CN115872843A - Novel synthesis process of ethyl tert-butyl ether - Google Patents
Novel synthesis process of ethyl tert-butyl ether Download PDFInfo
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- CN115872843A CN115872843A CN202211300485.7A CN202211300485A CN115872843A CN 115872843 A CN115872843 A CN 115872843A CN 202211300485 A CN202211300485 A CN 202211300485A CN 115872843 A CN115872843 A CN 115872843A
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- temperature
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- tert
- butyl ether
- synthesis process
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- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012043 crude product Substances 0.000 claims abstract description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000012074 organic phase Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003254 gasoline additive Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- -1 t-butanol forms carbenium ions Chemical class 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a new synthesis process of ethyl tert-butyl ether, which relates to the technical field of chemical industry and comprises the following steps: s1, adding ethanol and a catalytic amount of strong acid type cation exchange resin into a dry and clean 1L four-mouth bottle, magnetically stirring, and heating to raise the temperature; s2, raising the temperature in a reaction bottle to 65-75 ℃, starting to slowly dropwise add tert-butyl alcohol, controlling the reaction temperature to be 75-85 ℃, simultaneously dropwise adding while distilling at normal pressure, and collecting fractions with the top temperature of 55-70 ℃; s3, after the dropwise addition is finished, continuing distillation, slowly raising the temperature to 85-100 ℃, and stopping the reaction when no distillate is evaporated; s4, washing the obtained fraction with 100ml of multiplied by 3 water, standing, separating liquid, and drying an organic phase with anhydrous sodium sulfate to obtain a crude product; s5, rectifying the crude product at normal pressure by using a 30 cm column, collecting fractions with the top temperature of 70 ℃ to obtain a target product at the oil temperature of 90-100 ℃, wherein the method has the beneficial effects that: the synthesis method has the advantages of high reaction speed, mild conditions, safety and reliability, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a novel synthesis process of ethyl tert-butyl ether.
Background
The ethyl tert-butyl ether has higher octane value, can enhance the antiknock performance, and is an environment-friendly gasoline additive. Ethyl tert-butyl ether will gradually replace methyl tert-butyl ether. Therefore, in recent years, ethyl t-butyl ether has been a hot spot of research in the field of gasoline additives. There are two main routes for the synthesis of ethyl tert-butyl ether: (1) The reaction of isobutene in the C4 fraction with ethanol produces ethyl tert-butyl ether (2) the reaction of tert-butanol with ethanol produces ethyl tert-butyl ether. Both routes use acid catalysts, but experimental data show that t-butanol forms carbenium ions more readily than isobutylene, and that t-butanol reacts at much higher rates than isobutylene. Compared with a liquid acid catalyst, a heteropoly acid catalyst and a molecular sieve catalyst, the resin catalyst has the advantages of high activity, easy separation from a product, small corrosion to equipment, high selectivity and the like, but the prior synthesis process for the ethyl tert-butyl ether is not mature, so a new synthesis process for the ethyl tert-butyl ether is provided.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel process for synthesizing ethyl tert-butyl ether, which solves the problems in the background art.
In order to achieve the purpose, the invention is realized by the following technical scheme: a new process for synthesizing ethyl tert-butyl ether comprises the following steps:
s1, adding ethanol and a catalytic amount of strong acid type cation exchange resin into a dry and clean 1L four-mouth bottle, magnetically stirring, and heating to raise the temperature;
s2, raising the temperature in a reaction bottle to 65-75 ℃, starting to slowly dropwise add tert-butyl alcohol, controlling the reaction temperature to be 75-85 ℃, simultaneously dropwise adding while distilling at normal pressure, and collecting fractions with the top temperature of 55-70 ℃;
s3, after the dropwise addition, continuing distillation, slowly raising the temperature to 85-100 ℃, and stopping the reaction when no fraction is evaporated;
s4, washing the obtained fraction with 100ml of multiplied by 3 water, standing, separating liquid, and drying an organic phase with anhydrous sodium sulfate to obtain a crude product;
s5, rectifying the crude product by using a 30 cm column at normal pressure, wherein the oil temperature is 90-100 ℃, and collecting distillate with the top temperature of 70 ℃ to obtain a target product.
The chemical reaction formula is as follows:
optionally, the molar ratio of the reaction tert-butanol to ethanol is 1.
Optionally, the distillation time while adding tert-butanol dropwise is about 4 to 8 hours.
Alternatively, the strong acid cation exchange resin is a catalyst commonly used in the industry, such as D005, D-72, S-54, amberlyst-15, amberlyst-35.
Optionally, the dosage of the strong acid type cation exchange resin is 0.05 to 0.1 times of that of the tert-butyl alcohol.
