CN109251128A - A kind of method of high efficiency, low cost concentration 1,3- propanediol fermentation liquor - Google Patents
A kind of method of high efficiency, low cost concentration 1,3- propanediol fermentation liquor Download PDFInfo
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- CN109251128A CN109251128A CN201811010014.6A CN201811010014A CN109251128A CN 109251128 A CN109251128 A CN 109251128A CN 201811010014 A CN201811010014 A CN 201811010014A CN 109251128 A CN109251128 A CN 109251128A
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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
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
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Abstract
The present invention relates to a kind of high efficiency, low cost concentrations 1, the method of 3-propanediol fermentation liquid, it successively includes: remove the solid contents such as thallus limpid 1,3-propanediol fermentation liquid, during boiling off most of moisture concentrated broth by MVR technology, in secondary steam into one absorption tower of increase before compressor, the 1,3-PD that recycling evaporation process secondary steam is taken out of.It completes that the loss late of 1,3- propylene glycol can be greatly reduced when the concentration of fermentation liquid, reducing operating cost.1,3-PD fermentation liquid is concentrated using technical solution of the present invention, the loss late of 1,3-PD is minimum to be down to 0.1% or less.
Description
Technical field
The invention belongs to field of chemical engineering, are related to a kind of method of high efficiency, low cost concentration 1,3-PD fermentation liquid,
Specifically, be related to one kind utilizes MVR technology concentration 1,3- from fermentation liquid (obtaining using glycerol as substrate through microbial fermentation)
The method of propanediol fermentation liquor.
Background technique
1,3-PD (1,3-PDO) is a kind of widely used basic chemical industry raw material, especially excellent for synthesis performance
Good polyester product PTT(polypropylene terephthalate).
So far, the method for preparing 1,3-PD is broadly divided into two major classes: one is chemical synthesis (such as epoxyethane method
With acryladehyde method etc.), due to chemical synthesis there is severe reaction conditions, the defects of side reaction is more and higher cost, from
And limit the large-scale production and application of 1,3- propylene glycol；The second is biotransformation method [using glycerol or glucose as substrate,
Through Klebsiella pneumoniae (Klebsiella pneumoniae), Freund lemon bacterium (Citrobacterfreundii) or fourth
Sour clostridium (Clostridiumbutyricum) etc. strain fermentations obtain 1,3-PD], biotransformation method is with it
Unique advantage (fermentation condition is mildly environmentally friendly) and raw materials glycerine price are significantly dropped because of the development of biodiesel
It is low, just increasingly attract people's attention.
Bioanalysis synthesis 1,3- propylene glycol fermentation liquid have following feature: (1) in fermentation liquid 1,3- propylene glycol it is dense
Spend it is lower, existing bioanalysis by glycerol fermentation synthesize 1,3-PD technology in, the 1,3-PD in fermentation liquid is dense
Spend general < 10% (wt), i.e. 100g/L.(2) there is more acylate in fermentation liquid, generally 0.5%~3% or so.(3) it sends out
Protein in zymotic fluid is other than thallus (solid content), and there are also soluble proteins.Therefore how efficiently at low cost from fermentation
Separating and extracting 1,3-propanediol becomes this field research hotspot in liquid.
In various separation methods, the isolation technics that concentration and evaporation, rectifying are combined does not introduce fermentation because process is fairly simple
Substance other than liquid component, is paid attention to.In CN206799473U, CN106748648A, CN101891591A, US
In 5254467, JP2002-155000A, in order to reduce the consumption of energy, the method evaporative removal of multiple-effect evaporation is mostly used
Most of moisture in 1,3-PD fermentation liquid, achievees the purpose that concentrated broth.Since the boiling point of 1,3- propylene glycol is
210-211 DEG C, there is different saturated vapor pressures under different temperatures, in multiple-effect evaporation operation, evaporator in the backward is secondary
The partial pressure of 1,3- propylene glycol is higher in steam.According to the difference of each effect evaporator operation pressure, 1,3-PD is in multiple-effect evaporation
Loss amount in concentration process is bigger, and about 7% ~ 15%, greatly reduce the yield of 1,3-PD.
In conclusion still have some deficits place, such as 1,3-PD in the separating technology of existing multiple-effect evaporation concentrated broth
The disadvantages of loss amount is big, steam consumption is big, the operating cost of concentration and evaporation is high, thus it is efficient in 1,3-PD fermentation liquid
The concentration technique of low cost needs to be further increased.
Summary of the invention
Present invention aims at provide a kind of method of high efficiency, low cost concentration 1,3-PD fermentation liquid, substantially to subtract
The loss late of few 1,3-PD, while the operating cost of concentration and evaporation operation is greatly reduced, overcome existing multiple-effect evaporation technology
The disadvantage that middle 1,3- propanediol losses rate is big, operating cost is high.
