CN106117012A - A kind of separation and recovery method of fermentation liquid electrodialysis desalination dense room liquid - Google Patents
A kind of separation and recovery method of fermentation liquid electrodialysis desalination dense room liquid Download PDFInfo
- Publication number
- CN106117012A CN106117012A CN201610450527.3A CN201610450527A CN106117012A CN 106117012 A CN106117012 A CN 106117012A CN 201610450527 A CN201610450527 A CN 201610450527A CN 106117012 A CN106117012 A CN 106117012A
- Authority
- CN
- China
- Prior art keywords
- liquid
- solid
- crystallization
- crystalline mother
- magma
- 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.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
Abstract
The separation and recovery method of the present invention a kind of fermentation liquid electrodialysis desalination dense room liquid, mainly concentrated for the first time by dense for electrodialysis room liquid, the first step crystallizes, magma first step solid-liquid separation, second step crystallization after the first crystalline mother solution cooling, magma second step solid-liquid separation, second crystalline mother solution concentrates, 3rd step crystallization, magma the 3rd step solid-liquid separation, the 4th step crystallization after the 3rd crystalline mother solution cooling, magma the 4th step solid-liquid separation, the 4th crystalline mother solution electrodialysis secondary desalination.This method can effectively process the salt in the liquid of electrodialysis dense room, obtains sodium sulfate and the succinic acid nano-crystal body of higher degree, and reclaims 1,3 propylene glycol in the liquid of dense room, by 95%, the yield of electrodialysis desalination operation 1,3 propylene glycol is brought up to 98%.
Description
Technical field
The invention belongs to biological chemical field, be specifically related to the electrodialysis desalination of Production of 1,3-Propanediol by Fermentation Method process
Technique and high content of salt, the processing method of high-COD waste water.
Background technology
1,3-PD is the important source material of many synthetic reactions, especially as producing polyester PTT (poly terephthalic acid
Propylene glycol ester) and the monomer of polyurethane.Compared with chemical method synthesis, the advantage of Production of 1,3-Propanediol by Fermentation Method is selectivity
Height, operating condition is gentle, and raw material is renewable etc., has the most become the focus that domestic and international researcher is paid close attention to.But, in micro-life
During thing Production of 1,3-Propanediol by Fermentation Method, bacterial metabolism produces while 1,3-PD, also produce succinic acid, acetic acid,
The organic acid such as lactic acid, the ammonium ion being used as in the ammonium sulfate in nitrogen source in addition in fermentation medium is consumed, and fermentation liquid pH value reduces,
In order to the pH value maintaining fermentation liquid is neutral, in sweat, by pH robot control system(RCS) toward auto-feeding NaOH solution in fermentation liquid,
Make to ferment lower tank time, the salt content in fermentation liquid is up to 2-3%.
The method of the 1,3-PD in current isolated and purified fermentation liquid mainly has two kinds, and first method is without de-
Salt, is retained in salt in material, i.e. uses the material that filtration sterilization, thickening etc. are first readily able to separate from fermentation liquid system
Separating, then 1,3-PD is extracted from saline solution system by the step such as distillation, rectification.The magnificent biology in Zhangjiagang
Materials Co., Ltd proposes a kind of method (patent CN101891591A) extracting 1,3-PD from fermentation liquid, this patent
Proposing to add glycerol in fermentation liquid (or the fermentation liquid after concentrated dehydration) prevents the salt-pepper noise in fermentation liquid from separating out, then
By techniques such as evaporation, rectification, 1,3-propylene glycol is extracted from fermentation liquid.Second method is by first after filtration sterilization
Salt is separated from fermentation liquid, then the fermentation liquid after desalination is carried out isolated and purified, extract 1,3-PD therein.Clearly
The Wang Xiaolin of Hua Da proposes the electroosmose process desalinating process (patent CN1522997A) for 1,3-PD fermentation liquid, lake
All rivers run into sea that biological engineering company limited proposes a kind of heterogeneous membrane electrodialysis desalination work for 1,3-propanediol fermentation liquor in south
Skill (patent CN101298409A), the proposition of the method makes 1,3-PD fermentation liquid electrodialysis desalination cost be substantially reduced,
Promote electric dialysis desalinating process in the industrial applications in this field.
