CN114685407A - Method for preparing 2, 5-furan dimethanol dialkyl ether by etherification of 2, 5-furan dimethanol - Google Patents

Method for preparing 2, 5-furan dimethanol dialkyl ether by etherification of 2, 5-furan dimethanol Download PDF

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CN114685407A
CN114685407A CN202011590288.4A CN202011590288A CN114685407A CN 114685407 A CN114685407 A CN 114685407A CN 202011590288 A CN202011590288 A CN 202011590288A CN 114685407 A CN114685407 A CN 114685407A
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molecular sieve
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张建
干江
胡华雷
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Zhejiang Tangneng Technology Co ltd
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The application discloses a method for preparing 2, 5-furan dimethanol dialkyl ether by etherifying 2, 5-furan dimethanol, which is characterized in that raw materials of the 2, 5-furan dimethanol and alkyl alcohol are contacted with a catalyst to react to obtain the 2, 5-furan dimethanol dialkyl ether; the alkyl alcohol has a structural formula of R-OH; wherein R is C1-C10 alkyl; the catalyst contains at least one of modified ZSM-5 molecular sieve catalysts; the modification includes at least one of alkali treatment and acid treatment. The catalyst has high BHMF conversion rate and high BAMF yield, has good stability, and can be used repeatedly.

Description

Method for preparing 2, 5-furan dimethanol dialkyl ether by etherification of 2, 5-furan dimethanol
Technical Field
The application relates to a preparation method of a ZSM-5 molecular sieve catalyst and application of the ZSM-5 molecular sieve catalyst in catalyzing 2, 5-furandimethanol to prepare 2, 5-furandimethanol dialkyl ether, belonging to the field of molecular sieves.
Background
The 2, 5-furan dimethanol dialkyl ether (BAMF) has high energy density, is used as fuel, has good oxidation stability, can reduce the emission of harmful gases such as nitrogen oxides, sulfur oxides and the like, and is considered as a potential green fuel and an oil additive. The 2, 5-furan dimethanol dialkyl ether (BAMF) is prepared by etherifying 2, 5-furan dimethanol (BHMF) with alkyl alcohol. At present, researches on the preparation of monoether furfural (AMF) by etherification of 5-Hydroxymethylfurfural (HMF) with a monohydric alkyl alcohol are widely reported. The aldehyde groups remaining in the AMF greatly reduce its stability. Compared with the BAMF, the BAMF not only has better stability, but also has higher heat value and wider application value. The document [ Applied Catalysis A, General 565(2018) 146-. However, the catalysts used in this document are modified after synthesis and are relatively expensive to prepare. Therefore, it is of great interest to develop a catalyst for preparing a BAMF by etherification of a BHMF, which is relatively inexpensive and has excellent properties, so as to achieve high yields of the BAMF and excellent catalyst stability.
Disclosure of Invention
According to one aspect of the application, a preparation method of a ZSM-5 molecular sieve catalyst (the ZSM-5 molecular sieve is subjected to aftertreatment) is provided, the ZSM-5 molecular sieve catalyst has high catalytic activity and good stability in a 2, 5-furandimethanol (BHMF) catalytic etherification 2, 5-furandimethanol dialkyl ether (BAMF) reaction, can be used repeatedly, and has high practicability and industrial prospect in the field of catalysts.
According to one aspect of the application, the method for preparing the 2, 5-furan dimethanol dialkyl ether (BAMF) by etherifying the 2, 5-furan dimethanol has the advantages of high conversion rate of the 2, 5-furan dimethanol (BHMF), high yield of the BAMF, good stability and capability of realizing repeated use of the catalyst.
According to one aspect of the application, a method for preparing 2, 5-furan dimethanol dialkyl ether by etherifying 2, 5-furan dimethanol is provided, which is characterized in that raw materials of the 2, 5-furan dimethanol and alkyl alcohol are contacted with a catalyst to react to obtain the 2, 5-furan dimethanol dialkyl ether;
the alkyl alcohol has a structural formula of R-OH; wherein R is C1-C10 alkyl;
the catalyst contains at least one of modified ZSM-5 molecular sieve catalysts;
the modification includes at least one of alkali treatment and acid treatment.
