CN103467245B - Method for complexing and removing water contained in ethanol and water mixed solution by utilizing eutectic solvent - Google Patents
Method for complexing and removing water contained in ethanol and water mixed solution by utilizing eutectic solvent Download PDFInfo
- Publication number
- CN103467245B CN103467245B CN201310436608.4A CN201310436608A CN103467245B CN 103467245 B CN103467245 B CN 103467245B CN 201310436608 A CN201310436608 A CN 201310436608A CN 103467245 B CN103467245 B CN 103467245B
- Authority
- CN
- China
- Prior art keywords
- complexing
- eutectic solvent
- mixed solution
- water mixed
- moisture
- 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
Abstract
The invention belongs to the technical field of chemical engineering, and particularly relates to a method for complexing and removing water contained in an ethanol and water mixed solution by utilizing an eutectic solvent. The method is used for preparing anhydrous ethanol. The method disclosed by the invention can be used for complexing the water contained in the ethanol and water mixed solution by utilizing the eutectic solvent and then removing the water contained in the ethanol and water mixed solution through distillation, is especially suitable for preparing the anhydrous ethanol by removing the water contained in the 95% ethanol and water mixed solution and prevents the high energy consumption of an extractive distillation method and an azeotropic distillation method. According to the invention, the eutectic solvent which plays a complexing agent role can be recycled after being removed in water through evaporation. The method disclosed by the invention has the advantages of easiness for process operation, low cost, no wastewater discharge, mildness in complexing condition, operation at low temperature and normal pressure and high production safety and is suitable for small-scale device production and also suitable for large-scale device production.
Description
Technical field
The present invention relates to a kind of method utilizing eutectic solvent complexing to remove moisture in ethanol water mixed solution.
Background technology
Dehydrated alcohol is a kind of important industrial chemicals.Be widely used in the industries such as medicine, agricultural chemicals, paint, food, makeup, rubber, electronic industry.In addition, in dehydrated alcohol, add properties-correcting agent and can form fuel ethanol.Fuel ethanol, with certain proportion and gasoline blending, forms vehicle-use alcohol gasoline, can be used as the environment-friendly fuel of automobile.In recent years, along with the Continued of energy prices, national science and technology Outline Development Plan has been listed in the behave of saving petroleum resources in.Automobile-used dehydrated alcohol project is actively promoted in some provinces.
The purity that ethanol can reach is the important quality index of dehydrated alcohol.Most commercially available dehydrated alcohol generally can only reach 99.5% purity, needs, with the higher dehydrated alcohol of purity, often to need oneself to prepare in many organic synthesis.Usually the ethanol of industrial 95.5% direct distillation method can not produce dehydrated alcohol, because the water of 95.5% ethanol and 4.5% forms constant boiling mixture.Water be removed, the general the first step adds calcium oxide (unslaked lime) boiling reflux, makes the water in ethanol and unslaked lime effect generate calcium hydroxide, and then steamed by dehydrated alcohol.Obtain dehydrated alcohol like this, purity is the highest by about 99.5%.At present, the production method of dehydrated alcohol also has azeotropic distillation, extraction fractional distillation, molecular sieve adsorbing and dewatering method, calcium oxide evaporation, pervaporation method, vacuum dehydration method and biomass absorbent method etc.Wherein all there is certain deficiency, as energy consumption is high.And the higher dehydrated alcohol MAGNESIUM METAL of purity or sodium Metal 99.5 process.Thus from Energy Angle, lower, that product purity the is higher dehydrated alcohol of exploitation energy consumption is significant.
Summary of the invention
The present invention be overcome that prior art extraction fractional distillation exists remove the technical problems such as the higher and product purity of moisture energy consumption used in ethanol water mixed solution is lower, a kind of method utilizing eutectic solvent complexing to remove moisture in ethanol water mixed solution is provided.
The technology of the present invention is applicable to the moisture removed in 95% ethanol water mixed solution and produces dehydrated alcohol, avoid the high energy consumption of extraction fractional distillation and azeotropic distillation, the eutectic solvent playing complexing agent effect can be recycled after evaporation removing moisture, novel process significantly reduces production cost, and product quality indicator can reach the requirement of dehydrated alcohol high-quality product.
The present invention is achieved by the following technical solutions:
Utilize eutectic solvent complexing to remove a method for moisture in ethanol water mixed solution, it comprises the following steps:
A. ethanol water mixed solution ethanol content being less than or equal to 95% sends into complexing still kettle, the eutectic solvent that can form complex compound with water in proportion afterwards joins complexing still kettle under agitation, complexing pot temperature is 20 DEG C ~ 40 DEG C, pressure is 0.1 ~ 0.2MPa, and in described eutectic solvent and described ethanol water mixed solution, the mass ratio of moisture is 15 ~ 20:1;
Described eutectic solvent is the eutectic solvent that quaternary ammonium salt and hydrogen bond donor are formed, described quaternary ammonium salt is one in Dodecyl trimethyl ammonium chloride, choline chloride 60, beet alkali hydrochlorate, palmityl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, chitosan quaternary ammonium salt and tetrabutylammonium chloride or it is composite, and described hydrogen bond donor is one in urea, glycerine, ethylene glycol, formic acid, acetic acid and methane amide or it is composite;
B. in described step a, the complex liquid that moisture in described ethanol water mixed solution and eutectic solvent are formed is after distillation terminates, be driven into complex liquid storage tank, be sent to follow-up decompression dehydration operation afterwards in evaporating kettle, remove moisture in complex liquid, the eutectic solvent obtaining regenerating is for complexing next time.
The above-mentioned eutectic solvent complexing that utilizes removes the method for moisture in ethanol water mixed solution, and it is further comprising the steps of:
Complex liquid pump in complex liquid storage tank in step b is squeezed into evaporating kettle by c, before entering evaporating kettle, heater via heats, temperature be 70 DEG C ~ 90 DEG C, vacuum tightness removes moisture under being the condition of 0.5MPa ~ 0.8MPa, the moisture that evaporating kettle still top is flowed out is used for the complex liquid that preheating enters evaporating kettle;
D. the dewatered eutectic solvent stayed in evaporating kettle is sent to complexing still kettle to recycle.
Preferably, in described steps d, Heating temperature is 75 DEG C ~ 85 DEG C, and the best is 80 DEG C.
Preferably, the service temperature in the complexing still kettle of described step a is 30 DEG C, pressure 0.1MPa.
Preferably, in described ethanol water mixed solution, water-content scope is 85% ~ 95%.
The unusual effect that the present invention compared with prior art has is:
1. the present invention utilizes the method for eutectic solvent complexing to remove moisture in ethanol water mixed solution, ethanol water mixed solution contacts with the eutectic solvent added from complexing still kettle top, realize the complexing with moisture in ethanol water mixed solution, adopt the method for simple distillation dehydrated alcohol can be separated afterwards, purity of alcohol reaches 99.5% ~ 99.9%, adjusts the specification that the add-on of eutectic solvent, Complexation conditions and distillation condition can control product dehydrated alcohol.Present invention process is simple to operate, cost is low, non-wastewater discharge, is both applicable to small-scale device and is also applicable to large-scale device production.Complexation conditions of the present invention is gentle, and low-temperature atmosphere-pressure operates, and production security is high.
2. the present invention utilizes eutectic solvent high as complexing agent dewatering efficiency, and in complexing kettle, mixed once gets final product the almost whole moisture in complexing ethanol water mixed solution, and in product, water-content is extremely low.
3. the present invention be used as that the eutectic solvent cost of complexing agent is low, preparation easily and can be recycled, belong to biodegradable environmentally friendly machine.
4. the complexing that adopts of the present invention and the process characteristic that combines of distillation are that Complexation Efficiency is high, and dehydration thoroughly.Meanwhile, eutectic solvent also has removal effect to a small amount of metallic impurity in ethanol water mixed solution, significantly reduces energy expenditure and production cost, obtains high-quality dehydrated alcohol.
In a word, the present invention adopts eutectic solvent, and a kind of ionic liquid analogue, produces dehydrated alcohol as complexing agent in conjunction with simple distillation.Compared with existing extraction fractional distillation, energy consumption declines further.Thinking of the present invention is the good characteristic giving full play to eutectic solvent moisture absorption, removes the moisture in ethanol water mixed solution.Through exploratory development, we find eutectic solvent method can with the complexing well of the moisture in ethanol water mixed solution, adopt the method for distillation dehydrated alcohol can be separated afterwards, purity of alcohol reaches 99.5% ~ 99.9%.After dehydration by evaporation, eutectic solvent can be recycled.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
95% commercially available ethanol water mixed solution is joined in complexing still kettle 1, adds eutectic solvent, Keep agitation 1 hour.Leave standstill 20 minutes.In complexing still kettle, complexing phase temperature is 25 DEG C, and complexing staged pressure is 0.1MPa, and in described eutectic solvent and described ethanol water mixed solution, the mass ratio of moisture is 16.5:1; Eutectic solvent used is made from choline chloride 60 and urea, and choline chloride 60 and weight of urea are than being 1:2.Described complexing still kettle volume 3 cubic metres, aspect ratio is 2:1.
In complexing still kettle, distillation phase temperature is 80 DEG C, distillation staged pressure is 0.1MPa, the moisture that distillation terminates in rear ethanol water mixed solution and the complex liquid pump that eutectic solvent is formed are driven into evaporating kettle, under 80 DEG C of vacuum tightnesss with 0.7MPa, decompression dehydration obtains the eutectic solvent regenerated, and recycles.
The dehydrated alcohol yield that complexing still kettle still top steams reaches 97% of theoretical amount, after testing, distill ethanol mass fraction >99.6% in the product obtained, the mass fraction of water is less than 0.4%, evaporation residue is less than 0.001%, reaches the standard of dehydrated alcohol.
Embodiment 2
95% commercially available ethanol water mixed solution is joined in complexing still kettle, adds eutectic solvent, Keep agitation 2 hours.Leave standstill 10 minutes.In complexing still kettle, complexing phase temperature is 35 DEG C, and complexing staged pressure is 0.1MPa, and in described eutectic solvent and described ethanol water mixed solution, the mass ratio of moisture is 25:1; Described eutectic solvent is choline chloride 60 and glycerol mixture composition, and its weight ratio is 1:3.Described complexing still kettle volume 3 cubic metres, aspect ratio is 2:1.
Distillation phase temperature is 80 DEG C, distillation staged pressure is 0.1MPa, the moisture that distillation terminates in rear ethanol water mixed solution and the complex liquid pump that eutectic solvent is formed are driven into evaporating kettle, and under 80 DEG C of vacuum tightnesss with 0.7MPa, decompression dehydration obtains the eutectic solvent regenerated, and recycles.
The dehydrated alcohol yield that complexing still kettle still top steams reaches 98% of theoretical amount, after testing, distill ethanol mass fraction >99.8% in the product obtained, the mass fraction of water is less than 0.2%, evaporation residue is less than 0.001%, reaches the standard of dehydrated alcohol.
Embodiment 3
95% commercially available ethanol water mixed solution is joined in complexing still kettle, adds eutectic solvent, Keep agitation 0.5 hour.Leave standstill 15 minutes.In complexing still kettle, complexing phase temperature is 40 DEG C, and complexing staged pressure is 0.1MPa, and in described eutectic solvent and described ethanol water mixed solution, the mass ratio of moisture is 20:1; Described eutectic solvent is choline chloride 60 and urea admixture composition, and its weight ratio is 1:2.Described complexing still kettle volume 3 cubic metres, aspect ratio is 2:1.
Distillation phase temperature is 80 DEG C, distillation staged pressure is 0.1MPa, the moisture that distillation terminates in rear ethanol water mixed solution and the complex liquid pump that eutectic solvent is formed are driven into evaporating kettle, and under 80 DEG C of vacuum tightnesss with 0.7MPa, decompression dehydration obtains the eutectic solvent regenerated, and recycles.
The dehydrated alcohol yield that complexing still kettle still top steams reaches 95% of theoretical amount, after testing, distill ethanol mass fraction >99.7% in the product obtained, the mass fraction of water is less than 0.3%, evaporation residue is less than 0.001%, reaches the standard of dehydrated alcohol.
Embodiment 4
95% commercially available ethanol water mixed solution is joined in complexing still kettle, adds eutectic solvent, Keep agitation 0.5 hour.Leave standstill 10 minutes.In complexing still kettle, complexing phase temperature is 20 DEG C, and complexing staged pressure is 0.1MPa, and in described eutectic solvent and described ethanol water mixed solution, the mass ratio of moisture is 15:1; Described eutectic solvent is choline chloride 60 and ethylene glycol, and its weight ratio is 1:4.Described complexing still kettle volume 3 cubic metres, aspect ratio is 2:1.
Distillation phase temperature is 80 DEG C, distillation staged pressure is 0.1MPa, the moisture that distillation terminates in rear ethanol water mixed solution and the complex liquid pump that eutectic solvent is formed are driven into evaporating kettle, and under 80 DEG C of vacuum tightnesss with 0.7MPa, decompression dehydration obtains the eutectic solvent regenerated, and recycles.
The dehydrated alcohol yield that complexing still kettle still top steams reaches 99% of theoretical amount, after testing, distill ethanol mass fraction >99.5% in the product obtained, the mass fraction of water is less than 0.5%, evaporation residue is less than 0.001%, reaches the standard of dehydrated alcohol.
Claims (4)
1. utilize eutectic solvent complexing to remove a method for moisture in ethanol water mixed solution, it is characterized in that, it comprises the following steps:
A. ethanol water mixed solution ethanol content being equaled 95% sends into complexing still kettle, the eutectic solvent that can form complex compound with water in proportion afterwards joins complexing still kettle under agitation, complexing pot temperature is 20 DEG C ~ 40 DEG C, pressure is 0.1 ~ 0.2MPa, and in described eutectic solvent and described ethanol water mixed solution, the mass ratio of moisture is 15 ~ 20:1;
Described eutectic solvent is the eutectic solvent that quaternary ammonium salt and hydrogen bond donor are formed, described quaternary ammonium salt is one in Dodecyl trimethyl ammonium chloride, choline chloride 60, beet alkali hydrochlorate, palmityl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride and chitosan quaternary ammonium salt or it is composite, and described hydrogen bond donor is one in urea, glycerine and ethylene glycol or it is composite;
B. in described step a, the complex liquid that moisture in described ethanol water mixed solution and eutectic solvent are formed is after distillation terminates, be driven into complex liquid storage tank, be sent to follow-up decompression dehydration operation afterwards in evaporating kettle, remove moisture in complex liquid, the eutectic solvent obtaining regenerating is for complexing next time;
Complex liquid pump in complex liquid storage tank in step b is squeezed into evaporating kettle by c, before entering evaporating kettle, heater via heats, temperature be 70 DEG C ~ 90 DEG C, vacuum tightness removes moisture under being the condition of 0.5MPa ~ 0.8MPa, the moisture that evaporating kettle still top is flowed out is used for the complex liquid that preheating enters evaporating kettle;
D. the dewatered eutectic solvent stayed in evaporating kettle is sent to complexing still kettle to recycle.
2. utilize eutectic solvent complexing to remove the method for moisture in ethanol water mixed solution as claimed in claim 1, it is characterized in that, in described step c, Heating temperature is 75 DEG C ~ 85 DEG C.
3. utilize eutectic solvent complexing to remove the method for moisture in ethanol water mixed solution as claimed in claim 2, it is characterized in that, in described step c, Heating temperature is 80 DEG C.
4. utilize eutectic solvent complexing to remove the method for moisture in ethanol water mixed solution as claimed in claim 1, it is characterized in that, the service temperature in the complexing still kettle of described step a is 30 DEG C, pressure 0.1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310436608.4A CN103467245B (en) | 2013-09-23 | 2013-09-23 | Method for complexing and removing water contained in ethanol and water mixed solution by utilizing eutectic solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310436608.4A CN103467245B (en) | 2013-09-23 | 2013-09-23 | Method for complexing and removing water contained in ethanol and water mixed solution by utilizing eutectic solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103467245A CN103467245A (en) | 2013-12-25 |
| CN103467245B true CN103467245B (en) | 2015-07-01 |
Family
ID=49792327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310436608.4A Active CN103467245B (en) | 2013-09-23 | 2013-09-23 | Method for complexing and removing water contained in ethanol and water mixed solution by utilizing eutectic solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103467245B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829426A (en) * | 2015-05-21 | 2015-08-12 | 济南大学 | Continuous isopropyl ether-isopropyl alcohol azeotrope extraction and rectification technology based on choline chloride/urea low-co-melting solvent |
| CN105248416A (en) * | 2015-10-30 | 2016-01-20 | 陕西省石油化工研究设计院 | Application of low-melting-point insoluble substance to green pesticide solvent and low-melting-point insoluble substance |
| CN107760739A (en) * | 2017-09-30 | 2018-03-06 | 江南大学 | A kind of new dihydrogen bond eutectic solvent and the method for combining sodium carbonate pretreated water rice straw |
| CN107970187B (en) * | 2017-12-07 | 2019-06-21 | 珀莱雅化妆品股份有限公司 | A kind of preparation method of antiallergic plant composition |
| CN108553937B (en) * | 2018-05-15 | 2020-12-25 | 广州科帆生物科技有限公司 | Natural eutectic solvent and application thereof in plant extraction |
| CN109704919A (en) * | 2018-12-28 | 2019-05-03 | 浙江工业大学 | Water-methanol based on choline chloride eutectic solvent-alcohol mixture extraction and rectification separation method |
| CN109701361A (en) * | 2019-01-28 | 2019-05-03 | 辽宁科技大学 | For absorbing SO2And NO2Polyalcohol-choline eutectic solvent and preparation method |
| CN110540508B (en) * | 2019-08-30 | 2021-01-01 | 齐鲁工业大学 | Eutectic solvent and application thereof in extracting lignin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103313771A (en) * | 2010-12-30 | 2013-09-18 | 费伊肯私人有限公司 | Dehydration process that employs ionic liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2305787T3 (en) * | 2003-07-21 | 2008-11-01 | Basf Se | METHOD TO REMOVE IMPURITIES USING IONIC LIQUIDS. |
-
2013
- 2013-09-23 CN CN201310436608.4A patent/CN103467245B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103313771A (en) * | 2010-12-30 | 2013-09-18 | 费伊肯私人有限公司 | Dehydration process that employs ionic liquid |
Non-Patent Citations (1)
| Title |
|---|
| 络合萃取蒸馏法制备无水乙醇的工业生产技术;赵辉等;《西南民族学院学报自然科学版》;20001130;第26卷(第4期);第414-417页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103467245A (en) | 2013-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103467245B (en) | Method for complexing and removing water contained in ethanol and water mixed solution by utilizing eutectic solvent | |
| KR102535196B1 (en) | Manufacturing method and application of highly active lignin and by-product furfural | |
| CN103756787A (en) | Method for extracting essential oil from wood processing waste Chinese fir chips to co-produce chemical method activated carbon | |
| CN103435577A (en) | Method for preparing levulinic acid and co-producing gamma-valerolactone from biomass | |
| CN103012335A (en) | Method for co-producing furfural and 5-hydroxymethylfurfural by using lignocellulose-containing biomass | |
| CN104045518A (en) | Preparation method of 2-methyl-3-butyne-2-ol | |
| CN101429288A (en) | Method for treating process liquid generated in production process of polyphenylene sulfide | |
| CN103570568A (en) | Clean production process of glycine in coproduction with ammonium chloride | |
| CN103626642A (en) | Method for preparing vanillin | |
| CN105498801A (en) | Preparation method of sulfated carbonized corn cob catalyst and method for preparing furfural from xylose in presence of catalyst | |
| CN101880329B (en) | Method for preparing plant hemicellulose hydrolysis liquid and method for extracting xylose and arabinose | |
| CN102442917A (en) | Energy-saving and environment-friendly method for producing glycin based on chloroacetic acid method | |
| CN101948400B (en) | Preparation method of methyl anthranilate | |
| WO2018085174A1 (en) | Process for the recovery of furfural | |
| CN106750360A (en) | A kind of method of the reverse solution system separating lignin of utilization alkali ionic liquid | |
| CN102659088A (en) | Water-phase synthesis method of sodium azide | |
| CN104710285A (en) | Method for recycling ethylene glycol monomethyl ether | |
| CN102627551B (en) | Method for isomerizing rosin resin acid promoted by solid super acid | |
| CN114108350A (en) | Method for quickly separating main components of wood biomass by using eutectic solvent | |
| CN104529746A (en) | Method for synthesizing dimer acid by compounding catalyst | |
| CN105175746B (en) | A kind of homogeneous transesterification method of modifying of wood fibre | |
| CA3039603A1 (en) | Process for the recovery of furfural | |
| CN104557812A (en) | Method for producing furfural from biomass | |
| CN102899089B (en) | Production process for soft montan wax | |
| CN105669609B (en) | A kind of formic acid of tetrahydrofuran 2 industrializes Racemic of N |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Feng Danhua Inventor after: Song Liying Inventor before: Feng Danhua Inventor before: Song Liying Inventor before: Other inventor requests not to publish the name |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: FENG DANHUA SONG LIYING OTHER INVENTORS HAVE WAIVED THE RIGHT TO BE MENTIONED TO: FENG DANHUA SONG LIYING |
|
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Feng Danhua Inventor after: Song Liying Inventor after: Other inventor requests not to publish the name Inventor before: Song Liying Inventor before: Other inventor requests not to publish the name |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: SONG LIYING OTHER INVENTORS HAVE WAIVED THE RIGHT TO BE MENTIONED TO: FENGDANHUA SONG LIYING OTHER INVENTORS HAVE WAIVED THE RIGHT TO BE MENTIONED |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent for invention or patent application | ||
| CI01 | Correction of invention patent gazette |
Correction item: First inventor Correct: Feng Shubo False: The inventor has waived the right to be mentioned Number: 26 Volume: 31 |
|
| CI02 | Correction of invention patent application |
Correction item: First inventor Correct: Feng Shubo False: The inventor has waived the right to be mentioned Number: 26 Page: The title page Volume: 31 |
|
| ERR | Gazette correction |
Free format text: CORRECT: THE FIRST INVENTOR; FROM: REQUEST TO WITHHOLD NAME TO: FENG SHUBO |