CN112979428B - Method for preparing glycol dimethyl ether by series connection method - Google Patents
Method for preparing glycol dimethyl ether by series connection method Download PDFInfo
- Publication number
- CN112979428B CN112979428B CN201911286261.3A CN201911286261A CN112979428B CN 112979428 B CN112979428 B CN 112979428B CN 201911286261 A CN201911286261 A CN 201911286261A CN 112979428 B CN112979428 B CN 112979428B
- Authority
- CN
- China
- Prior art keywords
- reaction
- dimethyl ether
- catalyst
- glycol dimethyl
- ethylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a method for preparing glycol dimethyl ether by a series connection method. Under the action of carrier gas, materials containing glycol and methanol sequentially contact with a catalyst I and a catalyst II to react to obtain glycol dimethyl ether; wherein the catalyst I comprises at least one of a molecular sieve I and a super acid catalyst; the catalyst II comprises at least one of a molecular sieve II and an ion exchange resin. The method adopts a series reaction technology to prepare the end-capped glycol dimethyl ether by catalyzing and etherifying the glycol, and has important significance and application prospect for developing a new technical reaction route.
Description
Technical Field
The application relates to a method for preparing ethylene glycol dimethyl ether by a series connection method, belonging to the technical field of chemical synthesis.
Background
The end-capped glycol ether is an excellent solvent and a potential alcohol ether liquid fuel additive with wide application. Ethylene glycol dimethyl Ether (EDM) has stable property and is not easy to react; can dissolve various resins and celluloses and is miscible with water and many organic solvents such as alcohols, ethers, ketones, esters, hydrocarbons and chlorinated hydrocarbons in any proportion. The glycol dimethyl ether is mainly used in the technical fields of polymer chemistry, electrochemistry and boron chemistry, and also used as a solvent of resin, nitrocellulose and the like. With the development of new technologies, the application field is also continuously expanded: can be used as an air and military jet aircraft fuel antifreeze additive; the material is used for new energy battery materials; an excellent solvent for synthesizing an organic (rare earth) metal element compound; is used for the synthesis of pharmaceutical intermediates for resisting tumors, hypertension and the like and fluorine-containing weeding and pesticide crude drug intermediates.
The Williamson organic synthesis method is mainly adopted in industry, and ethylene glycol monoether is used as a raw material (mainly from an ethylene oxide reaction product), but the method has certain limitation, consumes chlorine and strong alkali, has serious pollution, harsh reaction conditions, is difficult to control and has high industrial production cost.
Disclosure of Invention
According to one aspect of the application, a method for preparing glycol dimethyl ether by a series method is provided, the method adopts a series reaction technology, and prepares the end-capped glycol dimethyl ether by catalyzing and etherifying glycol, so that the method has important significance and application prospect for developing a new technical reaction route.
A method for preparing glycol dimethyl ether by a series connection method comprises the steps of sequentially contacting a material containing glycol and methanol with a catalyst I and a catalyst II under the action of a carrier gas, and reacting to obtain the glycol dimethyl ether; wherein the catalyst I comprises at least one of a molecular sieve I and a super acid catalyst; the catalyst II comprises at least one of a molecular sieve II and an ion exchange resin.
Optionally, the carrier gas comprises nitrogen, an inert gas.
Optionally, the preparation method comprises:
a) under the action of carrier gas, a methanol solution containing glycol is contacted with the catalyst I to react I, so as to obtain an intermediate product;
b) and (3) contacting the intermediate product with the catalyst II under the action of a carrier gas to react II to obtain ethylene glycol dimethyl ether.
Optionally, in step a), the molecular sieve I comprises at least one of HZSM-5, H-beta, HY, SAPO34 and mordenite;
the super acid catalyst comprises at least one of zirconium sulfate and zirconium phosphate.
Optionally, the concentration of the ethylene glycol in the methanol solution containing ethylene glycol is 20-60 wt%.
Specifically, the upper limit of the concentration of ethylene glycol in the ethylene glycol-containing methanol solution is independently selected from 30 wt%, 40 wt%, 60 wt%; the lower and upper limits of the concentration of ethylene glycol in said ethylene glycol containing methanol solution are independently selected from the group consisting of 20 wt%, 30 wt%, 40 wt%.
Preferably, the concentration of the ethylene glycol in the methanol solution containing ethylene glycol is 30 to 60 wt%.
