substance is adsorbed, wherein the adsorption rate of the hydroxyl group is 40% to 60%.
In a second aspect, the present invention provides a method for preparing a modified zeolite membrane, comprising: and (3) reacting the zeolite membrane with hydrophobic organic steam at the temperature of 300-400 ℃ for 20-120min to obtain the modified zeolite membrane.
In a third aspect, the invention provides the use of a modified zeolite membrane for the separation of methanol from a crude alcohol.
The invention provides a system for separating methanol from crude alcohol, which comprises a raw material storage tank, a delivery pump and a zeolite membrane component which are sequentially connected in series, wherein the zeolite membrane component comprises a modified zeolite membrane.
Through the technical scheme, the zeolite membrane is treated by hydrophobic organic steam, so that hydrophobic organic matters cover the positions of hydroxyl groups in the zeolite membrane to obtain the zeolite membrane with high selectivity for methanol adsorption and desorption, thereby obtaining superior alcohol through zeolite membrane separation. Compared with the traditional rectification, the method can remove the first alcohol and the tail alcohol, has no raw material waste, does not need reflux refining, and has low equipment investment; compared with a zeolite adsorption method, high-temperature regeneration and intermittent operation are not needed, and the operation is simple; compared with a chemical method, no impurity is introduced. Therefore, the invention has the characteristics of low energy consumption, less pollution and convenient operation.
Drawings
FIG. 1 is a schematic diagram showing the structure of a system for separating methanol from crude alcohol according to the present invention.
Description of the reference numerals
1. Raw material storage tank 2 and delivery pump
3. Zeolite membrane module
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a modified zeolite membrane, wherein a hydrophobic organic substance is adsorbed on hydroxyl groups of the modified zeolite membrane, the adsorption rate of the hydroxyl groups is 40% to 60%, and molecules of the hydrophobic organic substance have a carbon number of 6 or less.
Further, the hydrophobic organic matter is selected from any one or more of methane, ethane, ethylene, benzene and methanol; the zeolite membrane is NaA (silicon-aluminum ratio is between 1 and 2) zeolite membrane, SSZ-13 (silicon-aluminum ratio is between 2 and 20) zeolite membrane, ZSM-5 (silicon-aluminum ratio is between 4 and 30) zeolite membrane or NaY (silicon-aluminum ratio is between 1 and 3) zeolite membrane, preferably ZSM-5 zeolite membrane and NaY zeolite membrane, wherein the names of the zeolite types are determined according to IUPAC naming rules, for example, ZSM-5 zeolite is zeolite with MFI structure, and NaY zeolite is zeolite with FAU structure. The hydrophobic organic matter species adsorbed by the zeolite modified hydroxyl comprises methanol, methane, benzene and ethylene steam, the methanol steam and the hydroxyl can generate chemical reaction on the surface of the zeolite membrane at the high temperature of more than 200 ℃ to generate alkyl substances or other complex hydrophobic substances to cover the pore canals of the zeolite, and other organic matters also have similar effects.
In a second aspect, the present invention provides a method for preparing the modified zeolite membrane, including: and (3) reacting the zeolite membrane with hydrophobic organic steam at the temperature of 300-400 ℃ for 20-120min to obtain the modified zeolite membrane.
In a third aspect, the present invention provides a use of the above modified zeolite membrane in the separation of methanol from crude alcohol, comprising the steps of: filtering and separating crude alcohol with the modified zeolite membrane with the pore diameter of 0.45-0.72 nm; or, filtering and separating the crude alcohol by using the modified zeolite membrane with the pore diameter of 0.6-0.72nm, and then filtering and separating the crude alcohol by using the modified zeolite membrane with the pore diameter of 0.45-0.6nm to obtain purified alcohol, wherein the content of methanol in the purified alcohol is lower than 60 mg/kg. Preferably, the crude alcohol is firstly filtered and separated by the modified zeolite membrane with the pore diameter of 0.6-0.72nm, and then the crude alcohol is filtered and separated by the modified zeolite membrane with the pore diameter of 0.45-0.6 nm.
In a fourth aspect, the present invention provides a system for separating methanol from crude alcohol, as shown in fig. 1, comprising a raw material storage tank 1, a delivery pump 2 and a zeolite membrane module 3, which are connected in series in sequence, wherein the zeolite membrane module comprises the modified zeolite membrane.
