CN103483149B - Method for preparing anhydrous ethanol based on property of magnesium chloride dihydrate - Google Patents
Method for preparing anhydrous ethanol based on property of magnesium chloride dihydrate Download PDFInfo
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- CN103483149B CN103483149B CN201310392320.1A CN201310392320A CN103483149B CN 103483149 B CN103483149 B CN 103483149B CN 201310392320 A CN201310392320 A CN 201310392320A CN 103483149 B CN103483149 B CN 103483149B
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- magnesium chloride
- ethanol
- chloride dihydrate
- alcohol
- dehydrated alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
- C07C29/92—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound by a consecutive conversion and reconstruction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing anhydrous ethanol from industrial ethanol, which comprises the following steps: solid magnesium chloride dihydrate is dissolved in industrial ethanol having a concentration of about 92wt%, thus obtaining a homogeneous hydrous-ethanol-magnesium chloride solution; the magnesium chloride dihydrate is complexed with water so as to destroy the ethanol-water azeotropic point, the hydrous-ethanol-magnesium chloride solution is subjected to simple evaporation at 70-120 DEG C, an ethanol solution having a concentration of 97wt% or above is obtained as the vapor phase, and magnesium chloride is precipitated as a magnesium chloride hexahydrate crystal part at the bottom of an evaporation kettle, thus obtaining magnesium chloride-ethanol slurry having a high water content; the 97wt% ethanol solution obtained by evaporation is further rectified, anhydrous ethanol is obtained from the tower bottom, and industrial ethanol is extracted from the tower top; the slurry is subjected to spray drying at 150-230 DEG C, so that the magnesium chloride hexahydrate and the like are dehydrolyzed into magnesium chloride dihydrate which is returned to next cycle; and the low-concentration (<50%) ethanol vapor generated by spray drying enters a rectification tower for producing industrial ethanol. The method aims to reduce energy consumption and environmental pollution in the anhydrous ethanol preparation process, and has the advantage that the magnesium chloride dihydrate is easy to recycle and reusable.
Description
Technical field
The present invention relates to the preparation of dehydrated alcohol, particularly a kind of character by magnesium chloride dihydrate and water complexing is destroyed ethanol-water azeotropic point and then is prepared the method for dehydrated alcohol.
Background technology
Industrial ethanol uses the biomass ferments such as the synthesis of ethene aquation method or sugar, corn and Chinese sorghum to produce usually.Ethanol, as a kind of important basic chemical industry raw material, is widely used in many industries such as makeup, medical science, food, pigment, electronic industry and automobile fuel.In recent years along with the fossil energies such as oil and gas are day by day exhausted, it is in widespread attention that the alcohol fuel come from biomass material fermentation cleaned recyclable fuel as one.In each purposes of current ethanol, having the call of alcohol fuel.In addition, ethanol, as the alternative conventional methyl tertiary butyl ether of oxygenation agent, reduces the discharge of objectionable impurities in vehicle exhaust.But automobile fuel requires low moisture content, otherwise can cause damage to engine.Therefore, alcohol fuel must use dehydrated alcohol (99.4-99.8wt%).
The difficult point that dehydrated alcohol is produced is that under being normal pressure, ethanol can be formed about containing the azeotrope of 95wt% ethanol with water.The boiling point of this azeotrope is 78.2 DEG C, with the boiling point 78.4 DEG C of dehydrated alcohol closely, the ethyl alcohol purification of 92wt% is accounted for the 40-60% of whole process energy consumption to dehydrated alcohol.What current industrial scale operation dehydrated alcohol adopted is the technique such as azeotropic distillation or extraction fractional distillation.
Azeotropic distillation uses three rectifying tower operated at ambient pressure usually.In the first rectifying tower, the coarse ethanol raw material of 6-10wt% is at the ethanol of tower top simmer down to 85-95wt%, and remaining moisture is discharged at the bottom of tower.Add as lower boiling entrainment agents such as benzene, hexanaphthene and pentanes in 85-95% ethanol, azeotropic distillation in Second distillation column.Entrainment agent and second alcohol and water form lower boiling ternary heteroazeotrope.At the bottom of tower, obtain required dehydrated alcohol product, tower top isolates ternary azeotrope with moisture.This ternary azeotrope is separated into two-phase at condenser: the oil phase be made up of ethanol and entrainment agent; And the aqueous phase of second alcohol and water composition.Oil phase reflux tower rectifying tower, aqueous phase is sent into the 3rd rectifying tower and is continued to be separated.The rectifying of benzene ternary azeotropic is traditional production technology of absolute alcohol by zeolite molecular sieve.But benzene has toxicity, exist environment and pollute, be entrained with the benzene of trace in dehydrated alcohol product, cause it not to be used for the high value industries such as makeup.Azeotropic distillation needs to consume mass energy in addition.
