Method and device system for separating and recovering 1, 3-PDO in electrodialysis concentration chamber liquid

Abstract

The invention relates to a method and a device system for separating and recovering 1, 3-PDO in electrodialysis concentrated chamber liquid, and the method comprises the following steps: (1) carrying out electrodialysis desalination treatment on 1, 3-PDO fermentation liquid to obtain electrodialysis concentrated chamber liquid and electrodialysis desalted liquid; (2) performing reverse osmosis filtration treatment on the electrodialysis concentrated chamber liquid obtained in the step (1) to obtain reverse osmosis filtrate; and (3) mixing the electrodialysis desalting solution obtained in the step (1) and the reverse osmosis filtrate obtained in the step (2) to obtain a purified solution of 1, 3-PDO. According to the invention, 1, 3-PDO in the electrodialysis concentration chamber liquid can be separated and recovered, the recovery rate of 1, 3-PDO is improved, subsequent preparation of a high-purity 1, 3-PDO product is facilitated, and the production cost and energy consumption are reduced.

Description

Technical Field

[0001] The invention relates to the technical field of bio-based new materials, and in particular to a method for separating and recovering 1,3-PDO in electrodialysis concentrate chamber liquid and a device system thereof. Background Art

[0002] 1,3-Propanediol (1,3-propanediol, abbreviated as 1,3-PDO) is a colorless, odorless, salty and hygroscopic viscous liquid. It is the raw material for the production of unsaturated polyesters, plasticizers, surfactants, emulsifiers and demulsifiers. In the polyurethane industry, it is often used as a raw material for polyester polyols, a starter for polyether polyols and a chain extender for polyurethanes. In the organic chemical industry, it is also an important monomer and intermediate, such as the monomer for the synthesis of polytrimethylene terephthalate (PTT).

[0003] At present, the production methods of 1,3-PDO mainly include chemical method and biological fermentation method. Among them, the chemical method uses the product from petroleum cracking as raw material, and catalytic hydrogenation is carried out under high temperature and high pressure to prepare 1,3-PDO, but this method has complex production process, harsh reaction conditions, and high requirements for equipment; the biological fermentation method uses renewable biomass as raw material to produce 1,3-PDO at room temperature and pressure. The biological fermentation method overcomes the conditional limitations of traditional chemical industry, and its raw materials are widely available and renewable, which meets the requirements of green chemical production.

[0004] However, during the production of 1,3-PDO by biological fermentation, organic acids are metabolized and produced at the same time. During the fermentation process, alkali needs to be added to neutralize and produce organic acid salts. In addition, components such as ammonium sulfate and phosphate are also added to the culture medium, which are not completely consumed during the fermentation process and remain in the fermentation liquid after the fermentation. Therefore, the final fermentation liquid contains about 2-3% salt. In the existing fermentation process of producing 1,3-PDO, electrodialysis is usually used for desalination, so that anions and cations pass through ion exchange membranes to the concentrate liquid respectively, so that the salt concentration is reduced. However, in this process, the uncharged 1,3-PDO product also diffuses into the concentrate liquid due to the concentration difference, resulting in product loss. According to production data, the concentration of 1,3-PDO in the concentrate liquid is 1-3%, and the mass of 1,3-PDO lost in the concentrate liquid accounts for 4-5% of the total amount in the fermentation liquid. In order to further improve the yield of 1,3-PDO products, the following methods are used for treatment: (1) selecting an ion exchange membrane with higher current efficiency and higher density, but this increases production costs; (2) recovering the concentrated liquid, such as concentrating and crystallizing, separating the salt crystals and subjecting the crystallization mother liquor to secondary electrodialysis desalination. However, the above methods require the addition of a concentrating crystallizer and electrodialysis equipment, which requires high investment and energy consumption.

