CN106117012B - A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination - Google Patents
A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination Download PDFInfo
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- CN106117012B CN106117012B CN201610450527.3A CN201610450527A CN106117012B CN 106117012 B CN106117012 B CN 106117012B CN 201610450527 A CN201610450527 A CN 201610450527A CN 106117012 B CN106117012 B CN 106117012B
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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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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination of the present invention, mainly the concentration for the first time of the dense room liquid of electrodialysis, the first step are crystallized, the magma first step is separated by solid-liquid separation, and second step crystallizes after the cooling of the first crystalline mother solution, and magma second step is separated by solid-liquid separation, second crystalline mother solution concentrates, third step crystallization, magma third step are separated by solid-liquid separation, and the 4th step crystallizes after the cooling of third crystalline mother solution, the 4th step of magma is separated by solid-liquid separation, the 4th secondary desalination of crystalline mother solution electrodialysis.The salt in the dense room liquid of electrodialysis can be effectively treated in this method, obtain the sodium sulphate and succinic acid nano-crystal body of higher degree, and recycle 1,3 propylene glycol in dense room liquid, and the yield of 1,3 propylene glycol of electrodialysis desalination process is increased to 98% by 95%.
Description
Technical field
The invention belongs to biological chemical fields, and in particular to arrive the electrodialysis desalination of Production of 1,3-Propanediol by Fermentation Method process
The processing method of technique and high content of salt, high-COD waste water.
Background technology
1,3-PD is the important source material of many synthetic reactions, especially as production polyester PTT（Poly terephthalic acid
Propylene glycol ester）With the monomer of polyurethane.Compared with chemical method synthesizes, the advantages of Production of 1,3-Propanediol by Fermentation Method is selectivity
Height, operating condition is mild, and raw material is renewable etc., has become the hot spot of domestic and international researcher concern in recent years.But in micro- life
During object Production of 1,3-Propanediol by Fermentation Method, bacterial metabolism generate 1,3-PD while, also generate succinic acid, acetic acid,
The organic acids such as lactic acid, the ammonium ion being used as in fermentation medium in addition in the ammonium sulfate of nitrogen source are consumed, and zymotic fluid pH value reduces,
In order to maintain the pH value of zymotic fluid neutral, in fermentation process, by pH robot control system(RCS)s into zymotic fluid auto-feeding NaOH solution,
So that under fermentation when tank, the salt content in zymotic fluid is up to 2-3%.
There are mainly two types of the methods for isolating and purifying the 1,3-PD in zymotic fluid at present, and first method is without de-
Salt is retained in material by salt, that is, filtration sterilization, thickening etc. is used first to be readily able to the substance of separation from zymotic fluid system
Separate, then distillation, rectifying and etc. 1,3-PD is extracted from salting liquid system.The magnificent biology in Zhangjiagang
Materials Co., Ltd proposes a kind of method for extracting 1,3- propylene glycol from zymotic fluid（Patent CN101891591A）, the patent
It proposes toward zymotic fluid（Or concentrated dewatered zymotic fluid）Middle addition glycerine prevents the crystallization of the salt in zymotic fluid to be precipitated, then
1,3- propylene glycol is extracted from zymotic fluid by techniques such as evaporation, rectifying.Second method is will be first after filtration sterilization
Salt is separated from zymotic fluid, then the zymotic fluid after desalination is isolated and purified, extracts 1,3-PD therein.Clearly
The Wang Xiaolin of Hua Da proposes desalinating process of the electroosmose process for 1,3- propanediol fermentation liquors（Patent CN1522997A）, lake
A kind of electrodialysis desalination work of All rivers run into sea in south bioengineering Co., Ltd proposes heterogeneous membrane is used for 1,3- propanediol fermentation liquors
Skill（Patent CN101298409A）, the proposition of this method makes 1,3-PD zymotic fluid electrodialysis desalination cost substantially reduce,
Push electric dialysis desalinating process in the industrial applications in the field.