Further, the zeolite membrane module comprises two or more of the modified zeolite membranes in series. Preferably, the zeolite membrane component comprises two modified zeolite membranes connected in series, the modified zeolite membrane at the crude alcohol inflow end is a large-aperture membrane, and the modified zeolite membrane at the crude alcohol outflow end is a small-aperture membrane. The large-aperture membrane has the characteristics of high flux and poor selectivity, and the small-aperture membrane has the characteristics of good selectivity and poor flux; and the selectivity is good when the concentration is high and poor when the concentration is low. The combination of the two pore diameter membranes can simultaneously utilize the advantages of the two membranes, and the selectivity is ensured while the flux is ensured. For example, the methanol removal at the former stage (crude alcohol inflow end) is rapidly performed by using a large-pore NaY zeolite membrane, and the methanol concentration at the latter stage (crude alcohol outflow end) is reduced, and then the methanol removal at the latter stage is completed by using a ZSM-5 zeolite membrane with higher selectivity and smaller pores.
Compared with the traditional separation technology, the membrane separation technology has the advantages of low energy consumption, less pollution, convenient operation and the like, thereby being widely concerned by the academic and industrial fields. However, no case of separating methanol from alcohol by using zeolite membrane is available at present. The kinetic diameter of methanol molecules is 0.38nm, the kinetic diameter of ethanol molecules is about 0.44nm, the prepared zeolite membrane with the pore diameter of about 0.44nm can effectively separate methanol from alcohol, and in addition, the rapid separation of methanol can be realized by utilizing the difference of the diffusion speeds of the methanol molecules and the ethanol molecules in pore channels in a mode of increasing the pore diameter of the zeolite. As can be seen from the premium grade pure alcohol, the methanol content needs to be below 62ppm, which is in the deep methanol removal range, and presents a significant challenge to both flux and selectivity of the zeolite membrane. According to the pervaporation principle, the flux of methanol and the partial pressure of methanol are related to the adsorption, diffusion and desorption of methanol on the membrane surface, wherein the adsorption and desorption are a pair of mutually restricted conditions, the stronger the adsorbability of zeolite is, the weaker the desorption is, the stronger the desorption of zeolite is, the weaker the adsorbability is, and both the stronger the adsorbability of zeolite is, the flux of the zeolite membrane is reduced, and a balance needs to be achieved between the two to exert the performance of the zeolite membrane to the utmost.
In order to achieve the purpose, methanol in alcohol is selectively separated by utilizing a zeolite membrane to obtain the ultra-high-quality alcohol, and the invention is researched from two angles. One is zeolite membrane selection, in which the pore diameters of NaA, ZSM-5 and NaY zeolite are respectively 0.41nm, 0.55nm and 0.72nm, and are near the molecular diameter of alcohol, so that said invention utilizes NaA, ZSM-5 and NaY zeolite membrane to separate methanol from alcohol. The other is to improve the adsorption and desorption performance of the zeolite membrane, the methanol has hydrophilic hydroxyl and hydrophobic methyl, the zeolite membrane also has a hydrophobic silicon region and a hydrophilic hydroxyl region, and the adsorption and desorption properties of the zeolite membrane on the methanol are reasonably adjusted by processing the hydroxyl region, so that the methanol removal performance of the zeolite membrane is effectively improved.
According to a particularly preferred embodiment of the present invention, a modified zeolite membrane having a hydrophobic organic material adsorbed on hydroxyl groups, wherein the adsorption rate of the hydroxyl groups is 45% to 51%, is produced by a method comprising: reacting the zeolite membrane with hydrophobic organic steam at the temperature of 300-400 ℃ for 20-40min to obtain the modified zeolite membrane. The application of the modified zeolite membrane in separating methanol from crude alcohol is specifically as follows: the crude alcohol is filtered and separated by a modified NaY zeolite membrane with the aperture of 0.63-0.70nm, and then the crude alcohol is filtered and separated by a modified ZSM-5 zeolite membrane with the aperture of 0.48-0.55nm, and the content of the methanol in the obtained purified alcohol is lower than 60 mg/kg.
The present invention will be described in detail below by way of examples. In the following examples, the test conditions for ethanol-methanol separation were: the feed solution was a 99.5 wt%/0.5 wt% ethanol/methanol solution, the pervaporation test temperature was 100 ℃, and the ethanol and methanol content on the permeate side as well as on the feed side was measured with a chromatographic analyzer. The raw materials are all commercial products.