Alternatively, the modified ZSM-5 molecular sieve catalyst preparation method comprises the steps of:
(1) treating an untreated ZSM-5 molecular sieve with a solution containing alkali and a surfactant, then carrying out ammonium exchange on the molecular sieve subjected to alkali treatment, and roasting to obtain an acidic alkali-treated molecular sieve;
(2) and (3) treating the acidic alkali-treated molecular sieve with an acid solution, and roasting to obtain the modified ZSM-5 molecular sieve catalyst.
Optionally, the ZSM-5 molecular sieve catalyst contains micropores and mesopores, wherein the pore diameter of the mesopores is 2-50 nm, and the pore volume of the mesopores is 0.1-0.5 cm3/g。
Optionally, the particle size of the ZSM-5 molecular sieve catalyst is 400-600 nm; the specific surface area is 200-400 m2/g。
Alternatively, the SiO of the ZSM-5 molecular sieve catalyst2/Al2O3The molar ratio is 25 to 100.
Optionally, the ratio of the untreated molecular sieve to the solution containing alkali and surfactant in the step (1) is 0.05-0.1 g/mL;
the treatment conditions are as follows: treating for 6-24 h at 80-100 ℃;
the concentration of alkali in the solution is 0.1-1.0M;
the concentration of the surfactant in the solution is 0.01-0.1M.
Optionally, the reaction is carried out in a tank reactor.
Optionally, the alkali used is at least one selected from sodium hydroxide, potassium hydroxide and ammonia water;
the surfactant is at least one selected from sodium stearate, sodium dodecyl benzene sulfonate and hexadecyl trimethyl ammonium bromide.
Alternatively, the molecular sieve to be treated in step (1) is a commercial microporous ZSM-5 molecular sieve, either purchased directly or prepared directly according to the prior art.
Optionally, the alkali treatment in step (1) at least comprises: adding a certain amount of alkali and a surfactant into deionized water, and heating to 80-100 ℃ under stirring and refluxing; adding the molecular sieve to be treated into the solution, continuously stirring for 6-24 h, and then carrying out ammonium exchange after washing, filtering and drying.
Optionally, the untreated molecular sieve in the step (1) is a microporous ZSM-5 molecular sieve, and the ratio of the untreated molecular sieve to the ammonium exchange solution is 0.1-0.2 g/mL;
the treatment conditions are as follows: treating for 0.5-2 h at 80-100 ℃;
the concentration of ammonium salt in the ammonium exchange solution is 0.05-0.1M;
the roasting condition is roasting for 6-8 hours at 500-600 ℃.
Optionally, the ammonium salt is selected from at least one of ammonium chloride and ammonium nitrate.
Optionally, the ammonium exchange in step (1) comprises at least: adding a certain amount of ammonia into deionized water, and heating to 80-100 ℃ under stirring and refluxing; and adding the alkali-treated molecular sieve into the solution, continuously stirring for 0.5-2 h, and then washing, filtering, drying and roasting to obtain the acidic alkali-treated molecular sieve.
Optionally, in the step (2), the ratio of the acidic alkali-treated molecular sieve to the acid solution is 0.1-0.2 g/mL.
Optionally, the acid in the acid solution is selected from at least one of oxalic acid, citric acid and glacial acetic acid.
Optionally, the treatment condition is that the treatment is carried out for 10-60 min at 80-100 ℃.
Optionally, the roasting condition is 500-600 ℃ for 6-8 h.
Optionally, the reaction is carried out in a tank reactor.
Optionally, the acid treatment in step (2) comprises at least: adding a certain amount of acid into deionized water, and heating to 80-100 ℃ under stirring and refluxing; and (2) adding the acidic alkali-treated molecular sieve obtained in the step (1) into the solution, continuously stirring for 10-60 min, and then washing, filtering, drying and roasting to obtain the post-treated ZSM-5 molecular sieve catalyst.
Alternatively, the post-treated ZSM-5 molecular sieve described above may be calcined for regeneration.
The post-treatment ZSM-5 molecular sieve prepared by the method is simple to operate, easily available in raw materials and low in cost, and is suitable for large-scale production and use.
Optionally, the alkyl alcohol is selected from at least one of methanol, ethanol, isopropanol and tert-butanol.
Optionally, the mass ratio of the modified ZSM-5 molecular sieve catalyst to the 2, 5-furandimethanol is 0.5-2.
