Device for preparing succinic acid from succinate fermentation liquor

Abstract

The utility model relates to a succinate fermentation liquor preparation succinic acid device belongs to the field of bio -chemical industry, the device includes: ceramic membrane is used for the filtration of succinate fermentation liquor and removes the impurity treatment, ultrafiltration membrane is connected in the permeation side of ceramic membrane and is used for the filtrate of ceramic membrane and carries out the filtration decoloring treatment, sodium type ion exchange resin is connected in the permeation side of ultrafiltration membrane and is used for the ion exchange treatment of the permeate of ultrafiltration membrane, and Mg 2+ Converts into Na + ; nanofiltration membrane is connected in the liquid outlet of sodium type ion exchange resin and is used for the concentration of the effluent of sodium type ion exchange resin, bipolar membrane electrodialyzer is used for the bipolar membrane electrodialysis treatment of the concentrated solution of nanofiltration membrane, obtains lye and the succinic acid solution after sodium removal.

Description

TECHNICAL FIELD

[0001] The utility model relates to a kind of succinate fermentation liquor preparation succinic acid device, belong to bio-chemical technology field. BACKGROUND

[0002] Succinic acid is also known as succinic acid because it is obtained from distillation succinum in 1550, molecular formula is C4H6O4, molecular weight 118.08, melting point is 185 DEG C, 20 DEG C when succinic acid solubility in water is 100mg / ml, slightly soluble in ethanol, diethyl ether, acetone, glycerol, pure succinic acid is colorless or white crystal, with sour taste, odorless.As intermediate product of tricarboxylic acid cycle also is the metabolic end product of some anaerobic microorganism, succinic acid is located in the first place of 12 important "building blocks" of industrial microbial conversion, is important platform compound for synthesizing bulk high value-added chemicals, has huge economic value.In pharmaceutical industry, succinic acid can be used to prepare hemostatic agent, antidote and diuretic and be widely used as pharmaceutical intermediate;In agriculture, after treatment, succinic acid can be used to improve the germination rate of seed, promote crop growth, also can be used as additive of weeding agent, also can be used as monogastric animal feed additive;In chemical industry, succinic acid can be used for synthesizing some high-performance polymer materials, also can be used for synthesizing biodegradable plastic.Currently, succinic acid production method is chemical synthesis, biological conversion and biological fermentation, but chemical synthesis method raw material is non-renewable petrochemical product, and process high energy consumption, high pollution, not in line with the requirement of sustainable development, biological conversion method uses substrate, so it is difficult to industrialize, biological fermentation method relies on substrate, so it is easy to get, low price and process environmental protection becomes mainstream process.But because of the need to add magnesium carbonate and other inorganic salts in fermentation process, therefore most of the obtained fermentation broth is succinate, and subsequent conversion is needed.

[0003] Existing purification method is mainly divided into (1) precipitation method: use calcium salt, zinc salt and ammonium salt to precipitate succinic acid, and then use sulfuric acid to acidify, followed by activated carbon decolorization, finally succinic acid is obtained, but the process consumes a large amount of chemical raw materials, and the recovery cost is high;(2) aqueous two-phase method: a system formed by organic solvent, inorganic salt and water with appropriate concentration, at this time, the salt does not precipitate, but forms two phases in liquid-liquid separation, after acidification of fermentation broth, add acid salt with high solubility and hydrophilic organic solvent to form aqueous two-phase system, separate the upper phase, recover the solvent by reduced pressure distillation, the mother liquor is decolorized by activated carbon, concentrated and crystallized to obtain succinic acid product, the lower phase is recovered by hydrophilic alcohol and inorganic salt and hydrophilic alcohol, but this method has the disadvantages of low yield and the inability to remove impurities;(3) complex extraction method: different tertiary amine extractants are used to extract succinic acid in different diluents, it is found that there are differences in succinic acid yield and purity of different extractants, but the amount of reagent used in extraction process is large, and the requirement for back extraction agent is high, therefore, it is urgent to combine process to realize the conversion of succinic acid salt in fermentation broth. UTILITY MODEL CONTENT

[0004] In order to solve the problem of complex purification steps and poor treatment effect of succinate fermentation broth in the prior art, a succinate fermentation broth preparation succinic acid method and device are provided.

[0005] The technical scheme is:

[0006] A succinate fermentation broth preparation succinic acid method comprises the following steps:

[0007] The fermentation broth containing succinate is filtered and impurities are removed by using a ceramic membrane;

[0008] The filtrate of the ceramic membrane is filtered and decolorized by using an ultrafiltration membrane;

[0009] The permeate of the ceramic membrane is subjected to ion exchange treatment by using a sodium type ion exchange resin, and Mg 2+ is converted into Na + .

[0010] After the permeate of the sodium type ion exchange resin is concentrated, bipolar membrane electrodialysis treatment is performed to obtain a lye and a succinic acid solution after sodium removal.