[0005] Therefore, how to recycle the concentrated liquid produced in the electrodialysis desalination process, improve the recovery rate of 1,3-PDO, and reduce equipment investment and energy consumption is a technical problem that needs to be solved in this field. Summary of the invention

[0006] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for separating and recovering 1,3-PDO in electrodialysis concentrate liquid and a device system thereof. Compared with the prior art, the method provided by the present invention can separate and recover 1,3-PDO in electrodialysis concentrate liquid, improve the recovery rate of 1,3-PDO, and facilitate the subsequent preparation of high-purity 1,3-PDO products.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a method for separating and recovering 1,3-PDO in an electrodialysis concentrate chamber solution, the method comprising the following steps:

[0009] (1) subjecting the 1,3-PDO fermentation broth to an ultrafiltration treatment and an electrodialysis desalination treatment in sequence to obtain an electrodialysis concentrated chamber solution and an electrodialysis desalted solution;

[0010] (2) subjecting the electrodialysis concentrated chamber liquid obtained in step (1) to reverse osmosis filtration to obtain reverse osmosis filtrate;

[0011] (3) The electrodialysis desalted liquid obtained in step (1) and the reverse osmosis filtrate obtained in step (2) are mixed to obtain a purified liquid of 1,3-PDO.

[0012] In the present invention, firstly, the 1,3-PDO fermentation liquid is subjected to electrodialysis desalination treatment, which can remove most of the salt in the fermentation liquid and obtain an electrodialysis desalted liquid with a high 1,3-PDO content; the electrodialysis concentrated chamber liquid with a high salt content is subjected to reverse osmosis filtration treatment, so that the salts are retained by the reverse osmosis membrane, and water and 1,3-PDO pass through the reverse osmosis membrane to obtain a reverse osmosis filtrate; finally, the reverse osmosis filtrate and the electrodialysis desalted liquid are mixed to obtain a purified 1,3-PDO liquid and enter a downstream purification process, such as multiple-effect evaporation, distillation, etc., to finally obtain a 1,3-PDO product with a high purity.

[0013] Preferably, the 1,3-PDO fermentation broth in step (1) comprises a fermentation broth obtained by fermentation with Klebsiella.

[0014] In the present invention, the method of preparing 1,3-PDO fermentation broth by fermentation with Klebsiella is a conventional method in the art, and uses renewable biomass as a substrate, and the renewable biomass may be, for example, glycerol, glucose, and the like.

[0015] Preferably, the 1,3-PDO fermentation broth comprises, by mass percentage, 85-90% of water, for example, 85%, 86%, 87%, 88%, 89% or 90%; 0.2-2% of succinic acid, for example, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8% or 2%; 0.2-2% of acetic acid, for example, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8% or 2%; 6-9% of 1,3-PDO, for example, 6%. %, 7.2%, 7.5%, 7.8%, 8%, 8.2%, 8.5%, 8.8% or 9%; 2-4% 2,3-butanediol, for example, can be 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8% or 4%; 0.2-2% glycerol, for example, can be 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8% or 2%; 0.1-0.8% ethanol, for example, can be 0.1%, 0.2%, 0.4%, 0.6% or 0.8%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0016] Preferably, the conductivity of the 1,3-PDO fermentation broth is 2000-20000 μs / cm, for example, 2000 μs / cm, 4000 μs / cm, 6000 μs / cm, 8000 μs / cm, 10000 μs / cm, 12000 μs / cm, 14000 μs / cm, 16000 μs / cm, 18000 μs / cm or 20000 μs / cm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0017] In the present invention, the pore size of the filter membrane treated by ultrafiltration is generally 5-100nm, for example, it can be 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm or 100nm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0018] Preferably, the ion exchange membrane used in the electrodialysis desalination treatment in step (1) comprises a heterogeneous membrane or a semi-homogeneous membrane.

[0019] Preferably, the voltage used in the electrodialysis desalination treatment is 0.8-1.5 V / pair of membranes, for example, it can be 0.8 V / pair of membranes, 0.9 V / pair of membranes, 1 V / pair of membranes, 1.2 V / pair of membranes, 1.3 V / pair of membranes, 1.4 V / pair of membranes or 1.5 V / pair of membranes, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0020] In the present invention, electrodialysis desalination treatment generally uses multiple pairs of ion exchange membranes (i.e., multiple membrane stacks) in series for electrodialysis, for example, 12 pairs of ion exchange membranes are used in series. The present invention can avoid the voltage of the electrodialysis desalination treatment being too low, which leads to a slow desalination rate and affects the production capacity of the equipment, and avoids the risk of membrane burning caused by excessive current in the membrane stack and excessive heat generation in the membrane stack due to excessive voltage, and avoids the reduction of desalination efficiency due to concentration polarization.