Optionally, the reaction temperature is 60-80 ℃.
Optionally, the concentration of 2, 5-furandimethanol in the raw material is 10-20 g/L.
Optionally, the reaction is carried out in a tank reactor.
Optionally, the method comprises at least: adding BHMF into a reactor containing alkyl alcohol, heating and refluxing under mechanical stirring, adding a molecular sieve catalyst for reaction after the temperature is raised to a target temperature, and stopping stirring and heating after the reaction is carried out for a period of time to obtain the BAMF. The reaction formula is as follows:
Figure BDA0002868774440000041
preferably, the concentration of the 2, 5-furandimethanol is 10-20 g/L.
Preferably, the mass ratio of the molecular sieve to the 2, 5-furandimethanol is 0.5-2;
preferably, the reaction temperature is 60-80 ℃;
preferably, the reaction is carried out in a tank reactor.
Alternatively, the alkyl alcohol has the formula R-OH; wherein R is C1-C10 alkyl; the alkyl alcohol is at least one selected from methanol, ethanol, isopropanol and tert-butyl alcohol.
According to the synthesis method of the 2, 5-furan dimethanol dialkyl ether, the catalyst of the synthesis method is high in conversion rate, and the selectivity of the target product is high. Good stability.
In the present application, "C1～C10"means that the number of carbon atoms is 1 to 10.
In this application, "alkyl" refers to a group formed by an alkane losing at least one hydrogen atom.
The beneficial effects that this application can produce include:
1) the post-treated ZSM-5 molecular sieve provided by the application has both mesopores and micropores, can promote the diffusion of macromolecular substances in the pore channels, and has a good application prospect in the field of catalysts; the catalyst shows excellent performance in the reaction of preparing 2, 5-furan dimethanol dialkyl ether by catalyzing and etherifying 2, 5-furan dimethanol, and the catalyst has stable performance and can be roasted and regenerated.
2) The post-treatment ZSM-5 molecular sieve catalyst provided by the application is prepared by taking a commercial catalyst as a precursor through a relatively low-cost post-treatment method. The catalyst has low cost, simple and convenient preparation method and can be produced in large scale.
3) The method for preparing the 2, 5-furan dimethanol dialkyl ether by using the 2, 5-furan dimethanol provided by the application is simple to operate and low in production cost; meanwhile, the method has the advantages of high conversion rate of the 2, 5-furan dimethanol, excellent yield of the 2, 5-furan dimethanol dialkyl ether, high reaction selectivity and few byproducts. After the reaction is finished, the target product, the catalyst and the solvent are easy to separate and can be regenerated and reused, so that the production cost and the energy consumption are effectively reduced.
Drawings
FIG. 1 shows sample 4 of example 1 of the present application#XRD pattern of (a).
FIG. 2 shows sample 4#N of (A)2Adsorption and desorption curves.
FIG. 3 shows sample 4#The aperture profile of (a).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
The analysis method in the examples of the present application is as follows:
in the examples, the structure of the photocatalyst sample was characterized by X-ray powder diffraction using a brooker D8 advanced Davinci model X-ray diffractometer imported from germany, using a Cu ka radiation source, scan range: 2 θ from 5 ° to 90 °, scan time: and 7 min.
In the examples, the concentrations of the reactants and products were analyzed by high performance liquid chromatography, model 1260, from Agilent.
