CN1560008A - Process for separating ethandiol, mono methyl ether, isopropyl alcohol and water combined by extracting and axeotropy - Google Patents
Process for separating ethandiol, mono methyl ether, isopropyl alcohol and water combined by extracting and axeotropy Download PDFInfo
- Publication number
- CN1560008A CN1560008A CNA2004100142545A CN200410014254A CN1560008A CN 1560008 A CN1560008 A CN 1560008A CN A2004100142545 A CNA2004100142545 A CN A2004100142545A CN 200410014254 A CN200410014254 A CN 200410014254A CN 1560008 A CN1560008 A CN 1560008A
- Authority
- CN
- China
- Prior art keywords
- monomethyl ether
- glycol monomethyl
- water
- ethylene glycol
- separating
- 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.)
- Granted
Links
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 19
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 45
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000605 extraction Methods 0.000 claims abstract description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 241000282326 Felis catus Species 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 238000004508 fractional distillation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- -1 ethylene glycol monomethyl ether glycerine benzene Chemical compound 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention is a method of combining extraction and azeotropism to separate glycol monomethyl ether, isopropyl alcohol and water, and its steps: using glycerol and benzene as extractant and azeotropic agent, respectively, adopting a rectifying device to separate a mixed solution with isopropyl alcohol plus water plus glycol monomethyl ether, after separating, the isopropyl alcohol plus water is on the tower top and the water plus glycol monomethyl ether is in the tower bottom; separating the distillate from the tower top by extract-rectification process with the glycerol as extractant; after extraction separation, feeding the water plus glycol monomethyl ether in the bottom to an azeotropic distilling device and adopting the benzene as azeotropic agent, where the benzene is recycled. The contents of glycol monomethyl ether and sopropyl alcohol can both reach 99.5% above; those in the water are both lower than below 0.23% and it can primarily obtain glycol monomethyl ether acetate, after separating, the isopropyl alcohol is recycled, the glycol monomethyl ether is returned as raw material.
Description
Technical field
The present invention relates to a kind of separating technology of chemical industry, the extraction of particularly a kind of ethylene glycol monomethyl ether, Virahol and water and the separation method that azeotropic combines.
Background technology
Along with developing rapidly of China's economic construction, people's top grade lacquer, coating constantly increase with the requirement of solvent-ethylene glycol monomethyl ether acetic ester, according to estimates, year demand is about 1,000,000 tons at present, and domestic annual production only is 100,000 tons, does not satisfy the demand in market far away, major part still needs import, the production of ethylene glycol monomethyl ether acetic ester is catalyzer with acid (solid acid or mineral acid) mainly, is raw material with ethylene glycol monomethyl ether and acetic acid, and adopting solid acid or mineral acid is catalyzer.The general acetic acid that adopts is excessive or ethylene glycol monomethyl ether is excessive in building-up process, adopt the excessive method of acetic acid, the each side technology is ripe, suitability for industrialized production, but adopt ethylene glycol monomethyl ether excessive, owing to add band aqua (Virahol) in synthetic excessive, band aqua and ethylene glycol monomethyl ether and water all can form azeotrope, the azeotropic point and the composition that form azeotrope are shown in Table 1
| Material | The azeotropic point temperature (℃) | Azeotropic is formed |
| Water+Virahol | ??80.3℃ | 12.6% water, 87.4% Virahol |
| Water+ethylene glycol monomethyl ether | ??99.9℃ | 15.3% water, 84.7% ethylene glycol monomethyl ether |
The azeotrope that produces is (Virahol+water+ethylene glycol monomethyl ether), and therefore, can Virahol+water+ethylene glycol monomethyl ether effectively separate, and can be related to the ethylene glycol monomethyl ether overflow method industrialization.Virahol+water in the industrial production+ethylene glycol monomethyl ether separation at present generally adopts siccative (as CaCl
2) wait first dehydration, adopt rectification method separating isopropanol and ethylene glycol monomethyl ether then, in industrial production, adopt CaCl
2The slurries that dehydration is produced, regeneration is difficult, and carries Virahol and the ethylene glycol monomethyl ether of 2-3% (mass ratio) in the slurries secretly, has not only wasted resource, and has easily caused certain problem to environment.