Alternatively, the conditions of the reaction I are as follows:
the reaction temperature is 100-300 ℃;
the reaction pressure is 0.1-0.5 MPa;
the space velocity of the methanol solution containing the ethylene glycol is 0.1-5h-1。
Specifically, in the reaction I, the upper limit of the reaction temperature is independently selected from 180 ℃, 220 ℃ and 300 ℃; the lower limit of the reaction temperature is independently selected from 100 ℃, 180 ℃, 220 ℃.
In the reaction I, the upper limit of the reaction pressure is selected from 0.2MPa, 0.3MPa and 0.5 MPa; the lower limit of the reaction pressure is selected from 0.1MPa, 0.2MPa and 0.3 MPa.
In the reaction I, the upper limit of the space velocity of the methanol solution containing ethylene glycol is independently selected from 0.18h-1、0.36h-1、1h-1、5h-1(ii) a The lower limit of the space velocity of the methanol solution containing ethylene glycol is independently selected from 0.1h-1、0.18h-1、0.36h-1、1h-1。
Preferably, the conditions of the reaction I are as follows: the reaction temperature is 100-250 ℃; the reaction pressure is 0.2-0.4 MPa; the space velocity of the methanol solution containing the ethylene glycol is 0.2-2h-1。
Further preferably, the conditions of the reaction I are as follows: the reaction temperature is 180-220 ℃; the reaction pressure is 0.2-0.3 MPa; the space velocity of the methanol solution containing the ethylene glycol is 0.2-1 h-1。
Optionally, the reaction time of the reaction I is 1-3 h;
preferably, the reaction time is 2 h.
Optionally, in step b), the molecular sieve II comprises at least one of HZSM-5, H-beta, HY, SAPO34 and mordenite;
the ion exchange resin comprises at least one of Amberlyst-15 and Nafion.
Alternatively, the conditions of the reaction II are as follows: the reaction temperature is 50-200 ℃; the reaction pressure is 0.1-0.5 MPa.
Specifically, in the reaction II, the upper limit of the reaction temperature is independently selected from 120 ℃ and 200 ℃; the lower limit of the reaction temperature is independently selected from 50 ℃ and 120 ℃.
In the reaction II, the upper limit of the reaction pressure is selected from 0.2MPa, 0.3MPa and 0.5 MPa; the lower limit of the reaction pressure is selected from 0.1MPa, 0.2MPa and 0.3 MPa.
Preferably, the conditions of the reaction II are as follows: the reaction temperature is 60-200 ℃; the reaction pressure is 0.2-0.4 MPa.
Further preferably, the conditions of the reaction II are as follows: the reaction temperature is 120-130 ℃; the reaction pressure is 0.2-0.3 MPa.
Optionally, the reaction temperature of reaction I is greater than the reaction temperature of reaction II.
In this application, tubular reactors in series are used, catalyst I being charged in the first reactor and catalyst II being charged in the second reactor.
The patent uses a series catalytic reaction technology to prepare glycol dimethyl ether by catalytic conversion of glycol. The glycol methanol solution passes through a first reactor (100-300 ℃) and a second reactor (50-200 ℃) in sequence under the nitrogen carrier gas, and is converted into a glycol dimethyl ether product under the action of the two reactors filled with different catalysts. The patent provides a new route for preparing glycol dimethyl ether by using a series-connected catalytic reaction technology.
The beneficial effects that this application can produce include:
1) according to the method for preparing the ethylene glycol dimethyl ether by the series connection method, the end-capped diether compound is synthesized by adopting a biomass derived ethylene glycol raw material, and the method is a sustainable resource conversion route;
2) according to the method for preparing the glycol dimethyl ether by the series connection method, the end-capped diether compound synthesized by the technology is an important ether compound and has important potential application in emerging industries;
3) according to the method for preparing the ethylene glycol dimethyl ether by the series connection method, the ethylene glycol is directly converted into the end-capped diether by adopting the series connection catalytic reaction technology, and an innovative reaction route is provided.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The invention aims to provide a method for preparing glycol dimethyl ether by a tandem technology. The ethylene glycol is catalytically converted to the ethylene glycol dimethyl ether product by using reactors in series.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the glycol methanol solution is converted into glycol dimethyl ether products in a serial tubular reactor in nitrogen carrier gas, specifically:
(1) the first reactor is filled with catalysts such as molecular sieve, super acid and the like, and the reaction temperature is 100-300 ℃;
(2) on the second reactor: the catalyst such as molecular sieve and ion exchange resin is filled in the reactor, and the reaction temperature is 50-200 ℃.
The specific process method comprises the following steps:
in the series reactor, the catalyst used in the first reactor is molecular sieve such as HZSM-5, H-beta, HY and the like, or superacid catalyst such as zirconium sulfate and the like, and the reaction temperature is 100-250 ℃.