The conversion and yield in the synthesis reaction of 2, 5-furandimethanol dialkyl ether were calculated as follows:
the purity of the 2, 5-furan dimethanol dialkyl ether product is the weight percentage of the target product 2, 5-furan dimethanol dialkyl ether in the reaction product. BHMF conversion and BAMF yield were calculated based on carbon moles:
Figure BDA0002868774440000051
Figure BDA0002868774440000052
EXAMPLE 1 preparation of the catalyst
# Sample 1 preparation
1.6g of sodium hydroxide, 2.92g of cetyltrimethylammonium bromide and 160ml of deionized water were charged into a 250ml three-necked flask, heated to reflux to 90 ℃ under mechanical stirring (350rpm), followed by addition of 8g of microporous ZSM-5 molecular sieve (silica to alumina atomic ratio of 50). Stirring for 24h, filtering, washing with deionized water, drying at 100 deg.C for 12h to obtain alkali-treated ZSM-5 molecular sieve, and marking as sample 1#。
#Sample 2 preparation
0.321g of ammonium chloride and 60ml of deionized water were charged into a 100ml three-necked flask, heated to reflux with mechanical stirring (350rpm) to 80 ℃ and then 6g of microporous ZSM-5 molecular sieve was added. Stirring for 1h, filtering, washing with deionized water, and drying at 100 deg.C for 12 h; repeating the operation for 3 times, roasting the obtained sample at 550 ℃ for 7 hours to obtain the acidic microporous ZSM-5 molecular sieve which is marked as sample 2#。
#Sample 3 preparation
12.50g of sodium hydroxide, 7.29g of cetyltrimethylammonium bromide and 400ml of deionized water were charged into a 1000ml three-necked flask, heated to reflux to 90 ℃ with mechanical stirring (350rpm), and then 20g of microporous ZSM-5 molecular sieve was added. And stirring for 12h, filtering, washing with deionized water, and drying at 100 ℃ for 12h to obtain the alkali-treated ZSM-5 molecular sieve.
0.48g of ammonium nitrate and 60ml of deionized water were charged into a 100ml three-necked flask, heated to reflux with mechanical stirring (350rpm) to 80 ℃ and then 6g of an alkali-treated ZSM-5 molecular sieve was added. Stirring for 1h, filtering, washing with deionized water, and drying at 100 deg.C for 12 h; repeating the operation for 3 times, and roasting the obtained sample at 550 ℃ for 7h to obtain the acidic alkali-treated ZSM-5 molecular sieve which is marked as sample 3#。
#Sample 4 preparation
8.33g of sodium hydroxide, 7.29g of cetyltrimethylammonium bromide and 400ml of deionized water were charged into a 1000ml three-necked flask, heated to reflux to 80 ℃ with mechanical stirring (350rpm), and then 20g of microporous ZSM-5 molecular sieve was added. And stirring for 12h, filtering, washing with deionized water, and drying at 100 ℃ for 12h to obtain the alkali-treated ZSM-5 molecular sieve.
0.321g of ammonium chloride and 60ml of deionized water were charged into a 100ml three-necked flask, heated to reflux to 80 ℃ under mechanical stirring (350rpm), and then 6g of an alkali-treated ZSM-5 molecular sieve was added. Stirring for 1h, filtering, washing with deionized water, and drying at 100 deg.C for 12 h; and repeating the operation for 3 times, and roasting the obtained sample at 550 ℃ for 7 hours to obtain the acidic alkali-treated ZSM-5 molecular sieve.
0.58g of citric acid and 30ml of deionized water were charged into a 100ml three-necked flask, heated to reflux with mechanical stirring (350rpm) to 80 ℃ and then 3g of an acidic, alkali-treated ZSM-5 molecular sieve was added. After stirring for 30min, filtration, washing with deionized water and drying at 100 ℃ for 12 h. And roasting the obtained sample at 550 ℃ for 7h to obtain the post-treated ZSM-5 molecular sieve.
#Sample 5 preparation
8.33g of sodium hydroxide, 6.97g of sodium dodecylbenzenesulfonate and 400ml of deionized water were charged into a 1000ml three-necked flask, heated to reflux to 80 ℃ with mechanical stirring (350rpm), followed by addition of 10g of microporous ZSM-5 molecular sieve. And stirring for 12h, filtering, washing with deionized water, and drying at 100 ℃ for 12h to obtain the alkali-treated ZSM-5 molecular sieve.
0.321g of ammonium chloride and 60ml of deionized water were charged into a 100ml three-necked flask, heated to reflux to 80 ℃ under mechanical stirring (350rpm), and then 6g of an alkali-treated ZSM-5 molecular sieve was added. Stirring for 1h, filtering, washing with deionized water, and drying at 100 deg.C for 12 h; and repeating the operation for 3 times, and roasting the obtained sample at 550 ℃ for 7 hours to obtain the acidic alkali-treated ZSM-5 molecular sieve.