1,3-PD fermentation liquid is after electrodialysis desalination, and salt content is reduced to 0.1～0.5%, enters downstream process and enters
One step is isolated and purified, and in desalination processes, the zwitterion in fermentation liquid enters dense room liquid through ion exchange membrane respectively so that
Salt content in the liquid of dense room is up to 5～15%, possibly together with the 1,3-PD come because of concentration difference diffusion in the liquid of the denseest room, and 1,
The infiltration capacity of ammediol accounts for 5～10% of 1,3-propylene glycol in fermentation liquid.The COD of this dense room liquid is up to 70000mg/L, directly
Processing as waste water, expense is high, but also cannot reclaim 1,3-PD therein.
Crystallization is the desalting technology of a kind of routine, also has document report to use crystal desalination technology to send out for 1,3-PD
The extraction of ferment liquid.The Liu Dehua of Tsing-Hua University proposes a kind of toward interpolation mineral acid in 1,3-PD fermentation liquid, by fermentation liquid
In acylate convert organic acid and inorganic salt after, the method (patent No. that inorganic acid salt crystallization is separated
CN101033171A).This patent has good effect for the inorganic acid salt in separation and fermentation liquid, but substantial amounts of organic acid is the most residual
Stay in fermentation liquid, affect follow-up distillation, distillation operation.
The fractional crystallization technique that the present invention proposes can organic by the liquid of 1,3-propanediol fermentation liquor electrodialysis desalination dense room
Salt and inorganic salt crystallization respectively, and crystalline mother solution is carried out secondary electrodialysis desalination, to reclaim 1,3-PD therein.
Not only solve the problem that electrodialysis dense room liquid waste water processing cost is high, also improve electrodialysis desalination process 1,3-PD and receive
Rate.
Summary of the invention
It is an object of the invention to provide a kind of separation and recovery by 1,3-propanediol fermentation liquor electrodialysis desalination dense room liquid
Method, receives the variation tendency of solubility with temperature in aqueous for sodium sulfate and succinic acid in the liquid of electrodialysis dense room and differs
The characteristic caused, it is proposed that the method for fractional crystallization, receives sodium sulfate, succinic acid and sodium acetate Crystallization Separation respectively, finally obtains
Crystalline mother solution remove remaining salt by electrodialysis again after, enter downstream process reclaim 1,3-PD therein.
Above-mentioned purpose is achieved through the following technical solutions.
The separation and recovery method of a kind of fermentation liquid electrodialysis desalination dense room liquid, mainly by the denseest for dense for electrodialysis room liquid
Contracting, first step crystallization, magma first step solid-liquid separation, second step crystallization after the first crystalline mother solution cooling, magma second step solid-liquid
Separating, the second crystalline mother solution concentrates, the 3rd step crystallization, magma the 3rd step solid-liquid separation, the 4th step after the 3rd crystalline mother solution cooling
Crystallization, magma the 4th step solid-liquid separation, the 4th crystalline mother solution electrodialysis secondary desalination, mainly comprise the steps that
(1) fermentation liquid is used in film filter and remove after somatic cells, protein through the first electrodialyzer 1 desalination, obtain
First desalinization liquor and the first dense room liquid；
(2) first dense room liquid condensing crystallizing in the first crystallizing evaporator 2, carries out first step crystallization, obtains the first magma；
(3) carry out solid-liquid separation for the first time in the first magma is sent into the first solid-liquid separator 3, obtain first crystal and the first knot
Brilliant mother solution；
(4) the first crystalline mother solution is sent into cooling in the first cooler crystallizer 4, carries out second step crystallization, brilliant by second after crystallization
Slurry carries out second time solid-liquid separation in sending into the second solid-liquid separator 5, obtain the second crystal and the second crystalline mother solution；
(5) second crystalline mother solutions concentrate in the second crystallizing evaporator 6, carry out the 3rd step crystallization, obtain the 3rd magma；
(6) the 3rd magma is sent into third time solid-liquid separation in the 3rd solid-liquid separator 7, obtain the 3rd crystal and the 3rd crystallization mother
Liquid；
(7) the 3rd crystalline mother solutions send into cooling in the second cooler crystallizer 8, carry out the 4th step crystallization, by the 4th magma after crystallization
Carry out the 4th solid-liquid separation in sending into the 4th solid-liquid separator 9, obtain four crystal and the 4th crystalline mother solution；
(8) by the 4th crystalline mother solution after heating, in delivering to the second electrodialyzer 10, carry out electrodialysis desalination, obtain second and take off
Saline solution and the second dense room liquid.