Extraction fractional distillation is different from azeotropic distillation, and what add is to dissolve each other completely extraction agent as high boiling points such as ethylene glycol, changes the relative volatility of second alcohol and water.From the ethanol of the first rectifying tower pre-concentration at Second distillation column underfeed, and high boiling extraction agent is in top charging.Dehydrated alcohol obtains from tower top as light constituent.The entrainment agent gone out from tower bottom flow is sent into the 3rd rectifying tower with water mixture and is separated.The solvent of extracting rectifying, except adopting conventional ethylene glycol, also can adopt the salts solutions such as Potassium ethanoate, sodium-chlor and calcium chloride.Compare organic reagent, salts solution polarity is larger, larger on the impact of ethanol-water system vapor-liquid equilibrium.Such as, disclose the composite extractant that a kind of use is made up of ethylene glycol and calcium chloride brine in its patent CN1323773A of people such as Duan Zhanting and prepare dehydrated alcohol method etc.But the use of salt usually brings the problems such as equipment blocking and corrosion.
In addition, also there is the method that rectification under vacuum method, membrane separation process, absorption method and ion-exchange-resin process etc. prepare dehydrated alcohol.
Rectification under vacuum method utilizes the ethanol-water system azeotropic point character that (<12.66kPa) disappears under certain vacuum degree, under low pressure rectifying ethanol-water solution, obtains dehydrated alcohol product.As Sun Defang etc. proposes at its paper " rectification under vacuum legal system is in the research of dehydrated alcohol " technique that dehydrated alcohol is produced in a kind of heat pump rectification under vacuum.Adopt a theoretical plate number 20 pieces of stuffing rectification columns, working pressure is 6.7kPa, makes the ethanol rectifying of 94.3wt% to 96.9wt%.Rectification under vacuum, owing to needing to maintain the vacuum tightness required, requires high to equipment sealing property.
Membrane separation process adopts selectively permeable membrane, make one in ethanol or water select through, reach the object of separating alcohol-water mixture.According to the difference selected by material, be divided into the Pervaporation Technology and the water vapour penetration technology selected through water selected through ethanol.Such as Xu Nan equality discloses a kind of ethanol produced from biological fermentation in patent CN1450166A, adopts infiltration evaporation and water vapour penetration Integration ofTechnology to prepare the production technique of dehydrated alcohol.3-20wt% ethanol in fermentor tank is extracted out by pump, sends into the inorganic alcohol permselective membrane of MFI-type molecular sieve.In the vacuum tightness keeping 1-5mmHg through side of alcohol permselective membrane, ethanol brings up to 40-95wt% by alcohol permselective membrane infiltration evaporation concentration.The ethanol of pre-concentration is heated to 100-150 DEG C, after vaporization, sends into NaA type molecular sieve water permeable membrane.Equally in the vacuum tightness keeping 1-5mmHg through side, infiltration removing water vapour.The dehydrated alcohol of >99.5wt% will be obtained after non-ventilation body cooling.But involving great expense of selectively permeable membrane, degradation after repeatedly using, limits the application of this technology in dehydrated alcohol suitability for industrialized production.
Absorption method uses glassware for drinking water selectively sorbent material, reaches the object dewatered from ethanol-water solution.Such as Zhong Yaling etc. have disclosed a kind of to adopt adsorbent of molecular sieve to prepare the method for dehydrated alcohol in patent CN102976893A.Alcohol-water superheated vapour is sent in adsorption tower, obtains dehydrated alcohol steam.Adsorbent reactivation realizes by being evacuated down to 6-9kPa.The shortcoming of this method is that sorbent material is expensive, and adsorbent reactivation needs high temperature (>300 DEG C) or low vacuum (<9kP) usually, increases process cost.
Ion-exchange-resin process is applied to SILVER REAGENT dehydrated alcohol more and produces.Such as patent CN102249848A mentions a kind of polystyrene acid ammonium-acrylamide macromolecule resin absorption moisture that adopts and prepares the dehydrated alcohol method that volumetric concentration is greater than 99.5%.Macromolecule resin after water suction is regenerated by put it in 10-20% salt solution and completes.Ion-exchange-resin process ubiquity output is little, alcohol loss and the defect such as labour intensity is large, is not suitable for scale operation dehydrated alcohol.
The each defectiveness of several production dehydrated alcohol method of above-mentioned introduction.The technical maturity such as azeotropic distillation and extracting rectifying, is suitable for scale operation.But energy consumption is comparatively large, economical not as alcohol fuel.And membrane separation process, the problems such as the ubiquity such as absorption method and ion exchange method technique is immature, and the little and agents useful for same of throughput is expensive.
Summary of the invention
The technology of the present invention is dealt with problems: the deficiency existed in producing for existing dehydrated alcohol, a kind of method utilizing magnesium chloride dihydrate character to prepare dehydrated alcohol is provided, reduces system energy consumption, eliminate environmental pollution, reduce production cost, make it be beneficial to large-scale industrial production.
The present invention is raw material with industrial alcohol, is mixed by magnesium chloride dihydrate with industrial alcohol, can obtain being greater than the ethanol of >97wt% and moisture higher magnesium chloride-ethanol slurries by simple step evaporation.Then the ethanol being greater than >97wt% is sent into rectifying tower and remove moisture further, prepare dehydrated alcohol.Simultaneous spray drying slurries, realize the regeneration of magnesium chloride dihydrate.
The mechanism that magnesium chloride dihydrate and ethanol-water solution react is:
MgCl
2·2H
2O+4H
2O=MgCl
2·6H
2O
Magnesium chloride dihydrate is combined with water, generates magnesium chloride hexahydrate, makes most of moisture in industrial alcohol be converted into crystal water.Meanwhile, magnesium chloride compares general organic molecule as salt larger polarity, larger to the change of ethanol and water relative volatility.Therefore the industrial alcohol concentration of about 92wt% can be realized to bring up to >97wt% by simple step evaporation, and this adopts common rectificating method to be difficult to realize.The magnesium chloride hexahydrate thermal degradation produced, to realize the regeneration of magnesium chloride dihydrate.Following is decomposition reaction corresponding under differing temps:
MgCl
2·6H
2O=MgCl
2·4H
2O+2H
2O(g) T=117℃
MgCl
2·4H
2O=MgCl
2·2H
2O+2H
2O(g) T=185℃
MgCl
2·2H
2O=MgCl
2·H
2O+H
2O(g) T=242℃
MgCl
2·H
2O=MgCl
2+H
2O(g) T=304℃
MgCl
2·H
2O=MgOHCl+H
2O(g) T=305℃
MgOHCl=MgO+HCl(g) T=554℃
Magnesium chloride dihydrate can be easy to be decomposed more than 185 DEG C by magnesium chloride hexahydrate obtain.If improve temperature further, likely can produce and there is corrosive hydrogen chloride gas.So, should drying temperature be controlled, avoid hydrogenchloride to produce.The high temperature alcohol-water steam obtained after drying can be used to heating evaporation still.
Method of the present invention is the character utilizing magnesium chloride dihydrate and water complexing, first obtain >97wt% ethanol by evaporation water-ethanol-magnesium chloride solution, then dehydrated alcohol prepared by rectifying >97wt% ethanol further, simultaneous spray drying regeneration magnesium chloride dihydrate.
Concrete technology flow process of the present invention is shown in Fig. 1, includes following steps:
(1) pass through rectifying tower 21 from ethanol raw material 1, preparation concentration is about 92wt% industrial alcohol 2;
(2) industrial alcohol 2 is sent in mixing tank 31, and be mixed into water-ethanol-magnesium chloride solution 4 with magnesium chloride dihydrate 3;
(3) water-ethanol-magnesium chloride solution 4 is added evaporative crystallization in evaporating kettle 41, obtain being greater than 97wt% ethanol 5 and the slurries 6 containing magnesium chloride hexahydrate and ethanol etc.;
(4) ethanol 5 is sent into rectifying tower 22, tower reactor obtains dehydrated alcohol product 7, overhead extraction industrial alcohol 8; Industrial alcohol 8 is returned and continues to mix with magnesium chloride dihydrate;
(5) by slurries 6 spraying dry in spray-dryer 51, magnesium chloride dihydrate powder 5 and alcohol vapour 9 is obtained;
(6) alcohol vapour 9 is returned rectifying tower 21 manufacture ethanol;
(7) magnesium chloride dihydrate 3 obtained in spray-dryer 51 is sent into mixing tank 31, enter next circulation.