[0021] Preferably, the mass percentage of 1,3-PDO in the electrodialysis concentrate is 1-3%, for example, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8% or 3%, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0022] Preferably, the conductivity of the electrodialysis concentrate liquid is 20000-60000 μs / cm, for example, it may be 20000 μs / cm, 25000 μs / cm, 30000 μs / cm, 35000 μs / cm, 40000 μs / cm, 45000 μs / cm, 50000 μs / cm, 55000 μs / cm or 60000 μs / cm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are equally applicable.

[0023] Preferably, the mass percentage of 1,3-PDO in the electrodialysis desalting solution is 7-9%, for example, it can be 7%, 7.2%, 7.4%, 7.6%, 7.8%, 8%, 8.2%, 8.4%, 8.6%, 8.8% or 9%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0024] Preferably, the conductivity of the electrodialysis desalting solution is ≤2000μs / cm, for example, it can be 2000μs / cm, 1900μs / cm, 1800μs / cm, 1700μs / cm, 1600μs / cm or 1500μs / cm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0025] Preferably, during the reverse osmosis filtration treatment in step (2), dialysis water is added to the electrodialysis concentration chamber fluid.

[0026] Preferably, the amount of dialysis water added is 0.5-1.5 times the mass of the electrodialysis concentration chamber fluid, for example, it can be 0.5 times, 0.6 times, 0.7 times, 0.8 times, 0.9 times, 1.0 times, 1.1 times, 1.2 times, 1.3 times, 1.4 times or 1.5 times, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0027] In the present invention, by continuously adding dialysis water to the electrodialysis concentration chamber liquid to dilute it and perform reverse osmosis, preferably controlling the amount of dialysis water added, the pressure required for reverse osmosis can be reduced, the recovery rate of 1,3-PDO can be improved, and the difficulty of subsequent separation and purification caused by excessive introduction of water can be avoided.

[0028] Preferably, the pressure of the reverse osmosis filtration treatment in step (2) is 3-6 MPa, for example, it can be 3 MPa, 3.2 MPa, 3.4 MPa, 3.6 MPa, 3.8 MPa, 4 MPa, 4.2 MPa, 4.4 MPa, 4.6 MPa, 4.8 MPa, 5 MPa, 5.2 MPa, 5.4 MPa, 5.6 MPa, 5.8 MPa or 6 MPa, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0029] In the present invention, the temperature of the reverse osmosis filtration treatment is not particularly limited, and the conventional temperature of reverse osmosis treatment in the art can be adopted, which is generally ≤40°C.

[0030] Preferably, the conductivity of the reverse osmosis filtrate in step (2) is ≤400 μs / cm, for example, it can be 400 μs / cm, 380 μs / cm, 360 μs / cm, 340 μs / cm, 320 μs / cm or 300 μs / cm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0031] Preferably, the recovery rate of 1,3-PDO in the electrodialysis concentrate liquid by the reverse osmosis filtration treatment in step (2) is ≥ 60%, for example, it can be 60%, 61%, 62%, 63%, 64% or 65%, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0032] As a preferred technical solution of the first aspect of the present invention, the method comprises the following steps:

[0033] (1) subjecting the 1,3-PDO fermentation broth to ultrafiltration to obtain an ultrafiltrate, subjecting the ultrafiltrate to electrodialysis desalination treatment at a voltage of 0.8-1.5 V / membrane pair to obtain an electrodialysis concentrate liquid and an electrodialysis desalted liquid, wherein the mass percentage of 1,3-PDO in the electrodialysis concentrate liquid is 1-3%, and the conductivity is 20000-60000 μs / cm, and the mass percentage of 1,3-PDO in the electrodialysis desalted liquid is 7-9%, and the conductivity is ≤2000 μs / cm;