Optionally, the reaction temperature in the S2 is 75-100 ℃.
The invention provides a new synthesis process of ethyl tert-butyl ether, which has the following beneficial effects:
the synthesis method has the advantages of high reaction speed, mild conditions, safety and reliability, and is suitable for industrial production; the selected raw materials are cheap and easily available, and the production cost is favorably controlled; the yield of the target product is improved by controlling the dripping temperature and speed of the tert-butyl alcohol.
(1) Cheap ethanol and tert-butyl alcohol are used as raw materials to replace expensive sodium ethoxide, sodium tert-butoxide, bromoethane, tert-butyl chloride and the like. The raw materials are easy to obtain and cheap, and the production cost is reduced;
(2) Compared with tertiary butanol, the ethanol has stable property and good safety coefficient, and is beneficial to the large-scale industrial production;
(3) The strong acid type cation exchange resin catalyst has the advantages of high activity, easy separation from products, little corrosion to equipment, repeated utilization after activation, little environmental pollution and the like;
(4) The product is removed from the system by a mode of distilling the product while dropping tertiary butanol for reaction, thereby promoting the reaction, reducing the generation of side reaction and improving the yield.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
Adding 276g of ethanol and 7.4g of strong acid type cation exchange resin into a dry and clean 1L four-mouth bottle, magnetically stirring, and heating to raise the temperature; raising the temperature in a reaction bottle to 65 ℃, and slowly dropwise adding 148g of tert-butyl alcohol, wherein the reaction temperature is controlled at 75 ℃; meanwhile, dropwise adding tert-butyl alcohol while distilling at normal pressure, and collecting fractions with the top temperature of 55-70 ℃; after the dropwise addition, continuing distillation, slowly raising the temperature to 85 ℃, stopping the reaction when no fraction is distilled out, and keeping the reaction time at 5h; washing the obtained fraction with 100ml of × 3 water, standing, separating, and drying the organic phase with anhydrous sodium sulfate to obtain 221g crude product; the crude product is rectified by a 30 cm column under normal pressure, the oil temperature is 90-100 ℃, and distillate with the top temperature of 70 ℃ is collected to obtain 132.6g of qualified product, the GC purity is 98.5%, and the yield is 65%.
Example 2
Adding 368g of ethanol and 7.4g of strong acid type cation exchange resin into a dry and clean 1L four-mouth bottle, magnetically stirring, and heating to raise the temperature; raising the temperature in a reaction bottle to 65 ℃, and slowly dropwise adding 148g of tert-butyl alcohol, wherein the reaction temperature is controlled at 75 ℃; meanwhile, dropwise adding tert-butyl alcohol while distilling at normal pressure, and collecting fractions with the top temperature of 55-70 ℃; after the dropwise addition, continuing distillation, slowly raising the temperature to 85 ℃, stopping the reaction when no fraction is distilled out, and keeping the reaction time at 5h; washing the obtained fraction with 100ml of 3 water, standing, separating, and drying the organic phase with anhydrous sodium sulfate to obtain 235g of crude product; the crude product is rectified by a 30 cm column under normal pressure, the oil temperature is 90-100 ℃, and distillate with the top temperature of 70 ℃ is collected to obtain 140.8g of qualified product, the GC purity is 98.5%, and the yield is 69%.
Example 3
368g of ethanol and 14.8g of strong acid type cation exchange resin are added into a dry and clean 1L four-mouth bottle, and the mixture is magnetically stirred, heated and heated; raising the temperature in a reaction bottle to 65 ℃, and slowly dropwise adding 148g of tert-butyl alcohol, wherein the reaction temperature is controlled at 75 ℃; meanwhile, dropwise adding tert-butyl alcohol while distilling at normal pressure, and collecting fractions with the top temperature of 55-70 ℃; after the dropwise addition, continuing the distillation, slowly raising the temperature to 85 ℃, stopping the reaction when no fraction is distilled out, and keeping the reaction time at 4h; washing the obtained fraction with 100ml of × 3 water, standing, separating, and drying the organic phase with anhydrous sodium sulfate to obtain 242g of crude product; the crude product is rectified by a 30 cm column under normal pressure, the oil temperature is 90-100 ℃, and distillate with the top temperature of 70 ℃ is collected to obtain 146.9g of qualified product, the GC purity is 98.5%, and the yield is 72%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. A new synthesis process of ethyl tert-butyl ether is characterized in that: the method comprises the following steps:
s1, adding ethanol and a catalytic amount of strong acid type cation exchange resin into a dry and clean 1L four-mouth bottle, magnetically stirring, and heating to raise the temperature;
s2, raising the temperature in a reaction bottle to 65-75 ℃, starting to slowly dropwise add tert-butyl alcohol, controlling the reaction temperature to be 75-85 ℃, simultaneously dropwise adding while distilling at normal pressure, and collecting fractions with the top temperature of 55-70 ℃;
s3, after the dropwise addition, continuing distillation, slowly raising the temperature to 85-100 ℃, and stopping the reaction when no fraction is evaporated;
s4, washing the obtained fraction with 100ml of multiplied by 3 water, standing, separating liquid, and drying an organic phase with anhydrous sodium sulfate to obtain a crude product;
s5, rectifying the crude product by using a 30 cm column at normal pressure, wherein the oil temperature is 90-100 ℃, and collecting distillate with the top temperature of 70 ℃ to obtain a target product.
2. The new synthesis process of ethyl tert-butyl ether according to claim 1, characterized in that: the molar ratio of the reaction tert-butanol to ethanol is 1.
3. The new synthesis process of ethyl tert-butyl ether according to claim 1, characterized in that: the distillation time while adding tert-butanol dropwise is about 4 to 8 hours.
4. The novel process for synthesizing ethyl tert-butyl ether according to claim 1, which is characterized in that: the strong acid type cation exchange resin is a catalyst commonly used in industry, and is D005, D-72, S-54, amberlyst-15, amberlyst-35.
5. The new synthesis process of ethyl tert-butyl ether according to claim 1, characterized in that: the dosage of the strong acid type cation exchange resin is 0.05 to 0.1 time of that of the tertiary butanol.
6. The new synthesis process of ethyl tert-butyl ether according to claim 1, characterized in that: the reaction temperature in the S2 is 75-100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211300485.7A CN115872843A (en) | 2022-10-24 | 2022-10-24 | Novel synthesis process of ethyl tert-butyl ether |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211300485.7A CN115872843A (en) | 2022-10-24 | 2022-10-24 | Novel synthesis process of ethyl tert-butyl ether |
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| Publication Number | Publication Date |
|---|---|
| CN115872843A true CN115872843A (en) | 2023-03-31 |
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| CN202211300485.7A Pending CN115872843A (en) | 2022-10-24 | 2022-10-24 | Novel synthesis process of ethyl tert-butyl ether |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5449839A (en) * | 1993-05-06 | 1995-09-12 | Texaco Chemical Inc. | One step synthesis of ethyl t-butyl ether from t-butanol using β-zeolite and multimetal-modified β-zeolite catalysts |
| US5527970A (en) * | 1995-02-02 | 1996-06-18 | Texaco Chemical Inc. | Synthesis of ethyl t-butyl ether from t-butanol in one step using acid catalysts |
| CN1780803A (en) * | 2003-11-07 | 2006-05-31 | 日本易能有限会社 | Method of synthesizing etbe with hydrous ethanol |
| JP2007126450A (en) * | 2005-10-04 | 2007-05-24 | Tokyo Electric Power Co Inc:The | Method for synthesizing etbe by microwave |
| CN105566550A (en) * | 2014-10-13 | 2016-05-11 | 中国石化扬子石油化工有限公司 | Preparation method of acidic polystyrene resin catalyst for synthesis of ethyl tert-butyl ether |
-
2022
- 2022-10-24 CN CN202211300485.7A patent/CN115872843A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5449839A (en) * | 1993-05-06 | 1995-09-12 | Texaco Chemical Inc. | One step synthesis of ethyl t-butyl ether from t-butanol using β-zeolite and multimetal-modified β-zeolite catalysts |
| US5527970A (en) * | 1995-02-02 | 1996-06-18 | Texaco Chemical Inc. | Synthesis of ethyl t-butyl ether from t-butanol in one step using acid catalysts |
| CN1780803A (en) * | 2003-11-07 | 2006-05-31 | 日本易能有限会社 | Method of synthesizing etbe with hydrous ethanol |
| JP2007126450A (en) * | 2005-10-04 | 2007-05-24 | Tokyo Electric Power Co Inc:The | Method for synthesizing etbe by microwave |
| CN105566550A (en) * | 2014-10-13 | 2016-05-11 | 中国石化扬子石油化工有限公司 | Preparation method of acidic polystyrene resin catalyst for synthesis of ethyl tert-butyl ether |
Non-Patent Citations (2)
| Title |
|---|
| 张颖等: "乙基叔丁基醚的绿色合成", 《化学教育》, no. 1, pages 3 - 11 * |
| 杨伯伦等: "数种阳离子交换树脂对合成乙基叔丁基醚的催化性能比较", 《化学反应工程与工艺》, vol. 16, no. 2, pages 148 * |
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