In step (2), mixing tank is liquid-solid mixing tank.After mixing, Chlorine in Solution magnesium density is 10-40wt%.Be converted into crystal water as far as possible for making moisture in industrial alcohol and reduce the problem that high density chlorination magnesium ribbon carrys out difficulty of transportation, preferred concentration is 12-18wt%.
In step (3), evaporating kettle operates at ambient pressure, and temperature of reaction is 70-120 DEG C.In order to improve the concentration of the rear ethanol of evaporation, avoid magnesium chloride hexahydrate to decompose, preferable reaction temperature is 85-98 DEG C simultaneously.The preferred evaporating kettle adopting band interchanger, the alcohol-water steam waste heat making it utilize to produce in flow process.
Because the alcohol concn of charging is greater than azeotropic point in step (4), so adopt atmospheric distillation to prepare dehydrated alcohol.At the bottom of tower, extraction is not containing the dehydrated alcohol product of toxic compounds.The industrial alcohol of overhead extraction returns and two magnesium chloride dihydrate mixing, again removes moisture.
Step (5) carries out drying to slurries, sloughs second alcohol and water, and makes magnesium chloride hexahydrate be regenerated as magnesium chloride dihydrate.In order to make uniformity of temperature profile, avoiding local temperature too high, adopting spray-drying tower.Drying temperature is 150-230 DEG C.For making magnesium chloride hexahydrate at utmost be converted into magnesium chloride dihydrate, and avoid having the generation of corrosive hydrogen chloride gas, preferred drying temperature is 185-195 DEG C.
The present invention is that to utilize magnesium chloride dihydrate to have good in water complexation property, reaches the object preparing dehydrated alcohol from industrial alcohol.The method is by water-ethanol-magnesium chloride mixture single vaporization, and obtain the ethanol of concentration on azeotropic point, further rectifying obtains dehydrated alcohol.Method of the present invention has good in economic efficiency, the advantage such as non-environmental-pollution and strong operability, is easy to realize industrialization.
Advantage of the present invention and active effect exist:
(1) magnesium chloride dihydrate crystallization is magnesium chloride hexahydrate, makes most of moisture in industrial alcohol be converted into crystal water.Magnesium chloride dihydrate has very large polarity as salt further simultaneously, changes much larger than organic entrainer ethanolic soln relative volatility.Therefore industrial alcohol concentration can be realized to bring up to more than 97wt% by simple step evaporation, energy consumption needed for flow process is greatly reduced, solve current rectification method and produce the larger problem of dehydrated alcohol energy consumption.
(2) compare organic entrainers such as benzene, magnesium chloride toxicological harmless and environmental pollution, and can not be entrained in dehydrated alcohol product.The dehydrated alcohol produced can be used for the high value industries such as makeup, medicine and food.
(3) magnesium chloride dihydrate can utilize by iterative cycles wherein.Magnesium chloride dihydrate compares the regeneration such as film, adsorbent of molecular sieve and macromolecule resin easily, and repeatedly the rear performance of regeneration does not decline, and reduces cost needed for regenerative process.
Accompanying drawing explanation
Fig. 1 process flow sheet of the present invention.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
Embodiment 1
Discussing below is based on laboratory scale periodical operation
(1) taking 242g magnesium chloride dihydrate adds in 1000ml92wt% ethanol, stirs and makes it dissolve, and obtains about containing the solution of 17wt% magnesium chloride;
(2) solution that step (1) obtains is added evaporating kettle, use condensing tube condensation to reclaim ethanol.Sampling analysis obtains the concentration of ethanol at set intervals, and the relation of alcohol concn and time and temperature of reaction is in table 1.Stop evaporation when temperature of reaction is greater than 120 DEG C, obtain 700ml98.0wt% ethanol.Collect remaining slurries, obtain 400g slurries;
Table 1. alcohol concn over time
(3) use the spray-drying tower slurries that drying step (3) takes out at 190 DEG C, obtain 240g solid, return step (2) and mix with 92wt% ethanol.
Embodiment 2
Discussion is below the continuously feeding draw operation based on pilot scale
(1) by the industrial alcohol of 92.5wt% with 21.4kgmin
-1pass into mixing tank, simultaneously with 5kgmin
-1feeding rate magnesium chloride dihydrate is passed into; Obtain containing ethanol 75.0wt% after mixing, the solution of water 11.3wt% and magnesium chloride 13.7wt%.
