CN100509727C - Method for separating purifying polyatomic alcohol - Google Patents
Method for separating purifying polyatomic alcohol Download PDFInfo
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- CN100509727C CN100509727C CNB2007100366639A CN200710036663A CN100509727C CN 100509727 C CN100509727 C CN 100509727C CN B2007100366639 A CNB2007100366639 A CN B2007100366639A CN 200710036663 A CN200710036663 A CN 200710036663A CN 100509727 C CN100509727 C CN 100509727C
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Abstract
The invention discloses a separating purifying method of low-grade polyol, which is characterized by the following: utilizing reacting-extracting coupled method to separate and purify low-grade polyol; selecting the reactant from C1-C6 fat aldehydo; making the extract as five-element or six-element cycloaliphatic ring or five-element or six-element cycloaliphatic ring substituted by C1-C6 alkyl; obtaining the low-grade polyol as C2-C6 binary or ternary alcohol or composition; protecting manufacturing equipment from eroding; recycling aldehydes in the water-phase; saving the cost obviously.
Description
Technical field
The present invention relates to a kind of separation purification method of polyvalent alcohol, specifically, relate to and a kind ofly preparing in the fermented liquid or reaction solution of lower polyol by fermentation method or chemical synthesis continuously, utilize the method for reaction-extraction coupling process separation and purification lower polyol.
Background technology
Lower polyol such as ethylene glycol, propylene glycol, butyleneglycol etc. are broad-spectrum Elementary Chemical Industry raw materials.Particularly 1, and ammediol (1,3-PDO) be the raw material of the Poly(Trimethylene Terephthalate) of production performance excellence.
So far, the preparation lower polyol obtains method fermentation method and chemical synthesis.To prepare 1, ammediol is an example, and chemical synthesis is to be raw material with oxyethane, under catalyst action, with synthetic gas (CO/H
2) reaction, generate the 3-hydroxy propanal, again the 3-hydroxy propanal is made 1 through shortening, ammediol; Fermentation method is to be substrate with glycerine or glucose, through Cray Bai Shi pneumobacillus (Klebsiella pneumoniae), Fu Shi lemon bacterium (Citrobacter freundii) or clostridium butyricum strain fermentations such as (Clostridium butyricum) obtain 1, ammediol.No matter be fermentation method or chemical synthesis, the concentration of its product all lower (generally below the 150g/L reaction solution), and also comprise some by products, as monohydroxy-alcohol, acid (chemical synthesis) and thalline and remaining (fermentation methods) such as substratum.Therefore, how efficiently, at low cost from low concentration solution the separation and purification lower polyol become this area research focus.
ZL 200410038300.5 and CN1634823A disclose reaction-extraction coupled method separation and purification 1, the method for ammediol of adopting.The defective of its existence is: (a) since used aldehyde compound not only as reagent but also as extraction agent, the consumption in leaching process is big, and in the system for a long time the circulation, easily be oxidized to corresponding carboxylic acid, cause production unit easily to be corroded.(b) these aldehyde compounds of Shi Yonging all have certain solubleness in water, need be reclaimed with the method for rectifying, have increased production cost.In addition, also there are problems such as sticking wall and coking in the disclosed method of CN1634823A, influences 1, the efficient of ammediol separation and Extraction.
Summary of the invention
The object of the invention is, the method for separation and purification lower polyol in a kind of reaction solution that is prepared polyvalent alcohol by fermentation method or chemical synthesis is provided, and overcomes the defective that exists in the prior art.That is: (a) in whole separation and purification process, the aldehyde compound consumption is excessive, and easily be oxidized to corresponding carboxylic acid, cause the corrosion of production unit; (b) the aqueous phase aldehyde compound need reclaim, and causes the separation and purification running cost to increase, and has defectives such as sticking wall and coking in the separation and purification process.
The said method that is prepared separation and purification lower polyol in the fermented liquid of polyvalent alcohol or the reaction solution continuously by fermentation method or chemical synthesis of the present invention comprises the steps:
(1) fermented liquid or the reaction solution (being got by chemical synthesis) that at first will contain lower polyol places the reaction, extraction device, and its pH value transferred to 1～5, in this reaction, extraction device, add reagent and extraction agent then, at 10～60 ℃ of two-phase things that must form by organic phase and water of reaction 10 minutes～3 hours down; At this moment, lower polyol and reaction reaction generate acetal, be extracted the agent extraction simultaneously and enter organic phase, and aqueous phase almost detects the existence less than reagent (aldehyde compound).
(2) enter rectifying tower by the organic phase of step (1) gained and separate, the cat head fraction of rectifying tower enters the extraction agent rectifying tower to be separated again, and the cat head of extraction agent rectifying tower and tower stilling part is reagent and extraction agent respectively, can be recycled; Tower stilling part of rectifying tower is placed hydrolysis reactor, under the condition that strongly acidic ion-exchange resin catalyst exists, reaction is hydrolyzed, the mol ratio of the product of water and lower polyol and reaction reaction (acetal) is (1～10): 1,80～150 ℃ of hydrolysis temperatures, reagent (aldehyde compound) is derived from hydrolysis reactor top, returns in the reaction, extraction device to recycle; Hydrolysate gets product (lower polyol) after rectifying separation;
Wherein: contain fermented liquid need pre-treatment (removing thalline) before separation and purification of lower polyol as adopting flocculation or supercentrifugal process through removing thalline; Said lower polyol is C
2～C
6Binary or trivalent alcohol, or its mixture; Said reagent is C
1～C
6Alkanoic; Said extraction agent is five yuan or hexavalent cycloaliphatic ring, or by C
1～C
6Five yuan or hexavalent cycloaliphatic ring alkane that alkyl replaces.
In a preferred version of the present invention, the mol ratio of lower polyol and reagent is 1: (1～10), said reagent are C
3～C
6Alkanoic, better reagent is butyraldehyde-n, isobutyric aldehyde, valeraldehyde or isovaleric aldehyde;
In another preferred version of the present invention, extraction agent with contain the fermented liquid of lower polyol or the volume ratio of reaction solution (being got by chemical synthesis) is 1: (0.1～5), better volume ratio are 1: (1～5); Said extraction agent is five yuan or hexa-atomic cycloaliphatic ring alkane or by C
1～C
3The hexa-atomic cycloaliphatic ring alkane that alkyl replaces;
In another preferred version of the present invention, said lower polyol is C
2～C
4Binary or trivalent alcohol, or its mixture; The lower polyol ethylene glycol, 1 that is more preferred from, 2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3 butylene glycol, 2,3-butyleneglycol or glycerol, or its two or more mixture.
In addition, in the present invention, the reaction, extraction device that recommendation is used is 3～10 perforated-plate extraction tower, pulse perforated-plate extraction tower, vibrating sieve plate extraction tower, turntable extracting tower or pulsed packed tower as number of transfer unit; The hydrolysis reactor of recommending to use is stirred-tank reactor or tubular reactor.
Adopt the polyvalent alcohol that technique scheme obtained, its purity is more than 99.5wt%.The present invention can overcome in the prior art and exists (a) in whole separation and purification process, and the aldehyde compound consumption is excessive, and easily is oxidized to corresponding carboxylic acid, causes the corrosion of production unit; (b) the aqueous phase aldehyde compound need reclaim (and in the present invention, aqueous phase almost detects the existence less than reagent (aldehyde compound)), causes the separation and purification running cost to increase, and has defectives such as sticking wall and coking in the separation and purification process.
Description of drawings
Fig. 1 is the schematic flow sheet of continuous separating purifying polyatomic alcohol from fermented liquid or chemosynthesis reaction liquid
The part nomenclature is as follows among Fig. 1:
5-reaction, extraction device, 6-acetal rectifying tower, 9-extraction agent rectifying tower, 13-hydrolysis reactor, 19-product rectifying tower.
Embodiment
Referring to accompanying drawing 1, the present invention is achieved in that
Polyvalent alcohol fermented liquid or chemical method synthesis reaction solution through pre-treatment (as flocculation, high speed centrifugation etc.) enter reaction, extraction device 5 through managing 1, the aldehyde reactant that reclaims enters from the middle part of reaction, extraction device 5, and the extraction agent of recovery enters from the bottom of reaction, extraction device 5.Organic phase after the extraction (cyclic acetal and the aldehyde reactant that contain extraction agent, reaction generation) flows out from the top of reaction, extraction device, enter acetal rectifying tower 6, raffinate (not containing polyvalent alcohol and aldehyde reactant substantially) flows out the decontaminated water treatment system from the bottom of reaction, extraction device 5 through managing 3.In acetal rectifying tower 6, atmospheric distillation, reflux ratio 0.5～10, cat head goes out aldehyde reactant and extraction agent, enters in the extraction agent rectifying tower 9 through managing 8; The tower still is a cyclic acetal, enters hydrolysis reactor 13 through managing 7.In extraction agent rectifying tower 9, aldehyde reactant separates with extraction agent, and cat head goes out aldehyde reactant, through manage 10 and the aldehydes that produces of hydrolysis reactor 13 merge, get back in the reaction, extraction device 5 through managing 11; The tower still of extraction agent rectifying tower 9 is an extraction agent, gets back in the reaction, extraction device 5 through pump 12, pipe 4.In hydrolysis reactor 13, be introduced into highly acidic resin in advance and make catalyzer, additional water (with the mol ratio of cyclic acetal be 1) enter hydrolysis reactor 13 from managing 16, the aldehyde reactant that reaction produces, merges with pipe 10 behind condenser 15 from managing 14.Hydrolyzed solution enters product rectifying tower 19 from managing 17 through pump 18, carries out rectification under vacuum, and pressure is 1～40kPa, reflux ratio 1～20; Water goes out from cat head, gets back to hydrolysis reactor 13 through managing 20, and tower still polyvalent alcohol product flows out through managing 21.
To originally being further elaborated, its purpose only is better to understand content of the present invention below by embodiment.Therefore, the cited case does not limit protection scope of the present invention:
Form (fermentative Production 1, ammediol) through pretreated fermented liquid: 1, ammediol 62g/L, 2,3-butyleneglycol 15g/L, ethanol 5g/L, soluble protein 0.5g/L, OD value 6.0, pH7.0.
(1) will be 4.0 with sulfuric acid or hydrochloric acid adjust pH through pretreated fermented liquid.
(2) fermented liquid is entered from reaction, extraction device top, reactant butyraldehyde-n (comprise additional with reclaim) enters from the middle part of reaction, extraction device.The mol ratio of polyvalent alcohol is 2.0: 1.0 in the amount of reagent butyraldehyde-n and the feed liquid, the extraction agent methylcyclohexane enters from the bottom of reaction, extraction device, (extraction agent and material liquid volume are than (0.2～3.0: 1) to be in a ratio of 0.5, organic phase flows out from the top of reaction, extraction device, and temperature is 30～40 ℃ in the reaction, extraction device.The reaction, extraction device adopts turntable extracting tower, 5 grades of extractions.1, ammediol, 2, the transformation efficiency of 3-butyleneglycol are all more than 99%, and the rate of recovery of acetal in organic phase is more than 98%.Aqueous phase has only 0.04% butyraldehyde, does not contain methylcyclohexane.
(3) organic phase in the step (1) is squeezed into the cyclic acetal rectifying tower continuously, interior dress wire packing, stage number 20, reflux ratio 0.4,85 ℃ of tower top temperatures, cat head goes out reagent butyraldehyde and toluene, and the tower still is a cyclic acetal, and content is more than 99%.
(4) with the cat head material in the step (2), enter the extraction agent rectifying tower, interior dress wire packing, atmospheric distillation, number of theoretical plate 50, reflux ratio 2.0,77 ℃ of tower top temperatures, cat head distillates butyraldehyde-n, and the tower still is a methylcyclohexane, returns the reaction, extraction device and recycles.
(5) squeeze into the cyclic acetal in the step (2) in the hydrolysis reactor continuously, replenish the water (water is Yu the mol ratio of diox) of 1:1, enter in the hydrolysis reactor with round-robin water (2: 1), hydrolysis reactor adopts the stirring tank formula, residence time 1h, in have strong acid type ion-exchange resin (HD-8) to make catalyzer, 120 ℃ of hydrolysis temperatures.The butyraldehyde that hydrolysis produces comes out from the reactor top, returns the reaction, extraction device after condensation.The hydrolysis conversion of cyclic acetal is more than 99%.
(6) hydrolysate in the step (4) is entered the product rectifying tower continuously from the middle part, interior dress wire packing, stage number 50, rectification under vacuum, pressure is 1～40kPa, reflux ratio 5,43 ℃ of tower top temperatures.Cat head water outlet, tower still are 1, the mixture of ammediol and 2,3-butyleneglycol.Separate through follow-up rectifying tower again, go out 2 from cat head, 3-butyleneglycol product, purity is at 99.5wt%, and the tower still is 1, the ammediol product, purity is more than the 99.7wt%.
Embodiment 2
Form (fermentative Production 2,3-butyleneglycol) through pretreated fermented liquid: 2,3-butyleneglycol 84g/L, 3-oxobutanol 10.5g/L, glucose 18g/L, pH7.0.
(1) will be 3.0 with sulfuric acid or hydrochloric acid adjust pH through pretreated fermented liquid.
(2) fermented liquid is entered from reaction, extraction device top, reactant butyraldehyde-n (comprise additional with reclaim) enters from the middle part of reaction, extraction device.The mol ratio of polyvalent alcohol is 2.0: 1.0 in the amount of reagent butyraldehyde-n and the feed liquid, the extraction agent methylcyclohexane enters from the bottom of reaction, extraction device, (extraction agent and material liquid volume are than (0.2～3.0: 1) to be in a ratio of 0.5, organic phase flows out from the top of reaction, extraction device, and temperature is 30～40 ℃ in the reaction, extraction device.The reaction, extraction device adopts turntable extracting tower, 5 grades of extractions.2, the transformation efficiency of 3-butyleneglycol is all more than 99%, and the rate of recovery of cyclic acetal in organic phase is more than 98%.Aqueous phase has only 0.05% butyraldehyde, does not contain methylcyclohexane.
(3) organic phase in the step (1) is squeezed into the cyclic acetal rectifying tower continuously, interior dress wire packing, stage number 20, reflux ratio 0.4,80 ℃ of tower top temperatures, cat head goes out reagent butyraldehyde and extraction agent toluene, and the tower still is a cyclic acetal, and content is more than 99%.
(4) with the cat head material in the step (2), enter the extraction agent rectifying tower, interior dress wire packing, atmospheric distillation, number of theoretical plate 60, reflux ratio 2.0,77 ℃ of tower top temperatures, cat head distillates butyraldehyde-n, and the tower still is a methylcyclohexane, returns the reaction, extraction device and recycles.
(5) squeeze into the cyclic acetal in the step (2) in the hydrolysis reactor continuously, replenish the water (mol ratio of water and cyclic acetal) of 1:1, (2:1) enters in the hydrolysis reactor with round-robin water, hydrolysis reactor adopts the stirring tank formula, residence time 1h, in have strong acid type ion-exchange resin (D72) to make catalyzer, 110 ℃ of hydrolysis temperatures.The butyraldehyde that hydrolysis produces comes out from the reactor top, returns the reaction, extraction device after condensation.The hydrolysis conversion of cyclic acetal is more than 99%.
(6) hydrolysate in the step (4) is entered the polyvalent alcohol rectifying tower continuously from the middle part, interior dress wire packing, stage number 50, rectification under vacuum, pressure is 1～40kPa, reflux ratio 5,43 ℃ of tower top temperatures.Cat head water outlet, tower still are 2,3-butyleneglycol, and purity is more than the 99.7wt%.
Chemical method synthetic 1, ammediol solution (containing 1, ammediol 10.5wt%).
(1) with chemical method synthetic 1, the ammediol dilute solution is 2.5 with sulfuric acid or hydrochloric acid adjust pH.
(2) with 1, the ammediol dilute solution enters from reaction, extraction device top, and reactant isobutyric aldehyde (comprise additional with reclaim) enters from the middle part of reaction, extraction device.In the amount of reagent butyraldehyde-n and the feed liquid 1, the mol ratio of ammediol is 2.0: 1.0, the extraction agent hexanaphthene enters from the bottom of reaction, extraction device, (extraction agent and material liquid volume are than (0.2～3.0: 1) to be in a ratio of 0.6, organic phase flows out from the top of reaction, extraction device, and temperature is 30～40 ℃ in the reaction, extraction device.The reaction, extraction device adopts turntable extracting tower, 6 grades of extractions.1, the transformation efficiency of ammediol is all more than 98%, and the rate of recovery of cyclic acetal in organic phase is more than 98%.Aqueous phase has only 0.03% isobutyric aldehyde, hexanaphthene 0.01%.
(3) organic phase in the step (1) is squeezed into the cyclic acetal rectifying tower continuously, interior dress wire packing, stage number 30, reflux ratio 1.0,75 ℃ of tower top temperatures, cat head goes out reagent isobutyric aldehyde and extraction agent hexanaphthene, and the tower still is a cyclic acetal, and content is more than 99%.
(4) with the cat head material in the step (2), enter the extraction agent rectifying tower, interior dress wire packing, atmospheric distillation, number of theoretical plate 60, reflux ratio 2.0,66 ℃ of tower top temperatures, cat head distillates isobutyric aldehyde, and the tower still is a hexanaphthene, returns the reaction, extraction device and recycles.
(5) squeeze into the cyclic acetal in the step (2) in the hydrolysis reactor continuously, replenish 1: 1 water (mol ratio of water and cyclic acetal), enter in the hydrolysis reactor with round-robin water (2: 1), hydrolysis reactor adopts the stirring tank formula, residence time 1h, in have strong acid type ion-exchange resin (Amberlyst15) to make catalyzer, 100 ℃ of hydrolysis temperatures.The isobutyric aldehyde that hydrolysis produces comes out from the reactor top, returns the reaction, extraction device after condensation.The hydrolysis conversion of cyclic acetal is more than 99.5%.
(6) hydrolysate in the step (4) is entered the polyvalent alcohol rectifying tower continuously from the middle part, interior dress wire packing, stage number 50, rectification under vacuum, pressure is 1～40kPa, reflux ratio 4,43 ℃ of tower top temperatures.Cat head water outlet, tower still are 1, ammediol, and purity is more than the 99.8wt%.
To variant production, carry out separation and purification (separation and purification condition except that reagent and extraction agent other all identical) with different reagents and extraction agent with embodiment, separation and purification the results are shown in Table 1.
Table 1
Claims (8)
1, a kind of method that is prepared separation and purification lower polyol in the fermented liquid of polyvalent alcohol or the reaction solution continuously by fermentation method or chemical synthesis is characterized in that said method comprises the steps:
(1) fermented liquid or the reaction solution that at first will contain lower polyol places the reaction, extraction device, and its pH value transferred to 1～5, in this reaction, extraction device, add reagent and extraction agent then, at 10 ℃～60 ℃ two-phase things that must form by organic phase and water of reaction 10 minutes～3 hours down;
(2) enter rectifying tower by the organic phase of step (1) gained and separate, the cat head fraction of rectifying tower enters the extraction agent rectifying tower to be separated again, and the cat head of extraction agent rectifying tower and tower stilling part are respectively reagent and extraction agent, can be recycled; Tower stilling part of rectifying tower is placed hydrolysis reactor, under the condition that strongly acidic ion-exchange resin catalyst exists, reaction is hydrolyzed, the mol ratio of the product of water and lower polyol and reaction reaction is (1～10): 1,80 ℃～150 ℃ of hydrolysis temperatures, reagent is derived from hydrolysis reactor top, returns in the reaction, extraction device to recycle; Hydrolysate gets product after rectifying separation;
Wherein: the fermented liquid that contains lower polyol needs before separation and purification through removing the pre-treatment of thalline; Said lower polyol is C
2～C
6Binary or trivalent alcohol; Said reagent is C
1～C
6Alkanoic; Said extraction agent is five yuan or hexavalent cycloaliphatic ring alkane, or by C
1～C
6Five yuan or hexavalent cycloaliphatic ring alkane that alkyl replaces.
2, the method for claim 1 is characterized in that, wherein the mol ratio of lower polyol and reagent is 1: (1～10).
3, method as claimed in claim 1 or 2 is characterized in that, wherein said reagent is C
3～C
6Alkanoic.
4, method as claimed in claim 3 is characterized in that, wherein said reagent is butyraldehyde-n, isobutyric aldehyde, valeraldehyde or isovaleric aldehyde.
5, the method for claim 1 is characterized in that, wherein extraction agent with contain the fermented liquid of lower polyol or the volume ratio of reaction solution is 1: (0.1～5).
As claim 1 or 5 described methods, it is characterized in that 6, wherein said extraction agent is a hexa-atomic cycloaliphatic ring alkane or by C
1～C
3The hexa-atomic cycloaliphatic ring alkane that alkyl replaces.
As claim 1,2 or 5 described methods, it is characterized in that 7, wherein said lower polyol is C
2～C
4Binary or trivalent alcohol.
8, method as claimed in claim 7 is characterized in that, wherein said lower polyol is an ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3 butylene glycol, 2,3-butyleneglycol or glycerol.
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| KR102237801B1 (en) * | 2009-06-04 | 2021-04-07 | 게노마티카 인코포레이티드 | Process of separating components of a fermentation broth |
| CN101898935A (en) * | 2010-07-09 | 2010-12-01 | 华东理工大学 | Method for extracting and separating 1,3-propylene glycol from fermentation liquor |
| CN102320922B (en) * | 2011-07-11 | 2013-08-28 | 华东理工大学 | Method for continuously separating 2, 3-butanediol from fermentation liquor |
| CN106866366B (en) * | 2015-12-12 | 2020-05-05 | 中国科学院大连化学物理研究所 | Method for removing dihydric alcohol or polyhydric alcohol impurities in ethylene glycol and increasing yield of ethylene glycol |
| CN114085128B (en) * | 2021-10-28 | 2024-02-20 | 中国科学院过程工程研究所 | Method for separating and purifying 1,2,4-butanetriol based on difunctional ionic liquid |
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| Title |
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| 发酵液中低浓度l,3-丙二醇浓缩提纯工艺研究进展. 周鹏，方云进.化学与生物工程，第2期. 2005 |
| 发酵液中低浓度l,3-丙二醇浓缩提纯工艺研究进展. 周鹏，方云进.化学与生物工程，第2期. 2005 * |
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Assignee: Zhangjiagang Huamei Bio-material Co., Ltd. Assignor: East China University of Science and Technology Contract record no.: 2011320000660 Denomination of invention: Method for separating purifying polyatomic alcohol Granted publication date: 20090708 License type: Exclusive License Open date: 20070926 Record date: 20110505 |