Electrodialysis desalination is carried out, the electricity of the first desalinization liquor obtained after fermentation liquid is carried out membrane filtration by described step (1)
Conductance is 1000～2000 μ s/cm, and the electrical conductivity of the first dense room liquid is 50000～100000 μ s/cm.
Described step (2) and (5) cycles of concentration 0.5～10 in the first crystallizing evaporator 2 and the second crystallizing evaporator 6
Times, the pressure of vaporizer is 40～200mmHg, and the temperature of evaporative crystallization is 60～80 DEG C.
In described step (3) and (6), in the first solid-liquid separator 3 and the 3rd solid-liquid separator 7, the temperature of solid-liquid separation is
60～80 DEG C.
In described step (4) and (7), the temperature of second step crystallization and the crystallization of the 4th step is 3～10 DEG C, second step and the 4th
The temperature of step solid-liquid separation is 2～10 DEG C.
Temperature after the heating of described step (8) the 4th crystalline mother solution is 25～35 DEG C, after the second electrodialyzer 10 desalination,
The electrical conductivity of the second desalinization liquor obtained is 1000～2000 μ s/cm.
In sum, the method for the present invention passes through Steppecd crystallization by the liquid of 1,3-PD fermentation liquid electrodialysis dense room
Salt is separated, and then the 4th crystalline mother solution uses the method for electrodialysis desalination remove salt therein, obtains after desalination
It is the most isolated and purified that second desalinization liquor and the first desalinization liquor are mixed into 1,3-PD downstream extraction technique, until obtaining end
Product 1,3-propylene glycol.
In operating process, the temperature of first step crystallization and the temperature of second step crystallization are to realize 1,3-PD electrodialysis to take off
In the liquid of salt dense room sodium sulfate and succinic acid receive separate key parameter.
The progressive effect of the present invention is: can effectively process the salt in the liquid of electrodialysis dense room, obtain the sodium sulfate of higher degree
With succinic acid nano-crystal body, and reclaim the 1,3-PD in the liquid of dense room, by the yield of electrodialysis desalination operation 1,3-PD by
95% brings up to 98%.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of separation and recovery method of the present invention.
Wherein: 1 is the first electrodialyzer；2 is the first crystallizing evaporator；3 is the first solid-liquid separator；4 is the first cooling
Crystallizer；5 is the second solid-liquid separator；6 is the second crystallizing evaporator；7 is the 3rd solid-liquid separator；8 is the second crystallisation by cooling
Device；9 is the 4th solid-liquid separator；10 is the second electrodialyzer.
Detailed description of the invention
Below in conjunction with embodiment, this present invention is described in detail.
Below by embodiment, the present invention is specifically described, it should be pointed out that following example are only intended to
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the person skilled in the art in this field
According to the invention described above content, the present invention can be made some nonessential improvement and adjustment.
Embodiment
(1) crystallize after 6500g 1,3-PD fermentation liquid electrodialysis dense room liquid evaporation removing 3800g water, the first magma warp
It is filtrated to get first crystal 257g and the first crystalline mother solution 1893g；
After (2) first crystalline mother solutions are cooled to 4 DEG C under agitation, carrying out second step crystallization, the second magma filters
To the second crystal 651g and the second crystalline mother solution 1232g；
(3) second crystalline mother solutions evaporation removing 503g water after crystallize, the 3rd magma be filtrated to get the 3rd crystal 73.55g with
3rd crystalline mother solution 635.6g；
After (4) the 3rd crystalline mother solutions are cooled to 4 DEG C under agitation, carrying out the 4th step crystallization, the 4th magma filters
To the 4th crystal 125g and the 4th crystalline mother solution 500g；
(5) carry out electrodialysis desalination after 500g the 4th crystalline mother solution dilute 5 times, finally give desalinization liquor 2800g.Each sample
Analytical data is as shown in the table；
1 tables of data is tested in table 1 1,3-propanediol fermentation liquor electrodialysis desalination dense room liquid fractional crystallization
Table 1 can be seen that, the fractional crystallization under condition of different temperatures of the 1,3-PD fermentation liquid electrodialysis dense room liquid, dense room
Salt-mixture in liquid realizes preliminary separation, first crystal and the 3rd crystal and is mainly sodium sulfate, and the second crystal is mainly fourth two
Acid is received, and the 4th crystal mainly succinic acid is received and the mixture of sodium acetate.After 4th crystalline mother solution passes through electrodialysis desalination, conductance
Rate drops to 2000 μ s/cm, can enter the isolated and purified 1,3-PD therein of downstream process.
Claims (6)
1. a separation and recovery method for fermentation liquid electrodialysis desalination dense room liquid, mainly comprises the steps that
(1) fermentation liquid is used in film filter and remove after somatic cells, protein through the first electrodialyzer (1) desalination,
To the first desalinization liquor and first dense room liquid；
(2) first dense room liquid condensing crystallizing in the first crystallizing evaporator (2), carries out first step crystallization, obtains the first magma；
(3) carry out solid-liquid separation for the first time in the first magma is sent into the first solid-liquid separator (3), obtain first crystal and first
Crystalline mother solution；
(4) the first crystalline mother solution is sent into cooling in the first cooler crystallizer (4), carries out second step crystallization, by second after crystallization
Magma carries out second time solid-liquid separation again in sending into the second solid-liquid separator (5), obtain the second crystal and the second crystalline mother solution；
(5) second crystalline mother solutions concentrate in the second crystallizing evaporator (6), carry out the 3rd step crystallization, obtain the 3rd magma；
(6) the 3rd magma is sent into third time solid-liquid separation in the 3rd solid-liquid separator (7), obtain the 3rd crystal and the 3rd crystallization
Mother solution；
(7) the 3rd crystalline mother solutions send into cooling in the second cooler crystallizer (8), carry out four step crystallizations, are sent into by magma after crystallization
Carry out the 4th solid-liquid separation in 4th solid-liquid separator (9), obtain four crystal and the 4th crystalline mother solution；
(8) by the 4th crystalline mother solution after heating, carry out electrodialysis desalination in delivering to the second electrodialyzer (10), obtain second
Desalinization liquor and the second dense room liquid.
Method the most according to claim 1, it is characterised in that carry out after fermentation liquid being carried out membrane filtration in described step (1)
Electrodialysis desalination, the electrical conductivity of the first desalinization liquor obtained is 1000～2000 μ s/cm, and the electrical conductivity of the first dense room liquid is
50000～100000 μ s/cm.
Method the most according to claim 1, it is characterised in that described step (2) and (5) at the first crystallizing evaporator (2) and
Cycles of concentration 0.5 in second crystallizing evaporator (6)～10 times, the pressure of crystallizing evaporator is 40～200mmHg, evaporative crystallization
Temperature be 60～80 DEG C.
Method the most according to claim 1, it is characterised in that in described step (3) and (6) the first solid-liquid separator (3) and
The temperature of the 3rd solid-liquid separator (7) interior solid-liquid separation is 60～80 DEG C.
Method the most according to claim 1, it is characterised in that second step crystallization and the 4th step in described step (4) and (7)
The temperature of crystallization is 3～10 DEG C, and the temperature of second step and the 4th step solid-liquid separation is 2～10 DEG C.