(2) solution that step (1) obtained sends into distillation crystallization reactor, keeps wherein that solution is at boiling state, and temperature of reaction is 96.1 DEG C.With 19.5kgmin
-1speed from the alcohol vapour of top extraction 98.2wt%, from bottom with 6.9kgmin
-1speed discharges slurries;
(3) it is the rectifying tower of 50 that 98.2wt% alcohol vapour step (2) obtained sends into stage number from 31 blocks of plates.0.1atm falls in pressure tower, and bottom temperature is 80.7 DEG C, tower top temperature 78.2 DEG C.From tower reactor with 11.6kgmin
-1extraction 99.4wt% dehydrated alcohol product, tower top is with 7.94kgmin
-1take out 96.4wt% ethanol;
(4) slurries using spray-drying tower drying step (2) to obtain, drying temperature is 190 DEG C.From top with 1.91kgmin
-1the alcohol vapour of extraction 34.7wt%, from bottom with 5kgmin
-1take out magnesium chloride dihydrate.
It should be noted that, according to the various embodiments described above of the present invention, those skilled in the art are the four corners that can realize independent claim of the present invention and appurtenance completely, implementation procedure and the same the various embodiments described above of method; And non-elaborated part of the present invention belongs to techniques well known.
Applicant states, the present invention illustrates processing method of the present invention by above-described embodiment, but the present invention is not limited to the steps such as above-mentioned distillation crystallization, does not namely mean that the present invention must rely on above-mentioned steps and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (4)
1. utilize magnesium chloride dihydrate character to prepare a method for dehydrated alcohol, it is characterized in that comprising the following steps:
(1) mixed in a mixer with magnesium chloride dihydrate by industrial alcohol, magnesium chloride dihydrate concentration is 10-40wt%, obtains water-ethanol-magnesium chloride solution;
(2) water-ethanol-magnesium chloride solution is placed in evaporating kettle evaporative crystallization, vaporization temperature is 70-120 DEG C, and vapour phase obtains being greater than the ethanol of 97wt% and containing the slurries of magnesium chloride hexahydrate and ethanol;
(3) ethanol being greater than 97wt% that obtains of rectification step (2), obtains being greater than 99.4wt% dehydrated alcohol product, from overhead extraction industrial alcohol from tower reactor; Industrial alcohol is returned and mixes with magnesium chloride dihydrate;
(4) step (2) is obtained slurries spraying dry, spray drying temperature is 150-230 DEG C, obtains magnesium chloride dihydrate and the low-concentration ethanol steam being less than 50wt%; Magnesium chloride dihydrate is returned and is mixed into next circulation with industrial alcohol; Low-concentration ethanol steam sends into the rectifying tower of manufacture ethanol.
2. the method utilizing magnesium chloride dihydrate character to prepare dehydrated alcohol according to claim 1, is characterized in that: in described step (1), magnesium chloride dihydrate concentration is 12-18wt%.
3. the method utilizing magnesium chloride dihydrate character to prepare dehydrated alcohol according to claim 1, is characterized in that: the evaporation water-ethanol-magnesium chloride solution temperature in described step (2) is 85-98 DEG C.
4. the method utilizing magnesium chloride dihydrate character to prepare dehydrated alcohol according to claim 1, is characterized in that: described step (4) spray drying temperature is 185-195 DEG C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005063832A1 (en) * | 2003-12-23 | 2005-07-14 | Basell Poliolefine Italia S.R.L. | Magnesium dichloride-ethanol adducts and atalyst components obtained therefrom |
| CN101585750A (en) * | 2008-05-22 | 2009-11-25 | 中国科学院过程工程研究所 | Novel method for dehydrating low-concentration ethanol |
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2013
- 2013-09-02 CN CN201310392320.1A patent/CN103483149B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005063832A1 (en) * | 2003-12-23 | 2005-07-14 | Basell Poliolefine Italia S.R.L. | Magnesium dichloride-ethanol adducts and atalyst components obtained therefrom |
| CN101585750A (en) * | 2008-05-22 | 2009-11-25 | 中国科学院过程工程研究所 | Novel method for dehydrating low-concentration ethanol |
Non-Patent Citations (1)
| Title |
|---|
| 无水乙醇制备方法的研究进展;唐艳红 等;《中国酿造》;20091231(第206期);第4-7页 * |
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