Summary of the invention
The present invention adopts extraction and the azeotropic method separating isopropanol+water+ethylene glycol monomethyl ether that combines, and separates afterwards that Virahol recycles, and ethylene glycol monomethyl ether can return raw material.
The technical scheme of finishing the foregoing invention task is: with glycerine and benzene is the extraction agent of extracting rectifying and the entrainer of component distillation, at first adopt rectifier unit separating isopropanol+water+ethylene glycol monomethyl ether mixing solutions, after the separation, cat head is Virahol+water, is water+ethylene glycol monomethyl ether at the bottom of the tower; Overhead distillate (Virahol+water) is delivered to extraction fractional distillation and is separated, and adopting glycerine in the extraction process is extraction agent, and after the extracting and separating, the Virahol water content can be reduced to below 0.5%; Ethylene glycol monomethyl ether+water is delivered to the component distillation device at the bottom of the tower, and employing benzene is entrainer, and benzene recycles in the azeotropic device, and the azeotropic device can be reduced to the ethylene glycol monomethyl ether water content below 0.5%, and therefore, ethylene glycol monomethyl ether can be returned to raw material and re-use.The technical process of sepn process is seen shown in Figure 1, and separating apparatus adopts optimizes processing condition, and Virahol, ethylene glycol monomethyl ether water content all can be taken off to below 0.5% after separating, and can reach the requirement that recycles.
Advantage of the present invention: adopt technology shown in Figure 1 and optimized parameters, raw material Virahol+water+ethylene glycol monomethyl ether, at first separate T-1 through rectifying tower, cat head separates with azeotropic device T-3 through extraction plant T-2 respectively with tower is low then, separates back Virahol and ethylene glycol monomethyl ether content and all can reach more than 99.5%; Separate and to contain Virahol in the water of back and the ethylene glycol monomethyl ether amount all is lower than below 0.23%, compare with present method therefor, in ethylene glycol monomethyl ether acetic ester building-up process, once excessive ethylene glycol monomethyl ether of reaction and water generation reaction can be separated, once can get the ethylene glycol monomethyl ether acetic ester, Virahol+water that reaction process is separated+ethylene glycol monomethyl ether azeotrope separates with the azeotropic device through extraction plant, all can be recycled, and is difficult for throwing into question to environment.
Adopt above method separating apparatus to adopt and optimize processing condition, Virahol, ethylene glycol monomethyl ether water content all can be taken off to below 0.5% after separating.
Description of drawings
Fig. 1 extraction and azeotropic process combined flow process.
Embodiment
The extraction with azeotropic in conjunction with the method for separating ethylene glycol monomethyl ether, Virahol and water, with reference to parameter shown in technology shown in Figure 1 and the table 2, raw material (F1) is ethylene glycol monomethyl ether+Virahol+water mixed liquid, the mass content of ethylene glycol monomethyl ether, Virahol and water (Xf1, Xf2, Xf3) is respectively 10%, 50%, 40%, flow is 4.1Kg/h, when precise rectification tower T-1 top, low temperature are respectively 80.4 ℃ and 87.5 ℃, top, low flow are respectively 2.7Kg/h, 1.4Kg/h, precise distillation ℃ trim the top of column is controlled at 4～6 than (R1), forms (x at the bottom of the cat head
Di, x
Wi) x
D1=0.0000, x
D2=0.7592, x
D3=0.2407, x
W1=0.2929, x
W2=0.0000x
W3=0.7071; The cat head component is delivered to extracting rectifying device (T-2), extraction agent (glycerine) and raw material ratio S/F2=2.5: 1, trim the top of column is controlled at 4～6 than R2, and the extracting rectifying cat head can get 99.6% Virahol, rich aqueous extraction agent is delivered to regenerator column regeneration at the bottom of the tower, recycles then; Precise distillation tower bottom flow part is delivered to azeotropic device T-3, adopts benzene as entrainer, and blend column overhead distillate is after condenser condenses, and the benzene layer refluxes, and water layer is discharged, and can get the ethylene glycol monomethyl ether more than 99.5% at the bottom of the azeotropic Tata.Among the figure, 1,4,5,8 is condenser; 3,11 is reboiler; 2 is rectifying tower; 6 is extraction tower; 7 is regenerator column; 9 are the layering return tank; 10 is azeotrope column.1.～9. be stream burst title (seeing Table 2).