The catalyst used in the second reactor is molecular sieve such as HZSM-5, H-beta, HY and the like, or ion exchange resin catalyst such as Amberlyst-15 and the like, and the reaction temperature is 60-200 ℃.
The concentration of the ethylene glycol methanol solution is between 20 and 60 weight percent, and the space velocity is about 0.1 to 5h-1。
The concentration of the ethylene glycol methanol solution is between 30 and 60 weight percent, and the space velocity is about 0.2 to 2h-1。
The glycol methanol solution is efficiently converted into glycol dimethyl ether products under the action of the reactors connected in series.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
HZSM-5 was purchased from catalyst works of southern Kai university with a silicon to aluminum atomic ratio of 50;
hbeta was purchased from southern kayak university catalyst works with a silicon to aluminum atomic ratio of 40;
HY purchased from catalyst works of southern Kai university with a silicon-aluminum atomic ratio of 7;
ion exchange resins were purchased from south large synthetic chemistry, ltd, and are available under the model amberlyst 15;
the gas chromatograph is model 7890 from Agilent.
The conversion, selectivity, in the examples of the present application were calculated as follows:
example 1
10ml of HZSM-5 was weighed and placed in the first stage and second stage reactors, respectively. The nitrogen gas of 20ml/min is introduced into the whole reaction system as carrier gas, and the pressure is about 0.3 MPa. The two reactors are heated up separately, the first reactor is heated to 180 deg.C and the second reactor is heated to 120 deg.C. After the two reactors are heated to the specified temperature, 30 wt% glycol methanol solution is pumped in at the pump speed of 0.17ml/min, and after the first reactor reacts for 2 hours for balance, the valve is switched to enter the second reactor. Samples were taken every two hours for analysis. The analysis adopts a gas chromatography analysis method.
TABLE 1
Example 2
10ml of Hbeta and 10ml of ion exchange resin were weighed and charged in the first stage reactor and the second stage reactor, respectively. The nitrogen gas of 20ml/min is introduced into the whole reaction system as carrier gas, and the pressure is about 0.3 MPa. The two reactors were heated up separately, the first reactor was heated to 220 ℃ and the second reactor to 120 ℃. After the two reactors are heated to the specified temperature, 40 wt% glycol methanol solution is pumped in at the pump speed of 0.06ml/min, and after the first reactor reacts for 2 hours for balance, the valve is switched to enter the second reactor. Samples were taken every two hours for analysis. The analysis adopts a gas chromatography analysis method.
TABLE 2
Example 3
20ml HY and 20ml HZSM-5 are respectively weighed and loaded into the first stage reactor and the second stage reactor. The nitrogen gas of 10ml/min is introduced into the whole reaction system as carrier gas, and the pressure is about 0.2 MPa. The two reactors were heated up separately, the first reactor was heated to 220 ℃ and the second reactor to 120 ℃. After the two reactors are heated to the specified temperature, 30 wt% glycol methanol solution is pumped in at the pump speed of 0.06ml/min, and after the first reactor reacts for 2 hours for balance, the valve is switched to enter the second reactor. Samples were taken every two hours for analysis. The analysis adopts a gas chromatography analysis method.
TABLE 3
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 (8)
1. A method for preparing glycol dimethyl ether by a series connection method is characterized in that,
the preparation method comprises the following steps: a) under the action of carrier gas, a methanol solution of ethylene glycol is contacted with a catalyst I to react with the catalyst I to obtain an intermediate product; b) under the action of carrier gas, the intermediate product is contacted with a catalyst II to react II to obtain ethylene glycol dimethyl ether;
wherein the catalyst I comprises at least one of a molecular sieve I and a super acid catalyst; the catalyst II comprises at least one of a molecular sieve II and ion exchange resin;
the reaction temperature of the reaction I is 100-300 ℃;
the reaction temperature of the reaction II is 50-200 ℃;
the reaction temperature of the reaction I is higher than that of the reaction II.
2. The method for preparing glycol dimethyl ether in series according to claim 1, wherein in step a), the molecular sieve I comprises at least one of HZSM-5, H-beta, HY, SAPO34 and mordenite; the super acidic catalyst comprises at least one of zirconium sulfate and zirconium phosphate.
3. The method for preparing glycol dimethyl ether in series according to claim 1, wherein the concentration of ethylene glycol in the methanol solution of ethylene glycol is 20-60 wt%.
4. The method for preparing glycol dimethyl ether in series according to claim 1, wherein the concentration of ethylene glycol in the methanol solution of ethylene glycol is 30-60 wt%.