[0034] The 1,3-PDO fermentation broth includes a fermentation broth obtained by fermenting Klebsiella, wherein the 1,3-PDO fermentation broth includes, by mass percentage, 85-90% of water, 0.2-2% of succinic acid, 0.2-2% of acetic acid, 6-9% of 1,3-PDO, 2-4% of 2,3-butanediol, 0.2-2% of glycerol and 0.1-0.8% of ethanol; the conductivity of the 1,3-PDO fermentation broth is 2000-20000 μs / cm;

[0035] (2) subjecting the electrodialysis concentrate liquid obtained in step (1) to reverse osmosis filtration, wherein dialysis water is added to the electrodialysis concentrate liquid during the reverse osmosis filtration, wherein the amount of dialysis water added is 0.5-1.5 times the mass of the electrodialysis concentrate liquid, and the pressure of the reverse osmosis filtration is 3-6 MPa to obtain a reverse osmosis filtrate, wherein the conductivity of the reverse osmosis filtrate is ≤400 μs / cm;

[0036] (3) The electrodialysis desalted liquid obtained in step (1) and the reverse osmosis filtrate obtained in step (2) are mixed to obtain a purified liquid of 1,3-PDO.

[0037] In a second aspect, the present invention provides a device system for separating and recovering 1,3-PDO in an electrodialysis concentrate chamber liquid, the device system is used in the method for separating and recovering 1,3-PDO in an electrodialysis concentrate chamber liquid according to the first aspect of the present invention, the device system comprises a fermentation device, an ultrafiltration device, an electrodialysis device and a reverse osmosis device;

[0038] The inlet of the ultrafiltration device is connected to the fermentation device, and the outlet of the ultrafiltration device is connected to the electrodialysis device;

[0039] The concentrated water chamber outlet of the electrodialysis device is connected to a reverse osmosis device;

[0040] The filtrate outlet of the reverse osmosis device and the outlet of the fresh water chamber of the electrodialysis device are respectively connected to the purified 1,3-PDO pipeline.

[0041] The device system provided by the present invention can perform reverse osmosis on the electrodialysis concentrated chamber liquid, thereby further improving the yield of 1,3-PDO, which is beneficial to the subsequent preparation of 1,3-PDO products.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] (1) The method and device system for separating and recovering 1,3-PDO in the electrodialysis concentrate liquid provided by the present invention can separate and recover 1,3-PDO in the electrodialysis concentrate liquid by reverse osmosis, and can improve the recovery rate of 1,3-PDO by adding dialysis water and controlling the amount of dialysis water added during the reverse osmosis process, so that the electrodialysis desalted liquid and the reverse osmosis filtrate are mixed to obtain a purified 1,3-PDO liquid, which is beneficial to the subsequent preparation of a high-purity 1,3-PDO product.

[0044] (2) In the present invention, 1,3-PDO in the electrodialysis concentrate is recovered by reverse osmosis filtration. Under optimal conditions, the recovery rate is more than 60.0%. The method provided by the present invention recovers 1,3-PDO in the 1,3-PDO ultrafiltrate by electrodialysis desalination and reverse osmosis filtration. Under optimal conditions, the total recovery rate is more than 98.0%. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 is a schematic diagram of the structure of the device system provided in Example 1;

[0046] Among them, 1-fermentation device; 2-ultrafiltration device; 3-electrodialysis device; 4-reverse osmosis device; 5-1,3-PDO purification pipeline. DETAILED DESCRIPTION

[0047] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0048] In a specific embodiment, the method for separating and recovering 1,3-PDO in the electrodialysis concentrate chamber liquid provided by the present invention is carried out in a device system for separating and recovering 1,3-PDO in the electrodialysis concentrate chamber liquid, such as Figure 1 As shown, the device system includes a fermentation device 1, an ultrafiltration device 2, an electrodialysis device 3 and a reverse osmosis device 4, the inlet of the ultrafiltration device 2 is connected to the fermentation device 1, the outlet of the ultrafiltration device 2 is connected to the electrodialysis device 3, the concentrated water chamber outlet of the electrodialysis device 3 is connected to the reverse osmosis device 4, and the filtrate outlet of the reverse osmosis device 4 and the fresh water chamber outlet of the electrodialysis device 3 are respectively connected to the purified 1,3-PDO pipeline 5.