Each tower process condition of table 1
| The T-1 tower | The T-2 tower | The T-3 tower | The T-4 | ||||
| 1. feed entrance point reflux ratio (R 1) the stage number tower top temperature, (℃) column bottom temperature, (℃) | ??27 ? ? ? ??4-6 ? ??56 ? ??80.5 ? ??87-89 | 2. feed entrance point S feed entrance point reflux ratio (R2) number of plates tower top temperature (℃) column bottom temperature (℃) | ???73 ? ???11 ? ???4-5 ? ???89 ? ???82-83 ? ???137-141 | 3. feed entrance point reflux ratio (R3) number of plates tower top temperature (℃) column bottom temperature (℃) | ??15 ? ??3-5 ? ??31 ??69-100 ? ??125-127 ? | 4. feed entrance point reflux ratio number of plates tower top temperature (℃) column bottom temperature (℃) | ??19 ? ? ??4-5 ? ? ??37 ??99-101 ? ??167-171 |
Table 2 separating resulting
| The stream thigh | Title | Flow (Kg/h) | Form (mass content) |
| Isopropanol water ethylene glycol monomethyl | |||
| ① ② ③ ④ ⑤ ⑥ ⑦ ⑧ ⑨ | Stock liquid (F 1) tower T-1 ejects material tower T-2 and eject at the bottom of the material tower T-2 discharging tower T-4 and eject at the bottom of the material tower T-4 at the bottom of the discharging tower T-1 discharging tower T-3 and eject discharging at the bottom of the material tower T-3 | ????4.10 ????2.70 ????2.06 ????7.39 ????0.63 ????6.76 ????1.4 ????1.04 ????0.36 | 0.5012???0.4103???0.0885????????/????????/ 0.7611???0.2389???/?????????????/????????/ 0.9968???0.0032???/?????????????/????????/ 0.0002???0.0864???/?????????????0.9133???/ 0.0023???0.9977???/?????????????/????????/ /????????0.0015???/?????????????0.9985???/ /????????0.7408???0.2592????????/????????/ /????????0.9992???/?????????????/????????0.0008 /????????0.0021???0.9979????????/????????/ |
Claims (1)
1, a kind of extraction and azeotropic the steps include: in conjunction with the method for separating ethylene glycol monomethyl ether, Virahol and water
With glycerine and benzene is the extraction agent of extracting rectifying and the entrainer of component distillation,
Adopt rectifier unit separating isopropanol+water+ethylene glycol monomethyl ether mixing solutions, after the separation, cat head is Virahol+water, is water+ethylene glycol monomethyl ether at the bottom of the tower;
Overhead distillate is delivered to extraction fractional distillation and is separated, and employing glycerine is extraction agent;
After the extracting and separating, ethylene glycol monomethyl ether+water is delivered to the component distillation device at the bottom of the tower, and employing benzene is entrainer, and benzene recycles in the azeotropic device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410014254 CN1238318C (en) | 2004-03-09 | 2004-03-09 | Process for separating ethandiol, mono methyl ether, isopropyl alcohol and water combined by extracting and axeotropy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410014254 CN1238318C (en) | 2004-03-09 | 2004-03-09 | Process for separating ethandiol, mono methyl ether, isopropyl alcohol and water combined by extracting and axeotropy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1560008A true CN1560008A (en) | 2005-01-05 |
| CN1238318C CN1238318C (en) | 2006-01-25 |
Family
ID=34440284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410014254 Expired - Fee Related CN1238318C (en) | 2004-03-09 | 2004-03-09 | Process for separating ethandiol, mono methyl ether, isopropyl alcohol and water combined by extracting and axeotropy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1238318C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584544A (en) * | 2012-01-11 | 2012-07-18 | 河北工业大学 | Process for separating ethylene glycol monomethyl ether and water with intermittent azeotropic distillation method |