The adsorption rate of hydroxyl on the modified zeolite membrane is NH3TPD test, the procedure of which is as follows:
1. determination of hydroxyl amount of untreated zeolite membrane:
firstly, the zeolite membrane is treated for 1h at 400 ℃ under inert gas, the temperature is reduced to 150 ℃, and 5 percent NH is used3Adsorbing for 1h, purging with inert gas for 0.5h, programming to 500 deg.C at a temperature rise rate of 5 deg.C/min, recording data with TCD, and obtaining NH of untreated zeolite by data integration3Adsorption amount according to hydroxyl group and NH3And (4) obtaining hydroxyl data 1 by the adsorption relation.
2 determination of hydroxyl group of zeolite membrane after treatment:
treating zeolite membrane at 400 deg.C under inert gas for 1 hr, treating with corresponding organic vapor at specific temperature for certain time, and treating with N2Purging for 30min to remove weakly adsorbed organic substances, cooling to 150 deg.C, and adding 5% NH3Adsorbing for 1h, purging with inert gas for 0.5h, programming to 500 deg.C at a temperature rise rate of 5 deg.C/min, recording data with TCD, and obtaining NH of untreated zeolite by data integration3Adsorption amount according to hydroxyl group and NH3And (4) obtaining hydroxyl data 2 by the adsorption relation.
3 the coverage of the hydroxyl group, i.e. the hydroxyl group adsorption rate, is obtained by dividing the difference between the hydroxyl group data 1 and 2 by the hydroxyl group data 1.
Example 1
The synthesis and methanol separation effect test of the modified ZSM-5 zeolite membrane:
(1) ZSM-5 seed Synthesis
Preparing 1SiO mol ratio2:0.5NaOH:0.05Al2O3：50H2O: 0.4TPAOH sol, transferring the sol into a 100ml reaction kettle, placing the reaction kettle in a 170 ℃ oven, and after crystallizing for 4 days, taking out and centrifuging to obtain ZSM-5 seed crystals;
(2) seed tube preparation
Putting 1g of ZSM-5 seed crystal into 99g of water, performing ultrasonic treatment for 1 minute to obtain suspended liquid crystal, putting an alumina support body with the length of 20cm into the liquid crystal, standing for 30 seconds, pulling out at the speed of 0.5cm/s, airing, putting into a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, roasting for 2 hours, and naturally cooling to room temperature to obtain a seed crystal tube;
(3) synthesis of ZSM-5 zeolite membrane by secondary growth method
Preparing 1SiO mol ratio2:0.57NaOH:137.5H2O:0.0050(Al2(SO4)3·18H2O)), then transferring the sol to a 300ml reaction kettle, then placing a seed crystal tube in the reaction kettle, transferring the reaction kettle to an oven with the temperature of 170 ℃, and after 1 day of crystallization, taking out and washing with deionized water to obtain a ZSM-5 zeolite membrane;
(4) synthesis of modified ZSM-5 zeolite membrane
At normal temperature, 1% methane/nitrogen is heated to 400 ℃, and is introduced into the obtained ZSM-5 zeolite membrane, after about 20 minutes of treatment, the temperature is naturally reduced to room temperature, and the modified ZSM-5 zeolite membrane with the aperture of 0.5nm is obtained, and the hydroxyl adsorption rate is 45%.
A modified ZSM-5 zeolite membrane was mounted to zeolite membrane module 3. Heating ethanol methanol (99.5/0.5) solution to 100 ℃, introducing the ethanol into the zeolite membrane component 3 by a delivery pump 2 at a speed of 50kg/h, wherein the methanol concentration content in the ethanol at the outlet of the zeolite membrane component 3 is 60ppm, the ethanol reaches the standard of superior ethanol, 0.78kg/h of industrial alcohol with the methanol concentration of about 32% is obtained at the permeation side, and the loss rate of raw materials is 1.5%.
Example 2
The synthesis and methanol separation effect test of the modified NaY zeolite membrane:
(1) preparing a synthetic solution according to the following method;
preparation of solution A1: 30.22g NaOH is dissolved in 360g deionized water, then 3.6g sodium metaaluminate is added and dissolved to obtain solution A1；
Solution B1: 30.22g of NaOH were dissolved in 360g of deionized water, and 66.6g of silica sol (containing SiO) was added thereto240 percent by mass) of the solution B is obtained after dissolution1；
Mixing the solution A1And solution B1Fully mixing to obtain a uniform and clear synthetic fluid. In the obtained synthetic solution, the substances contained in the synthetic solution are 70Na in terms of molar ratio2O:Al2O3:20SiO2:2000H2O。
(2) Transferring the synthetic liquid into a synthetic kettle; a tubular porous alumina ceramic support having a length of 20cm and a diameter of 1.2cm was completely immersed in the synthesis solution. Before microwave synthesis, placing the synthesis kettle in a 60 ℃ oven, and aging the support body for 8 hours in the presence of synthesis liquid; after aging, all synthesis kettles are placed in a microwave oven, and the temperature is raised to 95 ℃ at a constant speed within 4 minutes; then maintaining the temperature of the system at 95 ℃, taking out the synthesis kettle after reacting for 30 minutes, and taking out the support body.