[0049] The device system provided by the present invention can perform reverse osmosis on the electrodialysis concentrated chamber liquid, thereby further improving the yield of 1,3-PDO, which is beneficial to the subsequent preparation of 1,3-PDO products.

[0050] In the following examples, liquid chromatography was used to detect the materials at each stage, and the recovery rate of 1,3-PDO in the electrodialysis concentrate by reverse osmosis filtration was calculated as follows: the mass of 1,3-PDO in the reverse osmosis filtrate / the mass of 1,3-PDO in the electrodialysis concentrate × 100%; and the total recovery rate of 1,3-PDO in the 1,3-PDO ultrafiltrate was calculated as follows: the mass of 1,3-PDO in the purified solution of 1,3-PDO / the mass of 1,3-PDO in the 1,3-PDO ultrafiltrate × 100%, wherein the mass of 1,3-PDO in the purified solution of 1,3-PDO = the mass of 1,3-PDO in the reverse osmosis filtrate + the mass of 1,3-PDO in the electrodialysis desalting solution.

[0051] Example 1

[0052] This embodiment provides a method for separating and recovering 1,3-PDO in electrodialysis concentrate chamber fluid and a device system thereof. The device system is as follows: Figure 1 As shown, the device system includes a fermentation device 1, an ultrafiltration device 2, an electrodialysis device 3 and a reverse osmosis device 4, and the method includes the following steps:

[0053] (1) The 1,3-PDO fermentation liquid in the fermentation device 1 is sent to the ultrafiltration device 2, and ultrafiltration treatment is performed using a ceramic membrane with a pore size of 50 nm to obtain an ultrafiltrate, and the ultrafiltrate is sent to the electrodialysis device 3, and electrodialysis desalination treatment is performed using a heterogeneous membrane as an ion exchange membrane. Before the electrodialysis desalination treatment, water is added to the concentration chamber in advance. The voltage of the electrodialysis desalination treatment is 0.8 V / membrane pair, and an electrodialysis concentration chamber liquid and an electrodialysis desalted liquid are obtained;

[0054] (2) sending the electrodialysis concentrate liquid obtained in step (1) to a reverse osmosis device 4 for reverse osmosis filtration treatment, adding dialysis water to dilute the electrodialysis concentrate liquid during the reverse osmosis filtration treatment, wherein the amount of dialysis water added is 0.5 times the mass of the electrodialysis concentrate liquid, the pressure of the reverse osmosis filtration treatment is 5.5 MPa, and the temperature is 38° C., to obtain reverse osmosis filtrate and reverse osmosis concentrate;

[0055] (3) The electrodialysis desalted liquid obtained in step (1) and the reverse osmosis filtrate obtained in step (2) are mixed in the 1,3-PDO purification pipeline 5 to obtain a purified 1,3-PDO liquid.

[0056] The materials at each stage in this embodiment were tested, and the results are shown in Table 1.

[0057] Table 1

[0058]

[0059] In Table 1, “ / ” means that the data is not available.

[0060] According to the data in Table 1, it is calculated that the recovery rate of 1,3-PDO by reverse osmosis filtration is 60.0%, and the total recovery rate of 1,3-PDO in the 1,3-PDO ultrafiltrate is 98.0%. The present invention improves the recovery rate of 1,3-PDO, improves the economic benefits of production, and reduces production costs.

[0061] Example 2

[0062] This embodiment provides a method for separating and recovering 1,3-PDO in electrodialysis concentrate chamber fluid. The device system used in the method is the same as that in Example 1. The method comprises the following steps:

[0063] (1) ultrafiltration treatment of 1,3-PDO fermentation broth using a ceramic membrane with a pore size of 50 nm to obtain an ultrafiltrate, and electrodialysis desalination treatment of the ultrafiltrate using a heterogeneous membrane as an ion exchange membrane, water is added to the concentration chamber before the electrodialysis desalination treatment, and the voltage of the electrodialysis desalination treatment is 1.5 volts per membrane pair to obtain an electrodialysis concentration chamber liquid and an electrodialysis desalted liquid;