0.27g of oxalic acid and 30ml of deionized water were charged into a 100ml three-necked flask, heated to reflux to 80 ℃ with mechanical stirring (350rpm), followed by addition of 3g of an acidic, alkali-treated ZSM-5 molecular sieve. After stirring for 30min, filtration, washing with deionized water and drying at 100 ℃ for 12 h. And roasting the obtained sample at 550 ℃ for 7h to obtain the post-treated ZSM-5 molecular sieve.
#～ #Sample 610 preparation
Sample No. 6#Was prepared in the same manner as in sample 3#Except that the amount of sodium hydroxide added was 8.33 g.
Sample 7#The preparation method of (1) is the same as that of sample 4#Except that citric acid was changed to 0.27g oxalic acid.
Sample 8#The preparation method of (1) is the same as that of sample 4#Except that the temperature of the alkali treatment was 90 ℃.
Sample 9#The preparation method of (1) is the same as that of sample 5#Except that the time for the alkali treatment was 24 hours.
Sample 10#The preparation method of (1) is the same as that of sample 5#Except that the oxalic acid treatment time was 60 min.
EXAMPLE 2 characterization of the catalyst
Sample 1#-10#And (5) carrying out structural characterization on the catalyst. Sample No. 4#The XRD of the other samples is shown in figure 1, and the XRD spectrums of the other samples are similar to that of figure 1.
Sample 1#-10#The pore structure characterization is carried out by adopting a full-automatic specific surface adsorption instrument, and the specific surface area of the sample is 200-400 m2The mesoporous aperture is 2-10 nm, and the mesoporous volume is 0.1-0.5 cm3(iv) g. Sample No. 4#Is a typical sample, N thereof2The absorption and desorption curves and the pore size distribution diagrams are shown in fig. 2 and 3, clear hysteresis loops and pore size distribution conditions can be observed, and the mesoporous structure of the mesoporous silica gel is confirmed. .
Sample 1#-10#Characterization of catalyst composition by x-ray fluorescence Spectroscopy (XRF), sample 4#SiO of (2)2/Al2O3The molar ratio was 53. SiO of other samples2/Al2O3The molar ratio is in the range of 25-100.
Example 3 catalytic performance of post-treatment catalyst
1. Performance evaluation of post-treatment catalyst in preparation of 2, 5-furandimethanol dimethyl ether
With sample 1#～10#The specific steps of the catalyst for preparing the 2, 5-furan dimethanol dimethyl ether are as follows: 0.64g of 2, 5-furandimethanol (99.5%), 60ml of methanol were charged into a 100ml three-necked flask, heated to reflux to 80 ℃ with mechanical stirring (350rpm), and then 0.64g of catalyst was added to react for a while. The concentration of the reactant and the product was analyzed by high performance liquid chromatography after the reaction sample was diluted with methanol, and the conversion of 2, 5-furandimethanol and the yield of 2, 5-furandimethanol dimethyl ether were calculated as shown in table 1. In the present application, the post-treatment ZSM-5 molecular sieve is adopted as 25-furan dimethanol and methanol are used as raw materials to synthesize 2, 5-furan dimethanol dimethyl ether, the conversion rate of the 2, 5-furan dimethanol reaches 99.5 percent, and the yield of the 2, 5-furan dimethanol dimethyl ether reaches 94 percent.
TABLE 1 Performance results of the catalytic etherification of BMMF with the catalysts
Figure BDA0002868774440000081
2. Performance evaluation of post-treated catalyst in preparation of 2, 5-furandimethanol diethyl ether
With sample 1#～10#The specific steps of the catalyst for preparing 2, 5-furan dimethanol diethyl ether are as follows: 0.64g of 2, 5-furandimethanol (99.5%), 60ml of ethanol were charged into a 100ml three-necked flask, heated to reflux to 80 ℃ with mechanical stirring (350rpm), and then 0.64g of catalyst was added for a reaction time. The concentration of the reactant and the product was analyzed by high performance liquid chromatography after the reaction sample was diluted with methanol, and the conversion of 2, 5-furandimethanol and the yield of 2, 5-furandimethanol diethyl ether were calculated as shown in table 2. In the application, the post-treatment ZSM-5 molecular sieve is adopted, 2, 5-furan dimethanol and methanol are used as raw materials to synthesize the 2, 5-furan dimethanol dimethyl ether, the conversion rate of the 2, 5-furan dimethanol reaches 99%, and the yield of the 2, 5-furan dimethanol dimethyl ether reaches 92%.