(3) Repeating the step (1) and the step (2) once to obtain a NaY zeolite membrane;
(4) at normal temperature, 3% ethylene/nitrogen is heated to 300 ℃, introduced into the obtained NaY zeolite membrane, and after being treated for 40 minutes, the temperature is naturally reduced to the room temperature, so that the modified NaY zeolite membrane with the aperture of 0.67nm is obtained, and the hydroxyl adsorption rate of the modified NaY zeolite membrane is 51%.
The modified NaY zeolite membrane was mounted to zeolite membrane module 3. Heating ethanol methanol (99.5/0.5) solution in a raw material storage tank 1 to 60 ℃, introducing the ethanol methanol solution into a zeolite membrane component 3 by a delivery pump 2 at a speed of 50kg/h, setting the temperature of the zeolite membrane component 3 at 100 ℃, wherein the methanol concentration in the ethanol at the outlet of the zeolite membrane component 3 is 50ppm, the ethanol reaches the standard of high-grade ethanol, industrial alcohol with the methanol concentration of about 40% is obtained at the permeation side at 0.625kg/h, and the raw material loss rate is 1.25%.
Example 3
The 300-branch modified ZSM-5 zeolite membrane and the 300-branch modified NaY zeolite membrane synthesized in example 1 and example 2, respectively, were installed in the zeolite membrane module 3, the former-stage membrane module was installed with the modified NaY zeolite membrane having a higher flux, and the latter-stage membrane module was installed with the modified ZSM-5 zeolite membrane having a better selectivity.
At normal temperature, heating methanol steam with the mass concentration of 5% to 350 ℃, introducing the methanol steam into the zeolite membrane component 3, treating for 60 minutes, then naturally cooling to room temperature, and then purging the methanol steam in the component by using nitrogen. Heating ethanol methanol (99.5/0.5) solution in a raw material storage tank 1 to 60 ℃, introducing the ethanol methanol solution into a zeolite membrane component 3 by a delivery pump 2 at a speed of 50kg/h, setting the temperature of the zeolite membrane component 3 at 100 ℃, wherein the concentration of methanol in ethanol at the outlet of the zeolite membrane component 3 is 20ppm, the ethanol reaches the standard of high-grade ethanol, industrial alcohol with the methanol concentration of 29% is obtained at the permeation side at 0.86kg/h, and the loss rate of the raw material is 1.7%.
Comparative example 1
600 pieces of 20cm long ZSM-5 zeolite membranes obtained in example 1 were loaded into a zeolite membrane module 3, ethanol methanol (99.5/0.5) solution was heated to 60 ℃ in a raw material tank 1, and introduced into the membrane module at a rate of 50kg/h by a transfer pump 2, the temperature of the zeolite membrane module 3 was set to 100 ℃, the methanol concentration at the outlet of the zeolite membrane module 3 was 0.01 wt% close to the standard of the premium grade ethanol, the industrial alcohol with a methanol concentration of 32% was 0.78kg/h on the permeate side, and the raw material loss rate was 1.5%.
Comparative example 2
600 pieces of NaY zeolite membranes with the length of 20cm obtained in example 2 are loaded into a zeolite membrane component 3, ethanol methanol (99.5/0.5) solution is heated to 60 ℃ in a raw material storage tank 1, the ethanol methanol (99.5/0.5) solution is introduced into the zeolite membrane component 3 at the speed of 50kg/h by a delivery pump 2, the temperature of the zeolite membrane component 3 is set to 100 ℃, the methanol concentration at the outlet of the zeolite membrane component 3 is 150ppm, which is close to the standard of high-grade ethanol, 2.08kg of industrial alcohol with the methanol concentration of 12% is obtained at the permeation side, and the raw material loss rate is 4.2%.