| CN102603484A (en) * | 2012-02-23 | 2012-07-25 | 中国科学院过程工程研究所 | Method for separating allyl alcohol and water by extractive distillation with N-methyl-pyrrolidone |
| CN102952004A (en) * | 2012-01-11 | 2013-03-06 | 河北工业大学 | Technology for separating ethylene glycol monomethyl ether and water by use of continuous azeotropic distillation method |
| CN103183590A (en) * | 2011-12-28 | 2013-07-03 | 上海交通大学 | Separation method of water and propylene glycol monomethyl ether |
| CN103288581A (en) * | 2013-07-01 | 2013-09-11 | 济南大学 | Batch extractive distillation separation method of benzene-propyl alcohol azeotropic mixture |
| CN103740170A (en) * | 2013-12-30 | 2014-04-23 | 惠州市立美特环保油墨有限公司 | Method for removing benzene in UV (ultraviolet) monomer, UV monomer and UV ink |
| US9029615B2 (en) | 2012-09-05 | 2015-05-12 | Dynasep Inc. | Energy efficient method and apparatus for the extraction of lower alcohols from dilute aqueous solution |
| CN105561620A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | Water-containing high-boiling point solvent recovery process and apparatus thereof |
| US9630894B2 (en) | 2012-09-05 | 2017-04-25 | Dynasep Inc. | Energy efficient method and apparatus for the extraction of biomolecules from dilute aqueous solution |
| CN107698428A (en) * | 2017-09-27 | 2018-02-16 | 湖北绿色家园材料技术股份有限公司 | A kind of method of moisture in separation allyl alcohol |
-
2004
- 2004-03-09 CN CN 200410014254 patent/CN1238318C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183590A (en) * | 2011-12-28 | 2013-07-03 | 上海交通大学 | Separation method of water and propylene glycol monomethyl ether |
| CN102952004A (en) * | 2012-01-11 | 2013-03-06 | 河北工业大学 | Technology for separating ethylene glycol monomethyl ether and water by use of continuous azeotropic distillation method |
| CN102584544B (en) * | 2012-01-11 | 2013-12-18 | 河北工业大学 | Process for separating ethylene glycol monomethyl ether and water with intermittent azeotropic distillation method |
| CN102584544A (en) * | 2012-01-11 | 2012-07-18 | 河北工业大学 | Process for separating ethylene glycol monomethyl ether and water with intermittent azeotropic distillation method |
| CN102952004B (en) * | 2012-01-11 | 2015-01-21 | 河北工业大学 | Technology for separating ethylene glycol monomethyl ether and water by use of continuous azeotropic distillation method |
| CN102603484A (en) * | 2012-02-23 | 2012-07-25 | 中国科学院过程工程研究所 | Method for separating allyl alcohol and water by extractive distillation with N-methyl-pyrrolidone |
| US9630894B2 (en) | 2012-09-05 | 2017-04-25 | Dynasep Inc. | Energy efficient method and apparatus for the extraction of biomolecules from dilute aqueous solution |
| US9029615B2 (en) | 2012-09-05 | 2015-05-12 | Dynasep Inc. | Energy efficient method and apparatus for the extraction of lower alcohols from dilute aqueous solution |
| CN103288581A (en) * | 2013-07-01 | 2013-09-11 | 济南大学 | Batch extractive distillation separation method of benzene-propyl alcohol azeotropic mixture |
| CN103740170A (en) * | 2013-12-30 | 2014-04-23 | 惠州市立美特环保油墨有限公司 | Method for removing benzene in UV (ultraviolet) monomer, UV monomer and UV ink |
| CN103740170B (en) * | 2013-12-30 | 2016-05-18 | 惠州市立美特环保油墨有限公司 | The method of benzene and UV monomer, UV ink in expeling UV monomer |