[0011] The fermentation broth containing succinate is obtained in the preparation of succinic acid by fermentation method with magnesium carbonate as a neutralizing agent.

[0012] The pore size range of the ceramic membrane is 20-200 nm, the operating pressure range is 0.1-1 Mpa, and the pH range is 0-14.

[0013] The molecular weight cut-off range of the ultrafiltration membrane is 3000-5000 Da, the operating pressure is 0.5-1 MPa, the operating temperature is 5-45 DEG C, and the pH range is 3-10.

[0014] The concentration process adopts nanofiltration membrane concentration, the nanofiltration membrane molecular weight cut-off is between 300-550 Da, the operating pressure is 0.7-2.5 MPa, the operating temperature is 5-45 DEG C, and the pH range is 3-10.

[0015] In the process of bipolar membrane electrodialysis, the current density is kept at 400-800 A / m 2 .

[0016] A succinate fermentation broth preparation succinic acid device comprises:

[0017] A ceramic membrane is used for filtering and removing impurities of the succinate fermentation broth;

[0018] An ultrafiltration membrane is connected to the permeation side of the ceramic membrane, and is used for filtering and decolorizing the filtrate of the ceramic membrane;

[0019] Sodium type ion exchange resin connected to the permeation side of the ultrafiltration membrane, used for ion exchange treatment of the permeation liquid of the ultrafiltration membrane, converting Mg 2+ Into Na + ;

[0020] Nanofiltration membrane connected to the effluent outlet of the sodium type ion exchange resin, used for concentrating the effluent of the sodium type ion exchange resin;

[0021] Bipolar membrane electrodialyzer used for bipolar membrane electrodialysis treatment of the concentrated solution of the nanofiltration membrane, obtaining alkali liquor and sodium-removed succinic acid solution.

[0022] The pore size of the ceramic membrane ranges from 200 nm to 200 nm.

[0023] The molecular weight cut-off of the ultrafiltration membrane is between 3000 Da and 5000 Da.

[0024] The molecular weight cut-off of the nanofiltration membrane is between 300 Da and 550 Da.

[0025] The bipolar membrane electrodialyzer is connected to an alkali liquor storage tank, which is used to receive the alkali liquor obtained by the electrodialysis treatment.

[0026] Beneficial effects

[0027] The method for extracting succinic acid from succinic acid salt fermentation liquor by using resin + membrane method provided by the utility model, the whole conversion process can be roughly divided into the following steps: after the fermentation liquor is heated, the ceramic membrane is used to filter and remove proteins, part of fermentation strains and insoluble substances in the fermentation liquor; after the ceramic membrane clear liquid is concentrated after removing pigments and macromolecular proteins through an organic membrane, the concentrated liquid is replaced with calcium and magnesium ions through continuous exchange resin; since a small amount of succinic acid also exists in the fermentation liquor, the sodium succinate mixed with a small amount of succinic acid solution after the resin is evaporated and crystallized to obtain pure succinic acid crystals and mother liquor; the mother liquor is used to prepare high-purity succinic acid through a bipolar membrane, and then, crystallization is performed; the crystallization mother liquor can be further extracted through the bipolar membrane. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 is the flow chart of the patent;

[0029] Figure 2 is the device diagram of the patent.

[0030] Wherein, 1, ceramic membrane; 2, ultrafiltration membrane; 3, sodium type ion exchange resin; 4, nanofiltration membrane; 5, bipolar membrane electrodialyzer. DETAILED DESCRIPTION

[0031] The utility model discloses a fermentation broth with magnesium carbonate as neutralizer as raw material, insoluble substances and macromolecular proteins are removed through inorganic membrane separation, then organic membrane is used to carry out decoloring and concentration treatment, then resin is used to convert magnesium succinate into sodium succinate, the obtained sodium succinate and a small part of succinic acid are evaporated and crystallized, part of succinic acid crystal and evaporation mother liquor are obtained, the evaporation mother liquor is treated by sodium removal through bipolar membrane, and the obtained original chamber liquid is continuously evaporated and crystallized to obtain high-purity succinic acid crystal. The turbidity of the fermentation broth treated through the ceramic membrane is reduced to 1 NTU, the yield can reach more than 85%, the decoloring effect of the organic membrane is equivalent to that of activated carbon, but the generation of solid waste and the adsorption of activated carbon on succinic acid are avoided, the concentration multiple of the nanofiltration membrane can reach more than 5 times, the extraction rate is improved, and the water quantity in subsequent treatment is reduced, the continuous ion exchange device realizes the continuity of succinate adsorption and desorption, evaporation and crystallization can make a part of succinic acid precipitate first, the subsequent evaporation mother liquor enters the bipolar membrane, the treatment quantity of the bipolar membrane is reduced, the process of extracting succinic acid through the bipolar membrane is green and environmental protection, and the byproduct can be utilized again.

[0032] In some embodiments, the method of the utility model is realized by the following steps:

[0033] 1. A method for extracting succinic acid from succinate fermentation broth by resin+membrane method, characterized in that the fermentation broth with magnesium carbonate as neutralizer is used as raw material, impurities are removed and decolorized through inorganic membrane and organic membrane, concentrated, and then the salt is converted using resin, followed by evaporation and crystallization of part of succinic acid, and the mother liquor is further treated by bipolar membrane to prepare succinic acid, and the steps are as follows:

[0034] (1) Fermentation broth separation: the succinate fermentation broth is subjected to impurity removal experiment through ceramic membrane to remove fermentation bacteria and some insoluble substances, 50nm ceramic membrane is used, the operating pressure is 0.1-1MPa, the operating temperature is 20-80 DEG C, and the pH range is 0-14, and clear transparent clear liquid is obtained.

[0035] (2) Decolorization and concentration experiment is carried out through organic membrane, and the pigment and some macromolecular proteins are intercepted in the concentrated solution through ultrafiltration membrane, and the target product is recovered as much as possible through washing water in the later stage of the experiment, the molecular weight intercepted by the ultrafiltration membrane is between 3000-5000Da, the operating pressure is 0.5-1MPa, the operating temperature is 5-45 DEG C, the pH range is 3-10, the nanofiltration membrane is concentrated, and the concentration multiple is 4-10 times. The molecular weight intercepted by the nanofiltration membrane is between 300-550Da, the operating pressure is 0.7-2.5MPa, the operating temperature is 5-45 DEG C, and the pH range is 3-10.

[0036] (3) Continuous ion exchange resin is used for succinic acid conversion, realizing the conversion of succinate to sodium succinate. The resin used in this step is hard resin. By setting a continuous ion exchange device, adsorption and desorption can be synchronized. The resin type is Zhengguang D860. During the desorption process, 2%-4% NaOH and 2%-4% HCl are configured.

[0037] (4) After the solution is adsorbed by the resin, evaporation crystallization is performed to obtain succinic acid crystals and evaporation mother liquor. Bipolar membrane is used to convert sodium succinate to succinic acid. The final solution in the original chamber is continuously subjected to evaporation crystallization, so as to obtain as much pure succinic acid as possible. The bipolar membrane uses a two-chamber bipolar membrane. The current density is maintained at 400-800 A / m 2 membrane. The succinic acid content can reach 15-20%.

[0038] Based on the above process, the device structure used in the patent is as shown in Figure 2 , which comprises:

[0039] Ceramic membrane 1 is used for filtering and removing impurities from succinate fermentation liquor;

[0040] Ultrafiltration membrane 2 is connected to the permeation side of ceramic membrane 1 and is used for filtering and decolorizing the filtrate of ceramic membrane 1;

[0041] Sodium ion exchange resin 3 is connected to the permeation side of ultrafiltration membrane 2 and is used for ion exchange treatment of the permeate of ultrafiltration membrane 2, converting Mg 2+ to Na + ;

[0042] Nanofiltration membrane 4 is connected to the outlet of sodium ion exchange resin 3 and is used for concentrating the outlet liquid of sodium ion exchange resin 3;

[0043] Bipolar membrane electrodialyzer 5 is used for bipolar membrane electrodialysis treatment of the concentrated liquid of nanofiltration membrane 4 to obtain alkali and succinic acid solution after sodium removal.

[0044] The pore size of the ceramic membrane is 200-200 nm.

[0045] The molecular weight cut-off of the ultrafiltration membrane is between 3000-5000 Da.

[0046] The molecular weight cut-off of the nanofiltration membrane is between 300-550 Da.

[0047] The bipolar membrane electrodialyzer 4 is connected to an alkali storage tank, which is used to receive the alkali obtained by sodium removal through electrodialysis treatment.

[0048] Example 1

[0049] A ceramic membrane experiment was conducted using 40 kg of fermentation broth. The succinate content (mainly magnesium succinate with a portion of succinic acid) in the fermentation broth was approximately 8.51 g / L. The fermentation broth was clarified and purified using a 50 nm ceramic membrane. The inlet pressure was set to 0.2 MPa, the outlet pressure to 0.1 MPa, and the reflux was maintained at 3-4 m. 3 / L, with 10kg of wash water added during the process, a final 41.5kg of clear liquid was obtained through the ceramic membrane. The average flux of the ceramic membrane filtration was 120LMH, and the succinate content was 7.51g / L. The clear liquid was then decolorized using an ultrafiltration membrane with a molecular weight cutoff of 4000. The experimental feed was 41kg, the pressure was set at 0.7MPa, and the reflux was maintained at 1-2m. 3 / L, with 10kg of wash water added during the process, a final ultrafiltration solution of 42.8kg was obtained, with an average flux of 18.2LMH and a succinate content of 6.14g / L. The solution was then concentrated using a nanofiltration membrane with a molecular weight cutoff of 400Da. A feed of 42kg yielded a final effluent of 33.5kg, a concentration of 4.9 times, at which point the succinate content was 25.8g / L. The concentrated solution was then passed through a sodium-type ion exchange resin using a continuous ion exchange process, divided into adsorption, top-water, and desorption zones. The flow rate was controlled at 2 BV. After passing through the resin, the succinate (mainly sodium succinate containing a portion of succinic acid) content was 22.5 g / L. At this point, the calcium and magnesium ion content had decreased to 5 ppm, meeting the requirements for bipolar membrane feed water. The bipolar membrane voltage was set to 25 V, and the current was maintained at 4.4 A. After extraction by the bipolar membrane, the pure succinic acid concentration was approximately 21.3 g / L, and the resulting alkali solution concentration was approximately 2 mol / L. This alkali solution can be used to adjust the pH during fermentation and can also be used for acid-base regeneration in continuous ion exchange.

[0050] Example 2

[0051] A ceramic membrane experiment was conducted using 60 kg of fermentation broth. The succinate content in the fermentation broth was approximately 10.2 g / L. The fermentation broth was clarified and purified using a 50 nm ceramic membrane. The inlet pressure was set to 0.24 MPa, the outlet pressure to 0.12 MPa, and the reflux was maintained at 3.5 m. 3 / L, with 10kg of wash water added during the process, a final 58.4kg of clear liquid was obtained through the ceramic membrane. The average flux of the ceramic membrane filtration was 135LMH, and the succinate content was 9.21g / L. The clear liquid was then decolorized using an ultrafiltration membrane with a molecular weight cutoff of 4000. The experimental feed was 58kg, the pressure was set at 0.8MPa, and the reflux was maintained at 1.2m. 3 / L, process washing water 5 kg, finally get ultrafiltration clear liquid 54.5 kg, average flux 17.6 LMH, succinate content is 8.55 g / L, the subsequent clear liquid is concentrated by nanofiltration membrane with a molecular weight cut-off of 400 Da, feed 54 kg, finally clear 44 kg, concentrated 5.4 times, at this time the succinate content is 39.8 g / L, the concentrated liquid is passed through the resin, and the continuous ion exchange resin is used to remove hardness, which is divided into adsorption zone, water top zone and elution zone, the flow rate is controlled at 2 BV during the process, the succinate content (mainly sodium succinate containing a part of succinic acid) is 37.4 g / L after passing through the resin, at this time the calcium and magnesium ion content has been reduced to 5 ppm, meeting the requirements of bipolar membrane feed water, the bipolar membrane voltage is set to 25 V, and the current is maintained at 4.4 A, after bipolar membrane extraction, the pure succinic acid concentration is about 36.8 g / L, and the obtained alkali solution concentration is about 2 mol / L, which can be used for pH adjustment in fermentation, and also can be used for acid-alkali regeneration in continuous ion exchange.

Claims

1. A device for preparing succinic acid from a succinate fermentation broth, characterized by, The application relates to a method for producing sodium succinate, which comprises the following steps: a ceramic membrane (1) is used for filtering and removing impurities from a succinate fermentation liquor; an ultrafiltration membrane (2) is connected to the permeation side of the ceramic membrane (1) and is used for filtering and decoloring the filtrate of the ceramic membrane (1); Sodium type ion exchange resin (3) is connected to the permeation side of the ultrafiltration membrane (2) for ion exchange treatment of the permeation liquid of the ultrafiltration membrane (2) to convert Mg 2+ into Na + ; a nanofiltration membrane (4) is connected to the liquid outlet of a sodium type ion exchange resin (3) and is used for concentrating the liquid discharged from the sodium type ion exchange resin (3); a bipolar membrane electrodialyzer (5) is used for bipolar membrane electrodialysis treatment of the concentrated liquid of the nanofiltration membrane (4) to obtain an alkali liquor and a sodium-removed succinic acid solution.

2. The succinate salt fermentation broth to succinic acid apparatus according to claim 1, characterized by, The pore size of the ceramic membrane is 200-200 nm.

3. The succinate fermentation broth to succinate salt preparation apparatus according to claim 1, wherein The molecular weight cut-off of the ultrafiltration membrane is 3000-5000 Da.

4. The succinate fermentation broth to succinate salt preparation apparatus according to claim 1, wherein The molecular weight cut-off of the nanofiltration membrane is 300-550 Da.

5. The succinate fermentation broth to succinic acid plant of claim 1, wherein, The bipolar membrane electrodialyzer (5) is connected to an alkali liquor storage tank, which is used for receiving the alkali liquor obtained by the sodium-removed electrodialysis treatment.

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