Comparative example 3
300 pieces of ZSM-5 zeolite membranes and 300 pieces of NaY zeolite membranes which are respectively synthesized in the example 1 and the example 2 are arranged in the zeolite membrane component 3, the front stage membrane component is provided with the NaY zeolite membrane with higher flux, and the rear stage membrane component is provided with the ZSM-5 zeolite membrane with better selectivity. Heating ethanol methanol (99.5/0.5) solution in a raw material storage tank 1 to 60 ℃, introducing the ethanol methanol solution into a zeolite membrane component 3 by a delivery pump 2 at the speed of 50kg/h, setting the temperature of the zeolite membrane component 3 at 100 ℃, ensuring that the methanol concentration at the outlet of the zeolite membrane component 3 is 90ppm and approaches the standard of high-grade ethanol, obtaining 0.78kg/h of industrial alcohol with the methanol concentration of about 32% at the permeation side, and ensuring that the raw material loss rate is 1.5%. In the case of a loss rate of only 1.5%, the zeolite membrane module 3 combination can obtain a high-grade alcohol with a lower methanol content.
According to the separation results of examples 1 to 3 and comparative examples 1 to 3, respectively, after the zeolite membrane is treated by the hydrophobic organic gas, the deep methanol removal performance of the zeolite membrane can be improved, and the crude alcohol can meet the requirement of high-grade alcohol after the zeolite membrane is treated. From the separation results of examples 1 to 3, it is understood that the separation effect (i.e., the methanol concentration at the outlet of the zeolite membrane module 3 in examples 1 to 3) obtained by using the large pore size modified zeolite membrane and then the small pore size modified zeolite membrane is superior to the separation effect obtained by using the single pore size modified zeolite membrane.
Comparative example 4
To 1kg of an alcohol solution having a methanol concentration of 5000mg/kg, 300g of 4 kinds of conventional zeolites were added: the results of the methanol concentration of the filtrate after stirring for 3 hours at 100 ℃ with SSZ-13 zeolite, NaA zeolite, ZSM-5 zeolite and NaY zeolite are shown in Table 1, and it can be seen from the results that the methanol content of the alcohol solution adsorbed by these 4 kinds of conventional zeolites is much higher than 60mg/kg (methanol concentration at the outlet of the zeolite membrane module 3 in examples 1-3), indicating that the superior alcohol cannot be obtained by simple adsorption of the conventional zeolites.
TABLE 1 methanol content in alcohol before and after adsorption
According to the separation results of examples 1 to 3 and comparative example 4, after the zeolite membrane of the present invention is treated with hydrophobic organic gas, the methanol removal effect of the technical scheme of the present invention is significantly better than that of the conventional adsorption method.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A modified zeolite membrane is characterized in that hydrophobic organic matters are adsorbed on hydroxyl groups of the modified zeolite membrane, and the adsorption rate of the hydroxyl groups is 40-60%.
2. The modified zeolite membrane of claim 1, wherein the molecule of the hydrophobic organic has a carbon number of less than or equal to 6.
3. The modified zeolite membrane of claim 2, wherein the hydrophobic organic material is selected from any one or more of methane, ethane, ethylene, benzene, and methanol.
4. The modified zeolite membrane of any of claims 1-3, wherein the zeolite membrane is a NaA zeolite membrane, a SSZ-13 zeolite membrane, a ZSM-5 zeolite membrane, or a NaY zeolite membrane.
5. A method of preparing a modified zeolite membrane according to any one of claims 1 to 4, comprising: and (3) reacting the zeolite membrane with hydrophobic organic steam at the temperature of 300-400 ℃ for 20-120min to obtain the modified zeolite membrane.
6. Use of a modified zeolite membrane according to any one of claims 1 to 4 in the separation of methanol from crude alcohol.
7. Use according to claim 6, characterized in that it comprises the following steps:
and filtering and separating the crude alcohol by using the modified zeolite membrane to obtain purified alcohol.
8. The use according to claim 7, wherein the filtration separation of the crude alcohol with the modified zeolite membrane is in particular:
filtering and separating crude alcohol by using the modified zeolite membrane with the pore diameter of 0.45-0.72 nm;
or, filtering and separating the crude alcohol by using the modified zeolite membrane with the pore diameter of 0.6-0.72nm, and then filtering and separating the crude alcohol by using the modified zeolite membrane with the pore diameter of 0.45-0.6 nm.
9. Use according to claim 7, characterized in that the content of methanol in the purified alcohol is lower than 60 mg/kg.
10. A system for separating methanol from crude alcohol, which comprises a raw material storage tank, a delivery pump and a zeolite membrane module which are connected in series in sequence, wherein the zeolite membrane module comprises the modified zeolite membrane as claimed in any one of claims 1 to 4.
11. The system of claim 9, wherein the zeolite membrane module comprises two or more of the modified zeolite membranes in series.
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| CN117776873A (en) * | 2024-02-23 | 2024-03-29 | 天津市康科德科技有限公司 | Preparation method of high-purity isopropanol for scientific research |
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