For 1,3-PD zymotic fluid after electrodialysis desalination, salt content is reduced to 0.1~0.5%, into downstream process into
One step isolates and purifies, and in desalination processes, the zwitterion in zymotic fluid penetrates amberplex and enters dense room liquid respectively so that
Salt content in dense room liquid is up to 5~15%, in addition in dense room liquid also contain because concentration difference diffuse through come 1,3-PD, 1,
The infiltration capacity of 3-propanediol accounts for 5~10% of 1,3- propylene glycol in zymotic fluid.The COD of the dense room liquid is up to 70000mg/L, directly
As wastewater treatment, expense is high, but also can not recycle 1,3-PD therein.
Crystallization is a kind of conventional desalting technology, also has document report to be sent out for 1,3-PD using crystal desalination technology
The extraction of zymotic fluid.The Liu Dehua of Tsinghua University is proposed in a kind of zymotic fluid toward 1,3-PD and is added inorganic acid, by zymotic fluid
In acylate conversion organic acid and inorganic salts after, by inorganic acid salt crystallize be precipitated and detach method（The patent No.
CN101033171A）.The patent has good effect for the inorganic acid salt in separation and fermentation liquid, but a large amount of organic acid is also residual
It stays in zymotic fluid, influences subsequent distillation, distillation operation.
Fractional crystallization technique proposed by the present invention can will be organic in the dense room liquid of 1,3- propanediol fermentation liquor electrodialysis desalinations
Salt and inorganic salts crystallize precipitation respectively, and crystalline mother solution is carried out secondary electrodialysis desalination, to recycle 1,3-PD therein.
It not only solves the problems, such as that the dense room liquid wastewater treatment of electrodialysis is costly, also improves electrodialysis desalination process 1,3-PD receipts
Rate.
Invention content
The purpose of the present invention is to provide a kind of separation and recovery by the dense room liquid of 1,3- propanediol fermentation liquor electrodialysis desalinations
Method receives the variation tendency of solubility with temperature in aqueous solution for sodium sulphate in the dense room liquid of electrodialysis and succinic acid and differs
The characteristic of cause, it is proposed that the method for fractional crystallization, respectively by sodium sulphate, succinic acid receive with sodium acetate Crystallization Separation, finally obtain
Crystalline mother solution remaining salt is removed by electrodialysis again after, recycle 1,3-PD therein into downstream process.
Above-mentioned purpose is achieved through the following technical solutions.
A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination is mainly dense for the first time by the dense room liquid of electrodialysis
Contracting, first step crystallization, the magma first step are separated by solid-liquid separation, and second step crystallizes after the cooling of the first crystalline mother solution, magma second step solid-liquid
Separation, the concentration of the second crystalline mother solution, third step crystallization, magma third step are separated by solid-liquid separation, the 4th step after the cooling of third crystalline mother solution
Crystallization, the 4th step of magma are separated by solid-liquid separation, and the 4th secondary desalination of crystalline mother solution electrodialysis mainly includes the following steps that：
（1）By zymotic fluid using removing in membrane filter after somatic cells, protein by 1 desalination of the first electric dialyzator,
Obtain the 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）First magma is sent into the first solid-liquid separator 3 and carries out first time separation of solid and liquid, obtains first crystal and the
One crystalline mother solution；
（4）First crystalline mother solution is sent into cooling in the first cooler crystallizer 4, carries out second step crystallization, by the after crystallization
Two magmas, which are sent into the second solid-liquid separator 5, carries out second of separation of solid and liquid, obtains the second crystal and the second crystalline mother solution；
（5）Second crystalline mother solution concentrates in the second crystallizing evaporator 6, carries out third step crystallization, obtains third magma；
（6）Third magma is sent into third solid-liquid separator 7 and is separated by solid-liquid separation for the third time, third crystal and third knot are obtained
Brilliant mother liquor；
（7）Third crystalline mother solution is sent into cooling in the second cooler crystallizer 8, the crystallization of the 4th step is carried out, by the 4th after crystallization
Magma, which is sent into the 4th solid-liquid separator 9, carries out the 4th separation of solid and liquid, obtains four crystal and the 4th crystalline mother solution；
（8）It by the 4th crystalline mother solution after heating, send to electrodialysis desalination is carried out in the second electric dialyzator 10, obtains the
Two desalinization liquors and the second dense room liquid.
The step（1）Electrodialysis desalination is carried out after the middle progress membrane filtration by zymotic fluid, the electricity of the first obtained desalinization liquor
Conductance is 1000~2000 μ s/cm, and the conductivity of the first dense room liquid is 50000~100000 μ s/cm.
The step（2）With（5）Cycles of concentration 0.5~10 in the first crystallizing evaporator 2 and the second crystallizing evaporator 6
Times, the pressure of evaporator is 40~200mmHg, and the temperature of evaporative crystallization is 60~80 DEG C.
The step（3）With（6）In the temperature that is separated by solid-liquid separation in the first solid-liquid separator 3 and third solid-liquid separator 7 be
60~80 DEG C.
The step（4）With（7）The temperature of middle second step crystallization and the crystallization of the 4th step is 3~10 DEG C, second step and the 4th
The temperature that step is separated by solid-liquid separation is 2~10 DEG C.
The step（8）Temperature after the heating of 4th crystalline mother solution is 25~35 DEG C, after 10 desalination of the second electric dialyzator,
The conductivity of the second obtained desalinization liquor is 1000~2000 μ s/cm.
In conclusion the method for the present invention will be in the 1,3-PD fermentation dense room liquid of solution electrodialysis by Steppecd crystallization
What salt was separated, the 4th crystalline mother solution is then removed into salt therein using the method for electrodialysis desalination, is obtained after desalination
Second desalinization liquor is mixed into 1,3-PD downstream extraction technique with the first desalinization liquor and further isolates and purifies, 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 that 1,3-PD electrodialysis is de-
Sodium sulphate and succinic acid receive the key parameter of separation in the dense room liquid of salt.
The present invention progress effect be：The salt in the dense room liquid of electrodialysis can be effectively treated, obtain the sodium sulphate of higher degree
With succinic acid nano-crystal body, and recycle the 1,3-PD in dense room liquid, by the yield of electrodialysis desalination process 1,3-PD by
95% is increased to 98%.
Description of the drawings
Fig. 1 is the flow diagram of separation and recovery method of the present invention.
Wherein：1 is the first electric dialyzator；2 be the first crystallizing evaporator；3 be the first solid-liquid separator；4 be the first cooling
Crystallizer；5 be the second solid-liquid separator；6 be the second crystallizing evaporator；7 be third solid-liquid separator；8 be the second crystallisation by cooling
Device；9 be the 4th solid-liquid separator；10 be the second electric dialyzator.
Specific implementation mode
This present invention is described in detail with reference to embodiment.
The present invention is specifically described below by embodiment, it should be pointed out that following embodiment is only intended to
Invention is further explained, should not be understood as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made to the present invention according to aforementioned present invention content.