| CN105561620A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | Water-containing high-boiling point solvent recovery process and apparatus thereof |
| CN105561620B (en) * | 2014-10-09 | 2017-11-28 | 中国石油化工股份有限公司 | Aqueous high boiling solvent recovery process and device |
| CN107698428A (en) * | 2017-09-27 | 2018-02-16 | 湖北绿色家园材料技术股份有限公司 | A kind of method of moisture in separation allyl alcohol |
| CN107698428B (en) * | 2017-09-27 | 2022-09-20 | 湖北绿色家园材料技术股份有限公司 | Method for separating water in allyl alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1238318C (en) | 2006-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1238318C (en) | Process for separating ethandiol, mono methyl ether, isopropyl alcohol and water combined by extracting and axeotropy | |
| CN101244983B (en) | Process for separating and recovering organic matter in low-temperature Fischer-Tropsch synthesizing reaction | |
| CN101389587A (en) | A process for reactive distillation of a carboxylic acid | |
| CN101239886B (en) | Method for separating and reclaiming organic matter from high-temperature Fischer-Tropsch synthesis reaction water | |
| CN102153458A (en) | Method for recovering dilute acetic acid by virtue of extraction-azeotropic distillation of sec-butyl acetate | |
| CN102267889A (en) | Method for recovering spirit of vinegar by combining extraction with azeotropic distillation | |
| CN101792386B (en) | Method for treating solvent and by-product in aromatic carboxylic acid production | |
| CN105111079A (en) | Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol | |
| CN1821200A (en) | Method for rectifying and separating methylal-methanol-water by adding salt composite extracting | |
| CN102093163B (en) | Method for separating and purifying ethanol from Tropsch synthesis reaction water | |
| CN101148398A (en) | Method for separating Ethylene glycol monomethyl ether, methanol and water by rectification and azeotropy | |
| CN100469755C (en) | Azeotropic distillation process for separating butanol and butyl acetate | |
| CN101830788A (en) | Method for separating azeotropic mixture of ethyl methyl ketone and water through variable-pressure rectification | |
| CN101186575B (en) | Methyl acetate catalytic rectification hydrolysis process | |
| CN105439819B (en) | The separation method of methyl acetate preparation of ethanol by hydrogenating | |
| CN101709025A (en) | Compound cross-flow liquid-liquid extraction separation method of methylal-methanol azeotropic system | |
| CN101260016A (en) | Refining device for preparing high-pure isobutene by cracking methyl tertiary butyl ether and technique thereof | |
| CN102675094A (en) | Energy-saving and yield-improving production method of ethyl acetate | |
| CN101367723A (en) | Process and apparatus for preparing n-butyl acetate | |
| CN100371310C (en) | Method for separating ethyl ether, ethyl alcohol and acid water by combining rectifying and azeotropic distilling | |
| CN103044217A (en) | Method for separating and recovering non-acidic oxygenated organic substances in Fischer-Tropsch synthesis reaction water | |
| CN1212172A (en) | Process for separating azeotrope of methanol and dimethyl carbonate | |
| CN101555194A (en) | Method for separating aqueous phase byproduct from Fischer-Tropsch synthesis reaction | |
| CN104829451B (en) | Combined production method for acetic acid ester and glycol | |
| CN1226261C (en) | Liquid-liquid extraction process of dioxyethyl methane and water solution of ethanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |