CN1043225C - Process for synthesis of dimethyl ether by catalytic distillation - Google Patents
Process for synthesis of dimethyl ether by catalytic distillation Download PDFInfo
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- CN1043225C CN1043225C CN94112144A CN94112144A CN1043225C CN 1043225 C CN1043225 C CN 1043225C CN 94112144 A CN94112144 A CN 94112144A CN 94112144 A CN94112144 A CN 94112144A CN 1043225 C CN1043225 C CN 1043225C
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- methyl alcohol
- dme
- dimethyl ether
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- 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
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a process for synthesizing dimethyl ether by catalytic distillation, which is characterized in that a catalytic reaction and a rectification process are simultaneously carried out in a reactor, and outlet reaction products do not contain acidic material. After a methyl alcohol material enters the reactor and under the conditions that reaction temperature is from 60 to 180 DEG C, pressure is from 0 to 0.3MPa(absolute pressure) and sulfuric acid is used as a catalyst, dehydration is carried out to produce dimethyl ether. In the reaction process, the product dimethyl ether is continuously separated from methyl alcohol. The present invention has the advantages of simple manufacturing process, high product purity, low cost, no production of waste acid, waste slags and waste water containing acid in the process, etc.
Description
The present invention relates to the method that sulfuric acid process prepares dme, particularly about the catalytic distillation method of dme.
Dme is a kind of nontoxic, tasteless, has good aqueous solubility, oil-soluble lower boiling (24.8 ℃) aliphatics ethers.Be widely used in every field such as chemical industry, daily use chemicals, pharmacy, agricultural chemicals and refrigeration.The production method of dme mainly is to come synthetic with the solid acid as catalyst, and this method is partly cut catalyzed reaction and rectifying and left.Make catalyzer with sulfuric acid, methanol dehydration generates the method for dme, make dewatering agent owing to use sulfuric acid, the acid content that can make reactor outlet reaction lime set is up to 2～3% (weight), a large amount of acid-bearing wastewaters cause the environmental pollution this method except that meeting produces, bring serious corrosion also can for the recovery system of methyl alcohol, organic carbonization not only influences running period in the sulfuric acid liquid in addition, also produce a large amount of spent acid, waste residue, and in distillation system, need to consume lot of energy, so industrial never industrial application does not have bibliographical information yet.We have invented a kind ofly in the process of methanol dehydration dimethyl ether-preparing for the shortcoming that overcomes aforesaid method, and catalytic synthesis separates the novel process of carrying out simultaneously with the product dme.
The objective of the invention is to realize that by following technical scheme reactive distillation column is made up of reactor (1) and rectifying tower (4); It is characterized in that interior catalyzed reaction of reactor and rectifying carry out simultaneously, concentration is that the catalyst sulfuric acid (2) of 20～98% (weight) is closed in the reactor (1) of reaction zone, can supply life-time service.Material benzenemethanol is in position (5) charging of the 5th theoretical plate number at the most, 60～180 ℃ of temperature of reaction, be preferably 100～150 ℃, reaction pressure is 0～0.3MPa (absolute pressure), be preferably under 0.05～0.15MPa (absolute pressure) condition, reaction raw materials methyl alcohol is under the vitriolic katalysis, and dehydration generates dme, and produces methyl-hydrogen-sulfate monomethyl-sulfate and methyl-sulfate.Methyl-hydrogen-sulfate monomethyl-sulfate, methyl-sulfates etc. contain acid substance and are separated with dme in rectifying tower, the rectifying section theoretical plate number is 2～50, be preferably 5～30, heavy component methyl-hydrogen-sulfate monomethyl-sulfate in the rectifying, heavy components such as methyl-sulfate are toward the enrichment of tower bottom, and in the reactor (1) of reaction zone, continue to form chemical equilibrium with the methanol etherification reaction, light component dme, unreacted methanol and water are toward the enrichment of tower top, reaching raw material constantly separates with product, so just suppressed the generation of by product methyl-hydrogen-sulfate monomethyl-sulfate and methyl-sulfate, improved reaction preference, the cat head component is through condenser (7) condensation, again after vapour liquid separator (3) separates, the dme of gas phase is separated with the methyl alcohol of liquid phase and water, sour biomass have not wherein been contained in the dme product, acid content is less than 20ppm in the reaction lime set that unreacted methanol and water form, and the reaction lime set is entered distillation tower by partial reflux.
In the present invention, owing to adopt reactive distillation technology, make the reaction product dme not contain acidic substance.The reaction lime set methyl alcohol and the aqueous solution contain acidic substance hardly, it is simple that technical process also becomes, and exempted the particular requirement to equipment anticorrosion, eliminated acid-bearing wastewater, contains sour waste residue, spent acid three-waste pollution source, solve the shortcoming that exists in the conventional art, simplified the reaction process flow process.
Shown in Fig. 1 reactor (1), catalyst sulfuric acid (2), vapour liquid separator (3), rectifying tower (4), methanol feedstock feed entrance point (5), condenser (7), reaction lime set methyl alcohol and water (8), dme product (6).
Embodiment 1
In diameter was 40 millimeters catalytic distillation tower, reaction zone (1) was high 1500 millimeters, and the rectifying section theoretical plate number is 8, and the catalyzer in the reaction zone is the sulfuric acid (2) of 42% (weight) concentration; Add methyl alcohol in the 1st theoretical tray position (5), the methanol feeding amount is: 0.08mol/min, and 60 ℃ of temperature of reaction, under reaction pressure 0.005MPa (absolute pressure) condition, reaction generates dme, and the per pass conversion of its methyl alcohol is 68.7%; Dme product (6) selectivity is 99.9%, and acid content is zero in the product dme, and acid content is 20ppm in the outlet reaction lime set (8).
Embodiment 2
In diameter was 40 millimeters catalytic distillation tower, reaction zone (1) was high 1500 millimeters, and the rectifying section theoretical plate number is 40, and the catalyzer in the reaction zone is the sulfuric acid (2) of 69% (weight) concentration; Add methyl alcohol in the 4th theoretical tray position (5), the methanol feeding amount is: 0.12mol/min, and 90 ℃ of temperature of reaction, under reaction pressure 0.018MPa (absolute pressure) condition, reaction generates dme, and the per pass conversion of its methyl alcohol is 70%; Dme product (6) selectivity is 99.7%, and acid content is zero in the product dme, and acid content is 18ppm in the outlet reaction lime set (8).
Embodiment 3
In diameter was 40 millimeters catalytic distillation tower, reaction zone (1) was high 1500 millimeters, and the rectifying section theoretical plate number is 15, and the catalyzer in the reaction zone is the sulfuric acid (2) of 75% (weight) concentration; Add methyl alcohol in the 2nd theoretical tray position (5), the methanol feeding amount is: 0.17mol/min, and 100 ℃ of temperature of reaction, under reaction pressure 0.022MPa (absolute pressure) condition, reaction generates dme, and the per pass conversion of its methyl alcohol is 74%; Dme product (6) selectivity is 99.6%, and acid content is zero in the product dme, and acid content is 15ppm in the outlet reaction lime set (8).
Embodiment 4
In diameter was 40 millimeters catalytic distillation tower, reaction zone (1) was high 1500 millimeters, and the rectifying section theoretical plate number is 50, and the catalyzer in the reaction zone is the sulfuric acid (2) of 50% (weight) concentration; Add methyl alcohol in the 5th theoretical tray position (5), the methanol feeding amount is: 0.15mol/min, and 120 ℃ of temperature of reaction, under reaction pressure 0.1MPa (absolute pressure) condition, reaction generates dme, and the per pass conversion of its methyl alcohol is 77.5%; Dme product (6) selectivity is 99.5%, and acid content is zero in the product dme, and acid content is 16ppm in the outlet reaction lime set (8).
Embodiment 5
In diameter was 40 millimeters catalytic distillation tower, reaction zone (1) was high 1500 millimeters, and the rectifying section theoretical plate number is 3, and the catalyzer in the reaction zone is the sulfuric acid (2) of 96% (weight) concentration; Add methyl alcohol in the 2nd theoretical tray position (5), the methanol feeding amount is: 0.12mol/min, and 120 ℃ of temperature of reaction, under reaction pressure 0.1MPa (absolute pressure) condition, reaction generates dme, and the per pass conversion of its methyl alcohol is 76%; Dme product (6) selectivity is 99.4%, and acid content is zero in the product dme, and acid content is 19ppm in the outlet reaction lime set (8).
Embodiment 6
In diameter was 40 millimeters catalytic distillation tower, reaction zone (1) was high 1500 millimeters, and the rectifying section theoretical plate number is 20, and the catalyzer in the reaction zone is the sulfuric acid (2) of 21% (weight) concentration; Add methyl alcohol in the 2nd theoretical tray position (5), the methanol feeding amount is: 0.17mol/min, and 140 ℃ of temperature of reaction, under reaction pressure 0.15MPa (absolute pressure) condition, reaction generates dme, and the per pass conversion of its methyl alcohol is 90%; Dme product (6) selectivity is 99%, and acid content is zero in the product dme, and acid content is 18ppm in the outlet reaction lime set (8).