Embodiment
（1）It is crystallized after the dense room liquid evaporation removing 3800g water of 6500g 1,3-PDs fermentation solution electrodialysis, the first magma warp
First crystal 257g and the first crystalline mother solution 1893g is obtained by filtration；
（2）After first crystalline mother solution is cooled to 4 DEG C under agitation, second step crystallization is carried out, the second magma passed through
Filter obtains the second crystal 651g and the second crystalline mother solution 1232g；
（3）It is crystallized after second crystalline mother solution evaporation removing 503g water, third crystal is obtained by filtration in third magma
73.55g and third crystalline mother solution 635.6g；
（4）After third crystalline mother solution is cooled to 4 DEG C under agitation, the crystallization of the 4th step is carried out, the 4th magma passed through
Filter obtains the 4th crystal 125g and the 4th crystalline mother solution 500g；
（5）The 4th crystalline mother solutions of 500g carry out electrodialysis desalination after being diluted with water 5 times, finally obtain desalinization liquor 2800g.Respectively
Sample analysis data are as shown in the table；
1 tables of data is tested in the dense room liquid fractional crystallization of 1 1,3- propanediol fermentation liquor electrodialysis desalinations of table
Table 1 can be seen that the 1,3-PD fermentation dense room liquid of solution electrodialysis passes through the fractional crystallization under condition of different temperatures,
Salt-mixture in dense room liquid realizes that preliminary separation, first crystal and third crystal are mainly sodium sulphate, and the second crystal is mainly
Succinic acid is received, and the 4th crystal is mainly the mixture that succinic acid is received with sodium acetate.After 4th crystalline mother solution is by electrodialysis desalination,
Conductivity drops to 2000 μ s/cm, can isolate and purify 1,3-PD therein into downstream process.
Claims (3)
1. a kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination, mainly includes the following steps that：
(1) it by the first electric dialyzator (1) desalination after using membrane filter to remove somatic cells, protein zymotic fluid, obtains
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, the
One dense 0.5~10 times of room liquid cycles of concentration, the pressure of crystallizing evaporator are 40~200mmHg, the temperature of evaporative crystallization is 60~
80℃；
(3) the first magma is sent into the first solid-liquid separator (3) and carries out first time separation of solid and liquid, obtain first crystal and first
The temperature of crystalline mother solution, separation of solid and liquid is 60~80 DEG C；
(4) the first crystalline mother solution is sent into cooling in the first cooler crystallizer (4), second step crystallization is carried out, by second after crystallization
Magma, which is sent into the second solid-liquid separator (5), to carry out being separated by solid-liquid separation for second again, obtains the second crystal and the second crystalline mother solution,
The temperature of second step crystallization is 3~10 DEG C, and the temperature that second step is separated by solid-liquid separation is 2~10 DEG C；
The concentration in the second crystallizing evaporator (6) of (5) second crystalline mother solutions carries out third step crystallization, obtains third magma, and second
0.5~10 times of crystalline mother solution cycles of concentration, the pressure of crystallizing evaporator are 40~200mmHg, the temperature of evaporative crystallization is 60~
80℃；
(6) third magma is sent into third time in third solid-liquid separator (7) to be separated by solid-liquid separation, obtains third crystal and third crystallization
The temperature of mother liquor, separation of solid and liquid is 60~80 DEG C；
(7) third crystalline mother solution is sent into cooling in the second cooler crystallizer (8), carries out four step crystallizations, is sent into magma after crystallization
The 4th separation of solid and liquid is carried out in 4th solid-liquid separator (9), obtains four crystal and the 4th crystalline mother solution, the temperature of the 4th step crystallization
Degree is 3~10 DEG C, and the temperature that the 4th step is separated by solid-liquid separation is 2~10 DEG C；
(8) it by the 4th crystalline mother solution after heating, send to progress electrodialysis desalination in the second electric dialyzator (10), obtains second
Desalinization liquor and the second dense room liquid.
2. according to the method described in claim 1, it is characterized in that being carried out after zymotic fluid is carried out membrane filtration in the step (1)
The conductivity of electrodialysis desalination, the first obtained desalinization liquor is 1000~2000 μ s/cm, and the conductivity of the first dense room liquid is
50000~100000 μ s/cm.
3. according to the method described in claim 1, it is characterized in that the temperature after the heating of the 4th crystalline mother solution of the step (8) is
25~35 DEG C, after the second electric dialyzator (10) desalination, the conductivity of the second obtained desalinization liquor is 1000~2000 μ s/cm.
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| 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 |
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| 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 |
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- 2016-06-22 CN CN201610450527.3A patent/CN106117012B/en active Active
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| 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 | Process for purifying succinic acid by 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 |
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