MVR is the abbreviation of mechanical steam recompression technology (mechanical vapor recompression), is benefit
The secondary steam and its energy generated with vapo(u)rization system itself, is promoted to height through the mechanical work of compressor for low-grade steam
The steam source of grade.It so recycles to vapo(u)rization system and thermal energy is provided, to reduce an energy conservation of the demand to outside resources
Technology.MVR mainly applies to be concentrated by evaporation material, compared with traditional multiple-effect evaporation, has power savings advantages, successfully transports at present
Utilized used in wastewater from chemical industry zero-emission, the organic concentration of sugar alcohol, pharmaceutical intermediate concentration, rectifying steam exhaust etc..Therefore, MVR is
It can be used for the concentration and evaporation of 1,3-PD fermentation liquid, but due to 1,3-PD, the 2,3-butanediol etc. in fermentation liquid
Target product due to different pressures, at a temperature of have certain saturated vapor pressure, MVR evaporation when as multiple-effect evaporation, have
More 1,3-PD, 2,3-butanediol are taken away by secondary steam, cause the loss that target product is more.
Inventor passes through the study found that the secondary steam of MVR is by gas-liquid mass transfer (contact) equipment such as absorption tower, with secondary steam
Condensate liquid or water and secondary steam carry out vapour-liquid mass, then the 1,3-PD carried secretly in secondary steam, 2,3-butanediol etc.
It is just captured down, returns in fermentation liquid liquid phase, the 1,3-PD left in the secondary steam on absorption tower is just substantially complete
Portion without, achieved the purpose that reduce 1,3-PD loss late it is big, simultaneously as use MVR technology, concentration and evaporation water
Operating cost be greatly reduced.
A kind of method of high efficiency, low cost concentration 1,3-PD fermentation liquid described in the present invention comprising following steps:
(1) the limpid fermentation liquid for removing the solid contents such as thallus boils off most of moisture by MVR technology, is concentrated 1~10 times.
(2) increase an absorption tower before compressor in step (1), have tower internals inside absorption tower.
(3) secondary steam enters from the lower part on absorption tower, and the absorbing liquid from secondary steam condensate liquid or external water is from suction
The top for receiving tower enters, and the mass ratio of absorbing liquid and secondary steam is 0 ~ 1.
(4) the tower reactor liquid in step (3) returns in evaporator.
(5) part is expelled to later separation and extracts work when the 1,3- PG concentration of fermentation liquid reaches certain value in evaporator
In sequence.
(6) condensate liquid of secondary steam exchanges heat by heat exchanger with the fermentation liquid into evaporator, recycles energy therein
Amount returns and is used for ingredient in fermentation procedure.
The loss late of 1,3- propylene glycol is minimum 0.1% in the 1,3- propylene glycol concentrate obtained by adopting the above technical scheme
Hereinafter, greatly reducing the loss late of 1,3-PD in original multiple-effect evaporation technique, and reduce operating cost.
Detailed description of the invention
Fig. 1 is the flow diagram of concentrated broth method described in the present invention
Part of icon is described as follows:
1-evaporator, 2-vapour liquid separators, 3-absorption towers, 4-compressors, 5-circulating pumps, 6-condensate pumps, 7- heat exchange
Device.
Specific embodiment
The present invention is further elaborated with reference to embodiments, purpose be only that be best understood from the contents of the present invention and
Unrestricted protection scope of the present invention.
Embodiment 1
The zymotic fluid group of thallus is removed into 1,3-PD 60g/L, 2,3-butanediol 17.5g/L, glycerol 63.6g/L is solvable
Property protein 0.5g/L, salinity 1.7%, pH6.8, flow 22644kg/h are evaporated using MVR, and the pressure of evaporator is
68kPa.An absorption tower, diameter 800mm are increased among vapour liquid separator and compressor, tower is provided with structured packing 4m,
Absorbing liquid using the condensed water of secondary steam as absorption tower, flow 600kg/h.After MVR evaporates, in concentrate
Water content is 30.1%, and the 1,3-PD loss late in concentrated broth is 0.05%.
Embodiment 2
The zymotic fluid group of thallus is removed into 1,3-PD 60g/L, 2,3-butanediol 17.5g/L, glycerol 63.6g/L is solvable
Property protein 0.5g/L, salinity 1.7%, pH6.8, flow 22644kg/h are evaporated using MVR, and the pressure of evaporator is
43kPa.An absorption tower, diameter 1000mm are increased among vapour liquid separator and compressor, tower is provided with structured packing
4m, the absorbing liquid using the condensed water of secondary steam as absorption tower, flow 800kg/h.After MVR evaporates, concentrate
In water content be 28.8%, the 1,3-PD loss late in concentrated broth is 0.08%.