Embodiment 7
In diameter was 40 millimeters catalytic distillation tower, reaction zone (1) was high 1500 millimeters, and the rectifying section theoretical plate number is 30, and the catalyzer in the reaction zone is the sulfuric acid (2) of 21% (weight) concentration; Add methyl alcohol in the 3rd theoretical tray position (5), the methanol feeding amount is: 0.12mol/min, and 150 ℃ of temperature of reaction, under reaction pressure 0.2MPa (absolute pressure) condition, reaction generates dme, and the per pass conversion of its methyl alcohol is 95%; Dme product (6) selectivity is 98.5%, and acid content is zero in the product dme, and acid content is 20ppm in the outlet reaction lime set (8).
Embodiment 8
In diameter was 40 millimeters catalytic distillation tower, reaction zone (1) was high 1500 millimeters, and the rectifying section theoretical plate number is 35, and the catalyzer in the reaction zone is the sulfuric acid (2) of 50% (weight) concentration; Add methyl alcohol in the 4th theoretical tray position (5), the methanol feeding amount is: 0.12mol/min, and 180 ℃ of temperature of reaction, under reaction pressure 0.3MPa (absolute pressure) condition, reaction generates dme, and the per pass conversion of its methyl alcohol is 98%; Dme product (6) selectivity is 96%, and acid content is zero in the product dme, and acid content is 10ppm in the outlet reaction lime set (8).
Claims (5)
1, a kind ofly makes catalyzer with sulfuric acid, the method of methanol dehydration dimethyl ether-preparing, it is characterized in that catalyzed reaction and rectifying are carried out simultaneously in reactor, the temperature of methyl alcohol generation catalyzed reaction is 60～180 ℃, pressure is counted 0～0.3MPa with absolute pressure, and the concentration expressed in percentage by weight of catalyst sulfuric acid is 20～98%; Rectifying section theoretical plate number in the rectifying tower is 2～50, cat head component partial reflux.
2, method according to claim 1, the temperature that it is characterized in that methyl alcohol generation catalyzed reaction is 100～150 ℃.
3, method according to claim 1 is characterized in that the pressure of methyl alcohol generation catalyzed reaction is counted 0.05～0.15MPa with absolute pressure.
4, method according to claim 1 is characterized in that the rectifying section theoretical plate number in the rectifying tower is 5～30.
5, method according to claim 1, the feed entrance point that it is characterized in that methyl alcohol is the height of the 5th theoretical plate number at the most.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112144A CN1043225C (en) | 1994-05-03 | 1994-05-03 | Process for synthesis of dimethyl ether by catalytic distillation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112144A CN1043225C (en) | 1994-05-03 | 1994-05-03 | Process for synthesis of dimethyl ether by catalytic distillation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1111231A CN1111231A (en) | 1995-11-08 |
| CN1043225C true CN1043225C (en) | 1999-05-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94112144A Expired - Fee Related CN1043225C (en) | 1994-05-03 | 1994-05-03 | Process for synthesis of dimethyl ether by catalytic distillation |
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| Country | Link |
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| CN (1) | CN1043225C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895776B (en) * | 2005-07-14 | 2012-07-25 | 中国科学院大连化学物理研究所 | Catalyst for producing dimethyl ether by methanol liquid-phase or mixed-phase dewatering method |
| CN101058534B (en) * | 2006-04-18 | 2011-01-12 | 杭州林达化工技术工程有限公司 | Device and method for preparing dimethyl ether from methanol |
| CN101544545B (en) * | 2008-03-27 | 2013-06-05 | 中国石油化工股份有限公司 | Method for producing dimethyl ether from methanol |
| CN103446948A (en) * | 2013-08-27 | 2013-12-18 | 梧州市松桦化学品有限公司 | Reaction tower |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5535061A (en) * | 1978-09-05 | 1980-03-11 | Kuraray Co Ltd | Preparation of higher carbonyl compound |
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1994
- 1994-05-03 CN CN94112144A patent/CN1043225C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5535061A (en) * | 1978-09-05 | 1980-03-11 | Kuraray Co Ltd | Preparation of higher carbonyl compound |
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| CN1111231A (en) | 1995-11-08 |
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Granted publication date: 19990505 Termination date: 20110503 |