5. The method for preparing glycol dimethyl ether by a series process according to claim 1, wherein the conditions of the reaction I are as follows: the reaction pressure is 0.1-0.5 MPa; the space velocity of the methanol solution of the ethylene glycol is 0.1-5h-1。
6. The method for preparing glycol dimethyl ether by a series process according to claim 1, wherein the conditions of the reaction I are as follows: the reaction temperature is 100-250 ℃; the reaction pressure is 0.2-0.4 MPa; the space velocity of the methanol solution of the ethylene glycol is 0.2-2h-1。
7. The method for preparing glycol dimethyl ether in series according to claim 1, wherein in step b), the molecular sieve II comprises at least one of HZSM-5, H-beta, HY, SAPO34 and mordenite; the ion exchange resin comprises at least one of Amberlyst-15 and Nafion.
8. The method for preparing glycol dimethyl ether by a series process according to claim 1, wherein the conditions of the reaction II are as follows: the reaction pressure is 0.1-0.5 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911286261.3A CN112979428B (en) | 2019-12-13 | 2019-12-13 | Method for preparing glycol dimethyl ether by series connection method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911286261.3A CN112979428B (en) | 2019-12-13 | 2019-12-13 | Method for preparing glycol dimethyl ether by series connection method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112979428A CN112979428A (en) | 2021-06-18 |
| CN112979428B true CN112979428B (en) | 2022-06-03 |
Family
ID=76342558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911286261.3A Active CN112979428B (en) | 2019-12-13 | 2019-12-13 | Method for preparing glycol dimethyl ether by series connection method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112979428B (en) |
-
2019
- 2019-12-13 CN CN201911286261.3A patent/CN112979428B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Selective synthesis of dimethoxyethane via directly catalytic etherification of crude ethylene glycol;Weiqiang Yu et al;《green chemistry》;20170601;第19卷;3327-3333 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112979428A (en) | 2021-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104250256B (en) | A kind of method preparing isosorbide ether | |
| CN104725224B (en) | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate | |
| CN108947776B (en) | Method for catalyzing oxidative cracking of lignin model aryl ether | |
| CN105713642B (en) | Method for synthesizing high density aviation fuel from lignocellulose | |
| CN106866331A (en) | A kind of method that cyclopentadiene or dicyclopentadiene are prepared by furfuryl alcohol | |
| CN112608289A (en) | Method for efficiently preparing 5-hydroxymethylfurfural by catalyzing bio-based fructose through organic solvent-ionic liquid composite system | |
| US9708240B2 (en) | Method for preparing polyoxymethylene dimethyl ether carbonyl compound and methyl methoxyacetate | |
| CN104262117A (en) | Method for preparing dihydric alcohol mono-t-butyl ether | |
| CN104725225B (en) | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate | |
| CN112979428B (en) | Method for preparing glycol dimethyl ether by series connection method | |
| CN104693016B (en) | Method for preparing 4-methylbenzaldehyde from isoprene and acrolein | |
| CN112679346A (en) | Method for catalytically synthesizing p-tert-butyl methyl benzoate based on eutectic solvent | |
| CN104829559A (en) | Method of preparing Nu-valerolactone from methyl levulinate | |
| CN103420817A (en) | Method for synthesizing polyformaldehyde dimethyl ether from methylal and paraformaldehyde | |
| CN108212207B (en) | Solid acid catalyst for preparing methyl lactate by catalytic conversion of glucose and preparation method thereof | |
| CN102701988A (en) | Synthesis method of compound 2,6 -di-tert-butyl-4-nitrosophenol | |
| CN111434657B (en) | Preparation method of gamma-valerolactone and levulinate ester compound | |
| CN112979430B (en) | Method for preparing propylene glycol ether compound from glycerol | |
| CN102643263B (en) | Method for preparing glycerol carbonate by liquid-phase oxidation and carbonylation of glycerol | |
| CN109651124B (en) | Method for synthesizing p-tolualdehyde | |
| CN102649693B (en) | Method for preparing ethylene glycol through catalytic hydrogenation by oxalic ester | |
| CN112961038B (en) | Method for preparing mixed ether compound | |
| CN113145172B (en) | High-performance catalyst for preparing glycol by hydration of alkylene oxide, preparation method and application | |
| CN102649703B (en) | Method adopting oxalate to produce ethylene glycol | |
| CN114230429B (en) | Method for synthesizing methyl cyclopentadiene from 3-hydroxymethyl cyclopentanone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |