CN102249848A - Preparation method of absolute ethanol - Google Patents
Preparation method of absolute ethanol Download PDFInfo
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- CN102249848A CN102249848A CN2010101789384A CN201010178938A CN102249848A CN 102249848 A CN102249848 A CN 102249848A CN 2010101789384 A CN2010101789384 A CN 2010101789384A CN 201010178938 A CN201010178938 A CN 201010178938A CN 102249848 A CN102249848 A CN 102249848A
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Abstract
The invention relates to a preparation method of absolute ethanol. The preparation method comprises the following steps of: mixing macromolecular water absorption resin and 95 percent ethanol solution in a mass ratio of 1:6-1:2, performing constant temperature treatment for 30 to 150 minutes at the temperature of between 40 and 70 DEG C, filtering the macromolecular water absorption resin, and performing regeneration to obtain filtrate which is more than 99.5 percent absolute ethanol. By the method, the energy consumption for preparing the absolute ethanol by ethanol concentration and the discharge of waste water can be greatly reduced; and the method is simple in equipment, short in operation flow and low in treatment cost. Meanwhile, the macromolecular water absorption resin can be regenerated, the regeneration method is simple and feasible, and the macromolecular water absorption resin can be reused and is suitable for further concentration and recycle of organic waste solution of water-soluble methanol, ethanol, acetone and the like.
Description
Technical field
The present invention relates to a kind of preparation method of dehydrated alcohol, can cut down ethanol in a large number and concentrate carbonic acid gas and the discharge of wastewater of producing in the dehydrated alcohol process, belong to the energy-saving and emission-reducing technique of alcohol production.
Background technology
Ethanol is very easily water-soluble, it is the organic solvent that typically is difficult to water sepn, generally the ethanol in the fermented liquid is made water content dehydrated alcohol (the ethanol volumetric concentration is greater than 99.5%) seldom and will be occupied 50%～80% of energy consumption in the whole ethanol production process, and wherein most of energy consumption all occurs in 85% alcoholic acid and further concentrates.Because of there is lower azeotropic point in the alcohol-water system, adopt the prepared ethanol of usual way rectifying again, its ethanol volumetric concentration generally can be greater than 95.57%.
Ethanol with higher concentration concentrates the preparation dehydrated alcohol, and traditional method mainly adopts azeotropic distillation.Qin Ruibing is (Sichuan non-ferrous metal magazine in " edible ethanol adds the rectifying of benzene azeotropic column plate and produces the SILVER REAGENT dehydrated alcohol ", the third phase in 1998,28-33) disclosing based on the ethanol volumetric concentration is 96.8% edible ethanol, add the rectifying of benzene azeotropic column plate and produce the SILVER REAGENT dehydrated alcohol, the alcohol concn that obtains is more than 99%, though the dehydrated alcohol constant product quality that obtains, reliably, easy to operate, the level of automation height, but it is 2.2kWh that this method is produced the energy consumption of 1kg raw spirit, be equivalent to discharge the carbonic acid gas of 2.1934kg, water loss is 500Kg, and energy consumption and water consumption are big.Introduce in alcohol technology one book that Wuxi Light Industry College publishes, when adopting benzene sequence of constant boiling and rectification method, every production 80kg dehydrated alcohol consumes 175kg steam 370kg water.People such as E.L.Ligero are at Chem ical Engineering and Processing (2003, (42): 543-552) among the Dehydration of ethanol with salt Extractive distillation-acom parative betweenprocess with salt recovery that delivers) extracting rectifying of dehydrated alcohol is carried out computer mould and fitted calculating, this method is that spent glycol is that the moisture that solvent extracts in the ethanol obtains dehydrated alcohol, its advantage is the quality product height, be applicable to scale operation, ethylene glycol boiling point height, not volatile, loss is few, but it is big that ethylene glycol is made the solvent ratio of extraction, be generally 4: 1 the ratio of charging (solvent with), energy consumption is bigger simultaneously, and tray efficiency is low.In a word, though traditional azeotropic distillation technology maturation, energy consumption, water consume higher, bring emission amount of carbon dioxide big accordingly, and can cause environmental pollution when the entrainment agent misoperation.
There is report to come filtering and concentrating ethanol with PV (pervaporation) water permeable membrane material, can prepare the ethanol more than 99.8%, this water permeable membrane is to make the special-purpose cross linking membrane that has hydrophilic radical by hydroscopic high-molecular resin, though having changed traditional rectification method, this method prepares process of anhydrous ethyl alcohol, reduced the energy consumption of this technology itself, but because macromolecule water uptake resin water permeable membrane complicated process of preparation has increased additional energy greatly and has expended, the comprehensive cost costliness.And, therefore generally can't be directly used in the moisture that absorbs in the high concentration ethanol because hydroscopic high-molecular resin is difficult for swelling in the ethanol of high density.
Summary of the invention:
The present invention proposes a kind of method for preparing dehydrated alcohol, solved the swelling problem of hydroscopic high-molecular resin in high concentration ethanol, thereby directly concentrate ethanol with hydroscopic high-molecular resin, can cut down energy consumption and wastewater discharge that ethanol concentrates the preparation process of anhydrous ethyl alcohol in a large number, realize that energy-saving and emission-reduction and processing unit are simple, flow process is short, and processing cost is low.
The preparation method of dehydrated alcohol provided by the invention, by controlling suitable swelling suction processing condition, make hydroscopic high-molecular resin swelling in the ethanol of high density, directly absorb moisture wherein, separate the preparation dehydrated alcohol, main technical schemes is: mix greater than 95% ethanol with hydroscopic high-molecular resin and volumetric concentration, hydroscopic high-molecular resin and alcoholic acid mass ratio are 1: 6-1: 2, under 40 ℃ of-70 ℃ of temperature, constant temperature 30min-150min makes the suction of hydroscopic high-molecular resin swelling, filters out hydroscopic high-molecular resin then, recycles after regeneration, measure filtrate alcoholic acid volumetric concentration, obtain dehydrated alcohol greater than 99.5%.
In the method for the present invention, used hydroscopic high-molecular resin can be selected commercially available hydroscopic high-molecular resin for use, polymer water-absorbing resins such as, polyacrylate fine, polyvinyl alcohol or polyoxyethylene as polyacrylamide, polypropylene, optimization polypropylene Barbiturates hydroscopic high-molecular resin (commercially available).
The most preferred hydroscopic high-molecular resin of the present invention is ammonium polyacrylate-acrylamide.This hydroscopic high-molecular resin can be synthetic with aqua-solution method copolymerization well known in the art, and at first with a certain amount of vinylformic acid, dropping ammonia under cooling and stirring makes the ammonium acrylate monomer solution.Ammonium acrylate monomer solution and a certain amount of acrylamide and deionized water are placed reactor, under temperature of reaction, add pH regulator agent (NaOH), linking agent (N, N methylene-bisacrylamide) and initiator (NaHSO successively
3(NH)
4S
2O
8), in mass percent, dosage of crosslinking agent is 0.01%～10% in the reaction solution; Initiator amount is respectively 0.1%～5%; Regulate the NaOH consumption to the pH of reaction solution 9～10; Monomer (ammonium acrylate and acrylamide) total mass mark is 20%～30%, and wherein ammonium acrylate accounts for 60%～80% of monomer total mass; All the other are deionized water; With the oxygen in the nitrogen eliminating reactive system.Under polymerization temperature, react certain hour, finish polymerization process after, polymerisate promptly obtains ammonium polyacrylate-acrylamide through drying and crushing, water-intake rate is 1600g/g.The reactive polymeric temperature of above-mentioned water solution polymerization process and the conventional method of condition control design control.