Embodiment 3
The zymotic fluid group of thallus is removed into 1,3-PD 60g/L, 2,3-butanediol 17.5g/L, glycerol 63.6g/L is solvable
Property protein 0.5g/L, salinity 1.7%, pH6.8, flow 22644kg/h are evaporated using MVR, and the pressure of evaporator is
25kPa.An absorption tower, diameter 1200mm are increased among vapour liquid separator and compressor, tower is provided with structured packing
4m, the absorbing liquid using the condensed water of secondary steam as absorption tower, flow 1000kg/h.After MVR evaporates, concentrate
In water content be 27.5%, the 1,3-PD loss late in concentrated broth is 0.4%.
Embodiment 4
The zymotic fluid group of thallus is removed into 1,3-PD 60g/L, 2,3-butanediol 17.5g/L, glycerol 63.6g/L is solvable
Property protein 0.5g/L, salinity 1.7%, pH6.8, flow 22644kg/h are evaporated using MVR, and the operating pressure of evaporator is
13kPa.An absorption tower, diameter 1400mm are increased among vapour liquid separator and compressor, tower is provided with structured packing
4m, the absorbing liquid using the condensed water of secondary steam as absorption tower, flow 1000kg/h.After MVR evaporates, concentrate
In water content be 24.5%, the 1,3-PD loss late in concentrated broth is 0.9%.
Embodiment 5
The zymotic fluid group of thallus is removed into 1,3-PD 60g/L, 2,3-butanediol 17.5g/L, glycerol 63.6g/L is solvable
Property protein 0.5g/L, salinity 1.7%, pH6.8, flow 22644kg/h are evaporated using MVR, and the operating pressure of evaporator is
13kPa.After MVR evaporates, the water content in concentrate is 25.3%, and the 1,3-PD loss late in concentrated broth is
13.6%。
Claims (5)
1. a kind of method of high efficiency, low cost concentration 1,3-PD fermentation liquid, which is characterized in that remove the solid contents such as thallus
Limpid 1,3-PD fermentation liquid boils off most of moisture concentration fermentation by MVR (mechanical secondary steam recompression) method
When liquid, in secondary steam into increasing an absorption tower before compressor.
2. the method as described in claim 1, which is characterized in that equipped with selected from random packing, regular inside the absorption tower
One of filler, column plate, two or more tower internals constituted.
3. the method as described in claim 1, which is characterized in that the absorption tower top is equipped with absorbing liquid distributor, inhales
Top flow down of the liquid from tower is received, secondary steam enters absorption tower from the lower part on absorption tower, flows out absorption tower from top.
4. the method as described in claim 1,3, which is characterized in that the absorbing liquid is the condensed water of evaporator or outer
The water in portion.
5. method as claimed in claim 4, which is characterized in that the absorbing liquid and the secondary steam mass ratio into absorption tower
It is 0~1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811010014.6A CN109251128A (en) | 2018-08-31 | 2018-08-31 | A kind of method of high efficiency, low cost concentration 1,3- propanediol fermentation liquor |
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| CN201811010014.6A CN109251128A (en) | 2018-08-31 | 2018-08-31 | A kind of method of high efficiency, low cost concentration 1,3- propanediol fermentation liquor |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891591A (en) * | 2010-07-16 | 2010-11-24 | 张家港华美生物材料有限公司 | Method for separating and extracting 1,3-propylene glycol from fermentation liquor |
| CN103007553A (en) * | 2012-12-05 | 2013-04-03 | 中国科学院理化技术研究所 | Mechanical vapor recompression continuous evaporative crystallization system and method |
| CN103539299A (en) * | 2012-07-10 | 2014-01-29 | 南京大学 | Process for recycling wastewater containing low boiling-point organism such as formaldehyde and high-concentration inorganic salt |
| CN105000612A (en) * | 2015-07-22 | 2015-10-28 | 中国民用航空总局第二研究所 | Mechanical vapor recompression system of concentrated organic waste water and method |
| CN107628660A (en) * | 2017-11-03 | 2018-01-26 | 深圳市纯水号水处理科技有限公司 | A kind of high salinity waste water mechanical vapor recompresses MVR systems technologies |
-
2018
- 2018-08-31 CN CN201811010014.6A patent/CN109251128A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891591A (en) * | 2010-07-16 | 2010-11-24 | 张家港华美生物材料有限公司 | Method for separating and extracting 1,3-propylene glycol from fermentation liquor |
| CN103539299A (en) * | 2012-07-10 | 2014-01-29 | 南京大学 | Process for recycling wastewater containing low boiling-point organism such as formaldehyde and high-concentration inorganic salt |
| CN103007553A (en) * | 2012-12-05 | 2013-04-03 | 中国科学院理化技术研究所 | Mechanical vapor recompression continuous evaporative crystallization system and method |
| CN105000612A (en) * | 2015-07-22 | 2015-10-28 | 中国民用航空总局第二研究所 | Mechanical vapor recompression system of concentrated organic waste water and method |
| CN107628660A (en) * | 2017-11-03 | 2018-01-26 | 深圳市纯水号水处理科技有限公司 | A kind of high salinity waste water mechanical vapor recompresses MVR systems technologies |
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