[0064] (2) subjecting the electrodialysis concentrate liquid obtained in step (1) to reverse osmosis filtration, wherein dialysis water is added to the electrodialysis concentrate liquid for dilution during the reverse osmosis filtration, wherein the amount of dialysis water added is 1 times the mass of the electrodialysis concentrate liquid, and the reverse osmosis filtration pressure is 4 MPa and the temperature is 38° C., to obtain reverse osmosis filtrate and reverse osmosis concentrate;

[0065] (3) The electrodialysis desalted liquid obtained in step (1) and the reverse osmosis filtrate obtained in step (2) are mixed to obtain a purified liquid of 1,3-PDO.

[0066] The materials at each stage in this embodiment were tested, and the results are shown in Table 2.

[0067] Table 2

[0068]

[0069]

[0070] In Table 2, “ / ” indicates that the data is not available.

[0071] According to the data in Table 2, the recovery rate of 1,3-PDO by reverse osmosis filtration treatment is 62.4%, and the total recovery rate of 1,3-PDO in the 1,3-PDO ultrafiltrate is 98.1%. The present invention improves the recovery rate of 1,3-PDO, improves the economic benefits of production, and reduces production costs.

[0072] Example 3

[0073] This embodiment provides a method for separating and recovering 1,3-PDO in electrodialysis concentrate chamber fluid. The device system used in the method is the same as that in Example 1. The method comprises the following steps:

[0074] (1) ultrafiltration of 1,3-PDO fermentation broth using a ceramic membrane with a pore size of 50 nm to obtain an ultrafiltrate, and electrodialysis desalination of the ultrafiltrate using a heterogeneous membrane as an ion exchange membrane, water is added to the concentration chamber before the electrodialysis desalination, and the voltage of the electrodialysis desalination is 1 volt per membrane pair to obtain an electrodialysis concentration chamber liquid and an electrodialysis desalted liquid;

[0075] (2) subjecting the electrodialysis concentrate liquid obtained in step (1) to reverse osmosis filtration, wherein dialysis water is added to dilute the electrodialysis concentrate liquid during the reverse osmosis filtration, wherein the amount of dialysis water added is 1.5 times the mass of the electrodialysis concentrate liquid, and the pressure of the reverse osmosis filtration is 3.5 MPa and the temperature is 38° C., to obtain reverse osmosis filtrate and reverse osmosis concentrate;

[0076] (3) The electrodialysis desalted liquid obtained in step (1) and the reverse osmosis filtrate obtained in step (2) are mixed to obtain a purified liquid of 1,3-PDO.

[0077] The materials at each stage in this embodiment were tested, and the results are shown in Table 3.

[0078] Table 3

[0079]

[0080]

[0081] In Table 3, “ / ” indicates that the data is not available.

[0082] According to the data in Table 3, the recovery rate of 1,3-PDO by reverse osmosis filtration treatment is 64.6%, and the total recovery rate of 1,3-PDO in the 1,3-PDO ultrafiltrate is 98.2%. The present invention improves the recovery rate of 1,3-PDO, improves the economic benefits of production, and reduces production costs.

[0083] Example 4

[0084] This embodiment provides a method for separating and recovering 1,3-PDO in electrodialysis concentrate chamber fluid. The difference between the method and embodiment 3 is that no dialysis water is added in the reverse osmosis filtration process.

[0085] The results of this example show that as the reverse osmosis filtration process proceeds, the salt content on the liquid side of the electrodialysis concentrate chamber increases, and the osmotic pressure increases, resulting in a rapid decrease in flux until filtration becomes impossible.

[0086] The material in the reverse osmosis filtration treatment stage in this embodiment was tested, and the results are shown in Table 4.

[0087] Table 4

[0088]

[0089]

[0090] In Table 4, “ / ” indicates that the data is not available.

[0091] Compared with Example 3, the only difference in this example is that no dialysis water is added, the osmotic pressure on the electrodialysis concentration chamber liquid side is higher, the reverse osmosis flux is reduced, the reverse osmosis concentration multiple is reduced, the recovery rate of 1,3-PDO by reverse osmosis filtration treatment is only 15%, and the total recovery rate of 1,3-PDO in the 1,3-PDO ultrafiltrate is 95.7%.

[0092] Example 5

[0093] This embodiment provides a method for separating and recovering 1,3-PDO in electrodialysis concentrate chamber fluid. The difference between the method and embodiment 3 is that the amount of dialysis water added is 0.2 times the mass of the electrodialysis concentrate chamber fluid.

[0094] The material in the reverse osmosis filtration treatment stage in this embodiment was tested, and the results are shown in Table 5.

[0095] Table 5

[0096]

[0097]

[0098] In Table 5, “ / ” indicates that the data is not available.

[0099] Compared with Example 3, the only difference between this embodiment and Example 3 is that the amount of dialysis water added is not within the preferred range of the present invention. In this embodiment, the amount of dialysis water added is too little, the reverse osmosis filtration flux is low, the filtrate collection is small, the recovery rate of 1,3-PDO by reverse osmosis filtration treatment is only 29.9%, and the total recovery rate of 1,3-PDO in 1,3-PDO ultrafiltrate is 96.5%; if too much dialysis water is added, the concentration of 1,3-PDO in the reverse osmosis filtrate will be too low, and the subsequent evaporation and dehydration energy consumption will be high. It can be seen that the present invention can further improve the recovery effect of 1,3-PDO by preferably controlling the amount of dialysis water added, and reduce the processing cost and improve the economic efficiency of production.

[0100] Example 6

[0101] This embodiment provides a method for separating and recovering 1,3-PDO in electrodialysis concentrate chamber liquid. The difference between the method and embodiment 3 is that the pressure of reverse osmosis filtration treatment is 2.5 MPa.

[0102] The material in the reverse osmosis filtration treatment stage in this embodiment was tested, and the results are shown in Table 6.

[0103] Table 6

[0104]

[0105] In Table 6, “ / ” indicates that the data is not available.

[0106] The difference between this embodiment and embodiment 3 is that the pressure of the reverse osmosis filtration treatment is not within the preferred range of the present invention. In this embodiment, the pressure is too low, resulting in a small reverse osmosis filtration flux, less filtrate collection, and the recovery rate of 1,3-PDO by reverse osmosis filtration treatment is only 45.3%, and the total recovery rate of 1,3-PDO in the 1,3-PDO ultrafiltrate is 97.2%. If the pressure is too high, the filtration energy consumption is high. It can be seen that the present invention can further improve the recovery effect of 1,3-PDO by preferably controlling the pressure of the reverse osmosis filtration treatment, reduce the processing cost, and improve the economic efficiency of production.

[0107] In summary, the method provided by the present invention can separate and recover 1,3-PDO in the electrodialysis concentrate liquid, improve the recovery rate of 1,3-PDO, facilitate the subsequent preparation of high-purity 1,3-PDO products, reduce production costs and energy consumption, and improve economic and environmental benefits.

[0108] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention are within the protection scope and disclosure scope of the present invention.

Claims

1. A method for separating and recovering 1,3-PDO in electrodialysis concentrate chamber fluid, characterized in that: The method comprises the following steps: (1) subjecting the 1,3-PDO fermentation broth to an ultrafiltration treatment and an electrodialysis desalination treatment in sequence to obtain an electrodialysis concentrated chamber solution and an electrodialysis desalted solution; (2) subjecting the electrodialysis concentrated chamber liquid obtained in step (1) to reverse osmosis filtration to obtain reverse osmosis filtrate; (3) The electrodialysis desalted liquid obtained in step (1) and the reverse osmosis filtrate obtained in step (2) are mixed to obtain a purified liquid of 1,3-PDO.

2. The method according to claim 1, characterized in that The 1,3-PDO fermentation broth in step (1) includes a fermentation broth obtained by fermentation with Klebsiella; Preferably, the 1,3-PDO fermentation broth comprises, by mass percentage, 85-90% water, 0.2-2% succinic acid, 0.2-2% acetic acid, 6-9% 1,3-PDO, 2-4% 2,3-butanediol, 0.2-2% glycerol and 0.1-0.8% ethanol; Preferably, the conductivity of the 1,3-PDO fermentation broth is 2000-20000 μs / cm.

3. The method according to claim 1 or 2, characterized in that: The ion exchange membrane used in the electrodialysis desalination treatment in step (1) includes a heterogeneous membrane or a semi-homogeneous membrane; Preferably, the voltage used in the electrodialysis desalination treatment is 0.8-1.5 V / pair of membranes.

4. The method according to any one of claims 1 to 3, characterized in that: The mass percentage of 1,3-PDO in the electrodialysis concentrate solution of step (1) is 1-3%; Preferably, the conductivity of the electrodialysis concentrate liquid is 20000-60000 μs / cm; Preferably, the mass percentage of 1,3-PDO in the electrodialysis desalting solution is 7-9%; Preferably, the conductivity of the electrodialysis desalting solution is ≤2000 μs / cm.

5. The method according to any one of claims 1 to 4, characterized in that: During the reverse osmosis filtration treatment in step (2), dialyzate water is added to the electrodialysis concentrate solution; Preferably, the amount of dialysis water added is 0.5-1.5 times the mass of the electrodialysis concentration chamber fluid.

6. The method according to any one of claims 1 to 5, characterized in that: The pressure of the reverse osmosis filtration treatment in step (2) is 3-6 MPa.

7. The method according to any one of claims 1 to 6, characterized in that: The conductivity of the reverse osmosis filtrate in step (2) is ≤400 μs / cm.

8. The method according to any one of claims 1 to 7, characterized in that: The reverse osmosis filtration treatment in step (2) has a recovery rate of 1,3-PDO in the electrodialysis concentrate chamber liquid of ≥60%.

9. The method according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: (1) subjecting the 1,3-PDO fermentation broth to ultrafiltration to obtain an ultrafiltrate, subjecting the ultrafiltrate to electrodialysis desalination treatment at a voltage of 0.8-1.5 V / membrane pair to obtain an electrodialysis concentrate liquid and an electrodialysis desalted liquid, wherein the mass percentage of 1,3-PDO in the electrodialysis concentrate liquid is 1-3%, and the conductivity is 20000-60000 μs / cm, and the mass percentage of 1,3-PDO in the electrodialysis desalted liquid is 7-9%, and the conductivity is ≤2000 μs / cm; The 1,3-PDO fermentation broth includes a fermentation broth obtained by fermenting Klebsiella, wherein the 1,3-PDO fermentation broth includes, by mass percentage, 85-90% of water, 0.2-2% of succinic acid, 0.2-2% of acetic acid, 6-9% of 1,3-PDO, 2-4% of 2,3-butanediol, 0.2-2% of glycerol and 0.1-0.8% of ethanol; the conductivity of the 1,3-PDO fermentation broth is 2000-20000 μs / cm; (2) subjecting the electrodialysis concentrate liquid obtained in step (1) to reverse osmosis filtration, wherein dialysis water is added to the electrodialysis concentrate liquid during the reverse osmosis filtration, wherein the amount of dialysis water added is 0.5-1.5 times the mass of the electrodialysis concentrate liquid, and the pressure of the reverse osmosis filtration is 3-6 MPa to obtain a reverse osmosis filtrate, wherein the conductivity of the reverse osmosis filtrate is ≤400 μs / cm; (3) The electrodialysis desalted liquid obtained in step (1) and the reverse osmosis filtrate obtained in step (2) are mixed to obtain a purified liquid of 1,3-PDO.

10. A device system for separating and recovering 1,3-PDO in electrodialysis concentrate chamber fluid, characterized in that: The device system is used for the method for separating and recovering 1,3-PDO in electrodialysis concentration chamber liquid as claimed in any one of claims 1 to 9, and the device system comprises a fermentation device, an ultrafiltration device, an electrodialysis device and a reverse osmosis device; The inlet of the ultrafiltration device is connected to the fermentation device, and the outlet of the ultrafiltration device is connected to the electrodialysis device; The concentrated water chamber outlet of the electrodialysis device is connected to a reverse osmosis device; The filtrate outlet of the reverse osmosis device and the outlet of the fresh water chamber of the electrodialysis device are respectively connected to the purified 1,3-PDO pipeline.

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