In the method for the present invention, because of hydroscopic high-molecular resin is difficult to swelling in the ethanol of high density, if a spot of water in the ethanol will be removed the chance that must provide hydroscopic high-molecular resin and water fully to contact, therefore key of the present invention needs the CONTROL PROCESS condition, wherein:
Described hydroscopic high-molecular resin and alcoholic acid mass ratio need be controlled at proper range, when mass ratio during less than 1: 6, hydroscopic high-molecular resin is difficult to absorb the water in the complete ethanol, when mass ratio during greater than 1: 2, resin demand is too big, and economy is bad, and secondly the hydroscopic high-molecular resin surface can adhere to more ethanol when separating, impact effect, preferred quality than scope 1: 3-1: between 2.
Described hydroscopic high-molecular resin swelling temperature need be at limited range, and when temperature was lower than 30 ℃, no matter how hydroscopic high-molecular resin and ethanol amount ratio changed, and resulting alcohol concn does not all change substantially.This mainly is because temperature when low, and hydroscopic high-molecular resin is in the alcoholic acid environment of high density, can't swelling, and temperature is when being higher than 70 ℃, the ethanol overwhelming majority becomes steam, carry portion water secretly to become steam, thereby separating effect is bad.Preferred temperature range of the present invention is 40 ℃-50 ℃.
Described hydroscopic high-molecular resin absorbent time need be at restricted portion, ion network theory according to hydroscopic high-molecular resin, the absorption of hydroscopic high-molecular resin needs certain process, at first be that hydrophilic radical and water molecules form hydrogen bond, ionization is zwitterion then, with the carrying out of dissociation processes, the electrostatic repulsion between the ion makes resin swelling.Meanwhile, the inside and outside osmotic pressure of network increases thereupon, makes water molecules further enter hydroscopic high-molecular resin, still, along with water-swelling, its three-dimensional crosslinked network structure expansion also produces corresponding elastic contractile force, and the increase of water regain, makes the inside and outside permeable pressure head of resin level off to zero gradually, elastic contractile force increases gradually, when elastic contractile force equated with anionic electrostatic repulsion, High hydrophilous resin reached the suction balance, and the preferred time range of the present invention is 30min-120min in view of the above.
By optimized combination, make hydroscopic high-molecular resin sufficient the contact be arranged above-mentioned three conditions, thereby prepare volumetric concentration greater than 99.5% dehydrated alcohol with water in the ethanol.
In the method for the present invention, the hydroscopic high-molecular resin renovation process that filters out is: the hydroscopic high-molecular resin after the suction that will leach, in concentration is in the 10%-20% salt solution, normal temperature is handled 10min-60min, leach with screen cloth then, dry or directly reuse, the hydroscopic high-molecular resin of this moment has returned to the state before the suction substantially, this renovation process is very thorough, has compared greatly advantage with common renovation process.
Effect of the present invention: the present invention initiates and has realized directly separating second alcohol and water in the ethanol concentrated solution that is difficult to water sepn with hydroscopic high-molecular resin, produce the dehydrated alcohol of concentration more than 99.5%, be 3.1Kg and produce 1Kg dehydrated alcohol water consumption, energy consumption is 1.3KWh, is equivalent to discharge the 1.296Kg carbonic acid gas.Compare with traditional rectification method, cut down carbonic acid gas and wastewater discharge in a large number, have the considerable energy saving emission reduction effect; And the inventive method is simple, and in preparation dehydrated alcohol process, temperature requirement is lower, suitability is strong, and operating process is short, and equipment is simple, the processing efficiency height, production cost is low, and hydroscopic high-molecular resin is commercially available product, and can regenerate, the simple efficient height of renovation process, the time is short, can use repeatedly repeatedly, cost is low, and techno-economic effect is remarkable.Preparation method provided by the invention is applicable to and handles methyl alcohol soluble in water, ethanol, the further concentrated reuse of organic liquid wastes such as acetone.
Embodiment:
Can better understand the present invention by following example,, also should comprise: do not departing under the scope of the invention condition conspicuous for a person skilled in the art various changes although provided these embodiment.
Embodiment 1:
Earlier synthetic ammonium polyacrylate-acrylamide hydroscopic high-molecular resin, building-up process is as follows: adopt aqua-solution method copolymerization High hydrophilous resin, at first take by weighing vinylformic acid 7.2g, dropping ammonia 1.7g under cooling and stirring makes the ammonium acrylate monomer solution.Ammonium acrylate monomer solution 8.9g, acrylamide 3.81g and 40m1 deionized water are placed reactor, under temperature of reaction, add pH regulator agent (NaOH), linking agent (N, N methylene-bisacrylamide) 0.127g successively; , initiator NaHSO
3(NH)
4S
2O
8Each 0.19g; Regulating the NaOH consumption is adjusted at 9～10 to the pH of reaction solution; With the oxygen in the nitrogen removal system.React certain hour under polymerization temperature, drying and crushing promptly obtains ammonium polyacrylate-acrylamide, and water-intake rate is 1600g/g.With ammonium polyacrylate-acrylamide hydroscopic high-molecular resin and the concentration of preparation is that 95.5% industrial alcohol mixes by mass ratio at 1: 3, under 60 ℃ of temperature, behind the constant temperature 120min, with 120 purpose screen filtrations, the alcohol concn of measuring in the filtrate reaches more than 99.7%, adsorption process current consumption is 1.3KWh, and the discharging carbonic acid gas is 1.296Kg, and the water consumption is 3.1Kg.
Embodiment 2-5:
Adopt the ammonium polyacrylate-acrylamide and the processing step of embodiment 1 preparation, control different processing condition and prepare dehydrated alcohol, listed as following table:
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Resin/ethanol mass ratio | 1∶2 | 1∶4 | 1∶5 | 1∶6 |
| Swelling temperature | 50 | 60 | 70 | 70 |
| Absorbent time | 90 | 150 | 150 | 150 |
| Filtrate ethanol concentration expressed in percentage by volume | 99.55 | 99.62 | 99.66 | 99.58 |
| Water consumption/kg | 2.8 | 3.45 | 3.76 | 3.76 |
| Power consumption/KWh | 1.18 | 1.45 | 1.58 | 1.58 |
| Carbonic acid gas/the Kg of discharging | 1.176 | 1.446 | 1.575 | 1.575 |
Embodiment 6: selecting GS-700 polyacrylate hydroscopic high-molecular resin that Nanjing Sai Pugao molecular material company limited produces and concentration for use is that 95% industrial alcohol mixes by mass ratio at 1: 2, in the time of 50 ℃, behind the constant temperature 90min, with 120 purpose screen filtrations, the alcohol concn of measuring then in the filtrate is 99.55%.Current consumption is 1.18KWh, and the discharging carbonic acid gas is 1.176Kg, and the water consumption is 2.8Kg.
Embodiment 7: the polyacrylate hydroscopic high-molecular resin of selecting the KL-III type that Rugao City section power chemical plant produces for use and concentration are that 95% industrial alcohol mixes by mass ratio at 1: 4, in the time of 60 ℃, behind the constant temperature 150min, with 120 purpose screen filtrations, the alcohol concn of measuring in the filtrate is 99.62%, adsorption process current consumption is 1.45KWh, discharging carbonic acid gas 1.446Kg, and the water consumption is 3.45Kg.
Embodiment 8: the hydroscopic high-molecular resin after the suction among the embodiment 1-5 is put into 15% salt solution soak, behind the 40min, take out with 120 purpose screen clothes, filter excessive moisture, by this renovation process, hydroscopic high-molecular resin can use repeatedly regenerates 6 times.
Embodiment 9: the hydroscopic high-molecular resin after the suction among the embodiment 6-7 is put into 20% salt solution soak, behind the 30min, take out with 120 purpose screen clothes, filter excessive moisture, press this renovation process, hydroscopic high-molecular resin can be regenerated 6 times.
Claims (7)
1. the preparation method of a dehydrated alcohol, it is characterized in that, mix greater than 95% ethanol with hydroscopic high-molecular resin and volumetric concentration, hydroscopic high-molecular resin and alcoholic acid mass ratio are 1: 6-1: 2, under 40 ℃ of-70 ℃ of temperature, constant temperature 30min-150min makes the suction of hydroscopic high-molecular resin swelling, filters out hydroscopic high-molecular resin then, recycle after regeneration, filtrate is a volumetric concentration greater than 99.5% dehydrated alcohol.
2. preparation method according to claim 1 is characterized in that used hydroscopic high-molecular resin is a polyacrylate.
3. preparation method according to claim 1 is characterized in that used hydroscopic high-molecular resin is ammonium polyacrylate-acrylamide.
4. preparation method according to claim 1 is characterized in that, described hydroscopic high-molecular resin and ethanol mass ratio are 1: 3-1: between 2.
5. preparation method according to claim 1 is characterized in that, hydroscopic high-molecular resin swelling suction temperature is 40 ℃-50 ℃.
6. preparation method according to claim 1 is characterized in that, High hydrophilous resin swelling absorbent time is 30min-120min.
7. preparation method according to claim 1, it is characterized in that, the hydroscopic high-molecular resin renovation process that filters out is: the hydroscopic high-molecular resin after the suction that will leach is in the 10%-20% salt solution in concentration, normal temperature is handled 10min-60min, leach with screen cloth then, dry or directly reuse.
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| CN2010101789384A CN102249848A (en) | 2010-05-21 | 2010-05-21 | Preparation method of absolute ethanol |
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| CN2010101789384A CN102249848A (en) | 2010-05-21 | 2010-05-21 | Preparation method of absolute ethanol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435444A (en) * | 2013-09-26 | 2013-12-11 | 天津科林泰克科技有限公司 | Method for separating methanol-water mixture |
| CN103965017A (en) * | 2014-04-04 | 2014-08-06 | 湖南尔康制药股份有限公司 | Preparation method of medicinal absolute ethyl alcohol |
| CN104774292A (en) * | 2015-04-27 | 2015-07-15 | 新疆大学 | Method for concentrating low-concentration sulfamethoxazole in water solution by using high-water-absorptivity resin |
| CN105498286A (en) * | 2015-11-30 | 2016-04-20 | 新疆大学 | Method for concentrating low-concentration sulfamethoxazole in aqueous solution by using commercially available crystal ball |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348942A (en) * | 2001-06-21 | 2002-05-15 | 北京迈胜普技术有限公司 | Molecular sieve adsorbing and dewatering process of producing absolute alcohol |
| CN101289395A (en) * | 2007-04-16 | 2008-10-22 | 比亚迪股份有限公司 | Method for preparing methyl ethyl carbonate |
-
2010
- 2010-05-21 CN CN2010101789384A patent/CN102249848A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348942A (en) * | 2001-06-21 | 2002-05-15 | 北京迈胜普技术有限公司 | Molecular sieve adsorbing and dewatering process of producing absolute alcohol |
| CN101289395A (en) * | 2007-04-16 | 2008-10-22 | 比亚迪股份有限公司 | Method for preparing methyl ethyl carbonate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435444A (en) * | 2013-09-26 | 2013-12-11 | 天津科林泰克科技有限公司 | Method for separating methanol-water mixture |
| CN103965017A (en) * | 2014-04-04 | 2014-08-06 | 湖南尔康制药股份有限公司 | Preparation method of medicinal absolute ethyl alcohol |
| CN103965017B (en) * | 2014-04-04 | 2015-07-29 | 湖南尔康制药股份有限公司 | A kind of preparation method of pharmaceutical grade anhydrous ethanol |
| CN104774292A (en) * | 2015-04-27 | 2015-07-15 | 新疆大学 | Method for concentrating low-concentration sulfamethoxazole in water solution by using high-water-absorptivity resin |
| CN104774292B (en) * | 2015-04-27 | 2017-10-24 | 新疆大学 | A kind of method of low concentration sulfamethoxazole in use high hydroscopic resin concentrated aqueous solution |
| CN105498286A (en) * | 2015-11-30 | 2016-04-20 | 新疆大学 | Method for concentrating low-concentration sulfamethoxazole in aqueous solution by using commercially available crystal ball |
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Application publication date: 20111123 |