TABLE 2 Performance results of the catalyst catalyzed etherification of BEMF
Figure BDA0002868774440000091
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A method for preparing 2, 5-furan dimethanol dialkyl ether by etherification of 2, 5-furan dimethanol is characterized in that raw materials of the 2, 5-furan dimethanol and alkyl alcohol are contacted with a catalyst to react to obtain the 2, 5-furan dimethanol dialkyl ether;
the alkyl alcohol has a structural formula of R-OH; wherein R is C1-C10 alkyl;
the catalyst contains at least one of modified ZSM-5 molecular sieve catalysts;
the modification includes at least one of alkali treatment and acid treatment.
2. The process of claim 1, wherein the modified ZSM-5 molecular sieve catalyst is prepared by a process comprising the steps of:
(1) treating an untreated ZSM-5 molecular sieve with a solution containing alkali and a surfactant, then carrying out ammonium exchange on the molecular sieve subjected to alkali treatment, and roasting to obtain an acidic alkali-treated molecular sieve;
(2) and (3) treating the acidic alkali-treated molecular sieve with an acid solution, and roasting to obtain the modified ZSM-5 molecular sieve catalyst.
3. The method of claim 2, wherein the ZSM-5 molecular sieve catalyst comprises micropores and mesopores, wherein the pore diameter of the mesopores is 2-50 nm, and the pore volume of the mesopores is 0.1-0.5 cm3/g；
Preferably, the particle size of the ZSM-5 molecular sieve catalyst is 400-600 nm; the specific surface area is 200-400 m2/g；
Preferably, the ZSM-5 molecular sieve catalyst is SiO2/Al2O3The molar ratio is 25 to 100.
4. The method according to claim 2, wherein the ratio of the untreated molecular sieve to the solution containing the alkali and the surfactant in the step (1) is 0.05 to 0.1 g/mL;
the treatment conditions are as follows: treating for 6-24 h at 80-100 ℃;
the concentration of alkali in the solution is 0.1-1.0M;
the concentration of the surfactant in the solution is 0.01-0.1M;
preferably, the reaction is carried out in a tank reactor.
5. The method of claim 4, wherein the base used is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and aqueous ammonia;
the surfactant is at least one selected from sodium stearate, sodium dodecyl benzene sulfonate and hexadecyl trimethyl ammonium bromide.
6. The method according to claim 2, wherein the untreated molecular sieve in step (1) is a microporous ZSM-5 molecular sieve, and the ratio of the untreated molecular sieve to the ammonium exchange solution is 0.1-0.2 g/mL;
the treatment conditions are as follows: treating for 0.5-2 h at 80-100 ℃;
the concentration of ammonium salt in the ammonium exchange solution is 0.05-0.1M;
the roasting condition is roasting for 6-8 hours at 500-600 ℃.
7. The method of claim 6, wherein the ammonium salt is selected from at least one of ammonium chloride and ammonium nitrate.
8. The method according to claim 2, wherein in the step (2), the ratio of the acidic alkali-treated molecular sieve to the acid solution is 0.1-0.2 g/mL;
preferably, the acid in the acid solution is selected from at least one of oxalic acid, citric acid and glacial acetic acid;
preferably, the treatment condition is that the treatment is carried out for 10-60 min at 80-100 ℃;
preferably, the concentration of the acid in the solution is 0.05-0.1M;
preferably, the roasting condition is roasting for 6-8 hours at 500-600 ℃;
preferably, the reaction is carried out in a tank reactor.
9. The method according to claim 1, wherein the alkyl alcohol is at least one selected from the group consisting of methanol, ethanol, isopropanol, and tert-butanol.
10. The method according to claim 1, wherein the mass ratio of the modified ZSM-5 molecular sieve catalyst to the 2, 5-furandimethanol is 0.5-2;
preferably, the reaction temperature is 60-80 ℃;
preferably, the concentration of the 2, 5-furandimethanol in the raw materials is 10-20 g/L;
preferably, the reaction is carried out in a tank reactor.
CN202011590288.4A 2020-12-29 2020-12-29 Method for preparing 2, 5-furan dimethanol dialkyl ether by etherification of 2, 5-furan dimethanol Pending CN114685407A (en)

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