Method the most according to claim 1, it is characterised in that the temperature after the heating of described step (8) the 4th crystalline mother solution is
25～35 DEG C, after the second electrodialyzer (10) desalination, the electrical conductivity of the second desalinization liquor obtained is 1000～2000 μ s/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610450527.3A CN106117012B (en) | 2016-06-22 | 2016-06-22 | A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610450527.3A CN106117012B (en) | 2016-06-22 | 2016-06-22 | A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106117012A true CN106117012A (en) | 2016-11-16 |
| CN106117012B CN106117012B (en) | 2018-07-31 |
Family
ID=57471290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610450527.3A Active CN106117012B (en) | 2016-06-22 | 2016-06-22 | A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106117012B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185266A (en) * | 2017-06-07 | 2017-09-22 | 合山锌业科技有限公司 | Secondary crystallization system |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4711722A (en) * | 1983-10-12 | 1987-12-08 | Ajinomoto Co., Inc. | Method for preventing fouling of electrodialysis membrane |
| CN1951887A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Method for separating 1,3-propanediol from fermentation liquor |
| CN101328109A (en) * | 2008-07-07 | 2008-12-24 | 江苏汉邦科技有限公司 | Method for separating and purifying 1,3-propanediol in fermentation liquor by means of five-region simulated moving bed |
| CN101748161A (en) * | 2010-01-19 | 2010-06-23 | 南京工业大学 | Succinic acid purification process through anaerobic fermentation |
| CN102040476A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Method for separating and purifying 1,3-propylene glycol from fermentation liquor |
| CN202193691U (en) * | 2011-08-08 | 2012-04-18 | 常州化工设备有限公司 | Equipment for triple-effect waste water desalination process |
-
2016
- 2016-06-22 CN CN201610450527.3A patent/CN106117012B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4711722A (en) * | 1983-10-12 | 1987-12-08 | Ajinomoto Co., Inc. | Method for preventing fouling of electrodialysis membrane |
| CN1951887A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Method for separating 1,3-propanediol from fermentation liquor |
| CN101328109A (en) * | 2008-07-07 | 2008-12-24 | 江苏汉邦科技有限公司 | Method for separating and purifying 1,3-propanediol in fermentation liquor by means of five-region simulated moving bed |
| CN102040476A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Method for separating and purifying 1,3-propylene glycol from fermentation liquor |
| CN101748161A (en) * | 2010-01-19 | 2010-06-23 | 南京工业大学 | Succinic acid purification process through anaerobic fermentation |
| CN202193691U (en) * | 2011-08-08 | 2012-04-18 | 常州化工设备有限公司 | Equipment for triple-effect waste water desalination process |
Non-Patent Citations (1)
| Title |
|---|
| 郝建等: "1,3-丙二醇发酵液电渗析法脱盐", 《过程工程学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185266A (en) * | 2017-06-07 | 2017-09-22 | 合山锌业科技有限公司 | Secondary crystallization system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106117012B (en) | 2018-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104692574B (en) | Treatment method of high saline wastewater | |
| CN101293847B (en) | Method for extracting threonine with threonine fermentation liquor | |
| CN102583839B (en) | Integrated method for seawater desalination, salt manufacturing and heat and electricity generation | |
| CN105859809B (en) | A method of extracting beta-thymidine from fermentation liquid | |
| JP2013507953A (en) | Economic process for the production of xylose from saccharified liquid using electrodialysis and direct recovery methods | |
| CN102586496A (en) | Process for producing xylose | |
| CN102381782B (en) | Recovery treatment method for wastewater generated in production of carboxymethyl cellulose | |
| CN103232353A (en) | Method for separating and extracting L-valine from broth with high efficiency | |
| CN103172212A (en) | Treatment method of lignin production waste water | |
| CN102363594A (en) | Method for separating and purifying succinic acid from fermentation broth | |
| CN107416866A (en) | Polarizer manufactures the processing method of waste liquid | |
| JP2018520874A (en) | Reverse osmotic pressure method without osmotic pressure to concentrate solute-containing aqueous solution to high concentration | |
| CN106748648A (en) | A kind of 1,3 propanediol fermentation liquor desalination impurity removed systems and method | |
| CN101648898A (en) | Membrane concentration process of dimehypo mother liquor | |
| WO2012078651A2 (en) | Integration of fermentation with membrane | |
| CN101870639A (en) | Method for producing kelp mannitol with low energy consumption | |
| CN205974124U (en) | Coal chemical wastewater's processing system | |
| CN101205230B (en) | Method for extracting high-purity riboflavin directly from fermentation liquor | |
| CN106117012A (en) | A kind of separation and recovery method of fermentation liquid electrodialysis desalination dense room liquid | |
| CN204939142U (en) | A kind for the treatment of facility of desulfurization wastewater of flue gas desulphurization system discharge | |
| CN205838881U (en) | A kind of separating and reclaiming device of fermentation liquid electrodialysis desalination dense room liquid | |
| CN106588641B (en) | A kind of recovery method of 2-KLG primary crystallization mother liquor | |
| CN205662415U (en) | High salt waste water recycling treatment facility | |
| CN106277521B (en) | A kind of dimehypo recycling mother solution reclaiming system and technique based on membrane technology | |
| CN110723857B (en) | High-salinity water concentration and crystallization treatment system and process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |