CN106589099B - Desalination system and desalination method for soluble silk fibroin solution - Google Patents
Desalination system and desalination method for soluble silk fibroin solution Download PDFInfo
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- CN106589099B CN106589099B CN201710059839.6A CN201710059839A CN106589099B CN 106589099 B CN106589099 B CN 106589099B CN 201710059839 A CN201710059839 A CN 201710059839A CN 106589099 B CN106589099 B CN 106589099B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/43504—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates
- C07K14/43563—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects
- C07K14/43586—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects from silkworms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—Multistep processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A20/124—Water desalination
Abstract
The invention discloses a desalting system and a desalting method of a soluble silk fibroin solution. Introducing a silk fibroin solution into a raw material box of a diffusion dialysis module for diffusion dialysis to obtain a primary desalted silk fibroin solution; and then the primary desalted silk fibroin solution is led into a raw material box of an electrodialysis module to carry out electrodialysis, so as to obtain the secondary desalted silk fibroin solution. According to the invention, diffusion dialysis is combined with electrodialysis, and the method is used for desalting in a protein organic system for the first time, fully utilizes the high concentration difference of a silk fibroin solution, and performs desalination by using diffusion dialysis when the concentration difference is used as a driving force and the desalination efficiency is high; when the desalination efficiency is low by taking the concentration difference as the driving force, the electrodialysis is replaced by diffusion dialysis in time, and the desalination is performed by taking the potential difference as the driving force, so that the low energy consumption and the high desalination efficiency are ensured.
Description
Technical Field
The invention relates to the technical field of protein solution treatment, in particular to a desalting system and a desalting method of a soluble silk fibroin solution.
Background
Silk is composed of about 75% by weight of silk fibroin (core fiber) and 25% by weight of sericin (overcoat and adhesive layer). Silk fibroin is a functional material with very wide application prospect, and is widely applied to the fields of clothing, medicine, biology and the like. Natural silk fibroin is insoluble in water, but can be dissolved in strong acids, strong bases, and some neutral salt solutions. Since strong acids and bases destroy the protein structure of silk fibroin, some neutral salts such as chloride and iodide are harmful to human body, it is most common today to use a ternary system of calcium chloride-ethanol-water to dissolve silk fibroin.
The ternary system for dissolving the silk fibroin has high salt concentration, and desalination becomes an important link in the production of the soluble silk fibroin. The most traditional desalting method adopts dialysis bags for desalting, and the method has the advantages of long time consumption, less batch and high cost. With the development of membrane engineering, membrane technologies such as ultrafiltration, nanofiltration, electrodialysis and the like are increasingly used for desalination.
The patent applications with publication numbers CN1392265A and CN102172257a use nanofiltration technology to remove high concentration salt from the silk fibroin solution, and the desalination rates are 98% and 90%, respectively. The patent application publication CN101381758A uses a combination of ultrafiltration and nanofiltration to desalt: the macromolecular peptide segments in the solution are separated by ultrafiltration technology, and then the high-concentration salt is separated by nanofiltration technology, wherein the desalination rate is not more than 93.5%. Although the method shortens desalting time compared with the conventional dialysis bag, silk fibroin and CaCl are utilized in ultrafiltration and nanofiltration 2 The difference in molecular weight separates the two, so that the desalination rate is not high and the separation depends on the driving forceThe pressure difference gradually decreases the salt content in the silk fibroin solution, the desalination efficiency gradually decreases, the desalination time is prolonged, and the desalination efficiency becomes lower until the later stage of desalination. In addition, the pore diameter of the membrane used for nanofiltration and ultrafiltration is very small, the surface of the membrane is very compact, the viscosity of the solution after the silk fibroin is dissolved is high, the flow channel of the membrane can be blocked, and the nanofiltration membrane needs to be cleaned frequently in practical application, so that the desalination efficiency can be reduced, and the desalination time can be prolonged.
In the patent application with publication number CN103897021A, electrodialysis is adopted to desalt and prepare a silk peptide, and the total content of hetero ions in the finally obtained silk peptide is less than 1%. In the patent application publication No. CN103243145A, electrodialysis is used for desalting, and dialysis bag is used for filtering, so that the final desalting rate is 99.5%. The electrodialysis desalination can greatly shorten the desalination time and can also enable the desalination rate to reach nearly 100 percent. But CaCl in the initial silk fibroin solution 2 The concentration of (2) reaches 400g/L, and if the desalination rate reaches 99.5% by using electrodialysis technology, the energy consumption is very high. Moreover, electrodialysis desalination requires power all the time, and in fact, there is such a high concentration difference between the solution and deionized water, and desalination can be performed completely by using the concentration difference as a driving force for a long period of time from the start of desalination, and power consumption is not necessary. In general, caCl in desalted pre-silk fibroin solution 2 The concentration of the water is 150g/L-300g/L, and the water is desalted by using an electrodialysis technology, so that the problems of low desalination rate, large energy consumption, overlong desalination time and the like can occur, and the problems that electrodialysis equipment needs large current to operate and the like are easy to damage and leak.
Disclosure of Invention
The invention aims at overcoming the technical defects existing in the prior art, and in a first aspect, the invention provides a desalting system of a soluble silk fibroin solution with high desalting rate and energy conservation, which comprises a raw material box, a diffusion dialysis module and an electrodialysis module, wherein the raw material box is provided with two inlets of a diffusion dialysis liquid inlet and an electrodialysis raw material inlet and two outlets of a raw material outlet and an electrodialysis raw material outlet, the diffusion dialysis liquid inlet and the raw material outlet of the raw material box are connected with the diffusion dialysis module, and the electrodialysis raw material inlet and the electrodialysis raw material outlet of the raw material box are connected with the electrodialysis module.
The diffusion dialysis module comprises a diffusion dialysis material pump, a diffusion water pump, a diffusion dialyzer and a deionized water tank; the diffusion dialyzer is connected with the raw material box through a diffusion dialysis material pump, and the deionized water box is connected with the diffusion dialyzer through a diffusion water pump.
The diffusion dialyzer is provided with a raw material inlet, a diffusion dialysis liquid outlet, a diffusion water inlet and a diffusion water outlet; the raw material inlet and the diffusion dialysis liquid outlet are respectively connected with the raw material outlet and the diffusion dialysis liquid inlet of the raw material box; the diffusion water inlet and the diffusion water outlet are respectively connected with the water outlet and the water inlet of the deionized water tank; preferably, the positions of the raw material inlet and the diffusion dialysis liquid outlet of the diffusion dialysis device are arranged in a diagonal manner; the positions of the diffusion water inlet and the diffusion water outlet are also arranged diagonally.
A raw material flowmeter and a raw material pressure gauge are further arranged on a pipeline between the raw material box and the diffusion dialyzer; and a diffusion water flowmeter and a diffusion water pressure meter are further arranged on a pipeline between the deionized water tank and the diffusion dialyzer.
The electrodialysis module comprises an electrodialysis material pump, an electrodialysis water pump, an electrodialyzer and a water tank; the electrodialysis device is connected with a raw material box through an electrodialysis material pump, and a water tank is connected with the electrodialysis device through an electrodialysis water pump.
The electrodialysis device comprises a concentration chamber and a desalination chamber which are longitudinally and alternately arranged in parallel, and an electrodialysis raw material inlet of the raw material box is connected with an outlet of the desalination chamber; the electrodialysis raw material outlet of the raw material box is connected with the inlet of the concentration chamber; the inlet of the desalination chamber and the outlet of the concentration chamber are respectively connected with the fresh water outlet and the concentrated water inlet of the water tank.
A primary desalting solution flowmeter and a primary desalting solution pressure gauge are further arranged on a pipeline between the raw material box and the electrodialyzer; and an electroosmosis water flowmeter and an electroosmosis water pressure meter are further arranged on a pipeline between the water tank and the electrodialyzer.
In a second aspect, the present invention provides a method for desalting a soluble silk fibroin solution, wherein the desalting system is used to introduce the silk fibroin solution into a diffusion dialysis module from a raw material tank for diffusion dialysis to obtain a primary desalted silk fibroin solution; and introducing the primary desalted silk fibroin solution into a raw material box of an electrodialysis module for electrodialysis to obtain a secondary desalted silk fibroin solution, namely the desalted silk fibroin solution.
The method comprises the following steps:
(1) Primary desalting was performed by diffusion dialysis: opening diffusion dialysis module quickly, closing electrodialysis module, and feeding silk fibroin solution (silk is passed through Na from silk 2 CO 3 Degumming, namely dissolving a calcium chloride-ethanol-water ternary system), wherein the raw materials enter a diffusion dialyser from a raw material inlet of the diffusion dialyser at the liquid linear speed of 1-5cm/s by a diffusion dialyser pump, and come out from a diffusion dialyser liquid outlet after diffusion dialyser, and the circulating flow returns to a raw material box, deionized water in a deionized water box is pumped into the diffusion dialyser from a diffusion water inlet by a diffusion water pump at the linear speed of 1-5cm/s, flows out from a diffusion water outlet, and returns to a deionized water box; stopping diffusion dialysis when the salt content of deionized water in the deionized water tank is 60-70% (preferably 65%) of the initial salt content, so as to obtain a primary desalted silk fibroin solution; the linear velocity ratio of the silk fibroin solution to deionized water is (1-2): 1, (preferably 2:1);
(2) Secondary desalting by electrodialysis: closing a diffusion dialysis module quickly, opening an electrodialysis module, switching on a power supply (the current is not more than 0.3A, preferably 0.2A), pumping primary desalted silk fibroin solution in a raw material box into a desalting chamber of an electrodialyzer through an electrodialysis liquid inlet by an electrodialysis material pump at the liquid linear speed of 1-5cm/s, desalting by electrodialysis, flowing out of an electrodialysis product outlet of the desalting chamber, circulating into the raw material box, simultaneously enabling deionized water in a water tank to enter a concentration chamber from a fresh water outlet of the electrodialyzer at the liquid linear speed of 1-5cm/s, performing ion exchange with the primary desalted silk fibroin solution, and then flowing out of the concentration chamber outlet and circularly flowing into the water tank; stopping electrodialysis when the conductivity of the silk fibroin solution in the raw material box is below 200 mu S/cm to obtain a secondary desalted silk fibroin solution, namely a desalted silk fibroin solution, and leading out the desalted silk fibroin solution from an electrodialysis product outlet;
preferably, the concentration of the silk fibroin solution before diffusion dialysis in the raw material box is below 6wt%, the thickness of a baffle plate in a diffusion dialyzer is 2-3mm, the thickness of a baffle plate in a desalting chamber in an electrodialysis apparatus is 2-3mm, and the thickness of a baffle plate in a concentration chamber is 0.5mm; preferably, the ion exchange resin filled in the desalting chamber is a mixed resin obtained by mixing anion exchange resin and cation exchange resin in a mass ratio of 1:1-1:1.5.
In a third aspect, the invention provides a method for producing soluble silk fibroin, taking Na for silk 2 CO 3 Degumming, dissolving a calcium chloride-ethanol-water ternary system to obtain a silk fibroin solution, desalting the silk fibroin solution by the desalting method according to claim 8 or 9 to obtain a secondary desalted silk fibroin solution, and finally freeze-drying to obtain silk fibroin.
Compared with the prior art, the invention has the beneficial effects that:
(1) The desalting system and the desalting method combine diffusion dialysis with electrodialysis, are used for desalting in a protein organic system for the first time, fully utilize the high concentration difference of the silk fibroin solution, and use diffusion dialysis for desalting when the concentration difference is used as the driving force to realize higher desalting efficiency; when the desalination efficiency is low by taking the concentration difference as the driving force, the electrodialysis is replaced by diffusion dialysis in time, and the desalination is performed by taking the potential difference as the driving force, so that the low energy consumption and the high desalination efficiency are ensured.
(2) In the diffusion dialysis process, the solution and the deionized water are operated in a countercurrent mode, so that the contact area can be increased, and the desalination efficiency can be improved.
(3) The deionized water can be recycled in a certain range, and the water can be changed when the TDS value of the solution changes slowly in unit time, so that the water consumption is reduced to the greatest extent.
Drawings
FIG. 1 is a schematic diagram of the principle of diffusion dialysis desalination in the desalination system of the present invention;
FIG. 2 is a schematic diagram of the desalination system of the present invention;
FIG. 3 is a schematic diagram of another embodiment of the desalination system of the present invention.
Detailed Description
The invention provides a desalting system and a desalting method of a soluble silk fibroin solution, namely a diffusion dialysis module and an electrodialysis module are integrated for desalting. The invention fully utilizes the high concentration difference of the silk fibroin solution, firstly utilizes diffusion dialysis to carry out primary desalination, reduces the salt concentration in the silk fibroin solution to a certain extent, and then uses electrodialysis to carry out desalination, thereby fully playing the respective technical advantages of the silk fibroin solution and the electrodialysis, reducing the damage of the solution with larger initial concentration to the ion exchange membrane in the electrodialysis device, reducing the electric energy required to be consumed in the part, and being efficient and energy-saving. Because diffusion dialysis is to utilize the concentration difference of the solution at two sides of the diffusion dialysis membrane as the driving force to realize desalination; electrodialysis is carried out by directional movement of ions under the action of an external electric field, and the two are combined to desalt the silk fibroin solution, so that the advantages of the two are fully exerted, high desalting efficiency and high desalting rate can be realized, and the safety of the desalting process can be ensured. Wherein, the liquid crystal display device comprises a liquid crystal display device,
diffusion dialysis is used as a membrane separation technology with concentration difference as driving force, and has the advantages of simple operation, low energy consumption, no secondary pollution and the like. However, diffusion dialysis is often used for recycling waste acid and waste alkali in inorganic waste liquid at present, and no report on the use of the waste acid and waste alkali in desalting of silk fibroin solution is available. This is because the principle of diffusion dialysis is the competitive diffusion of ions, namely: h during the recovery of waste acid + The acid can be separated by penetrating the negative film to the water side more easily than other metal cations; OH during the recovery of spent caustic - The alkali can be separated by penetrating the membrane to the water side more easily than other acid radical ions. It can be seen that diffusion dialysis is due to H + And OH (OH) - Competitive separation from other ions is easier to penetrate the membrane to the water side and is currently used to recover spent acid and spent alkali, not for desalination.
In the invention, desalination is carried out by diffusion dialysis, and the core of the method is that: firstly, the concentration difference of the solutions at two sides of the diffusion dialysis membrane; and secondly, the selective permeability of the diffusion dialysis membrane. As shown in fig. 1, if the diffusion dialysis membrane in the diffusion dialysis module is cation-exchangedFilm change only allows Ca 2+ By the principle of conservation of charge in the solution and the larger concentration difference at the two sides of the membrane, cl - Will follow Ca 2+ Gradually diffuses to the other side of the membrane, thereby achieving the purpose of desalination. In order to effectively desalt the silk fibroin solution, the invention creatively proposes to arrange a plurality of partition boards in a diffusion dialyzer aiming at the high viscosity of the silk fibroin solution, and to fill cation exchange resin in a compartment formed by the partition boards, so that the diffusion speed of ions in the solution on the resin is faster than that of ions in the aqueous solution, the resin can play a good stirring role in a runner, the thickness of a liquid film is reduced, the resistance of ion diffusion is greatly reduced, and the desalting efficiency is improved. And, the thickness of the separator was determined to be 2-3mm by a great deal of research, and the two ends of the diffusion dialyzer were provided with a grate for preventing resin leakage.
In the patent application with publication number CN105645644a, two-stage diffusion dialysis, two-stage electrodialysis and bipolar membranes are used to recover sulfuric acid from sulfuric acid and sodium sulfate wastewater; in the patent application with publication number of CN103362010A, a diffusion dialysis pretreatment process for recovering electrodialysis alkali from black liquor in pulp manufacture is proposed, wherein the black liquor is pretreated by diffusion dialysis, and electrodialysis treatment is performed after dilute alkali liquor is obtained; in the patent application CN103349912a, diffusion dialysis is also used to pre-treat the viscose fiber, and then electrodialysis is used to recover alkali from the waste liquid generated in the viscose fiber production process. The above methods are all combined with diffusion dialysis and electrodialysis to recover waste acid and waste alkali in an inorganic system, but there is no report of using the waste acid and the waste alkali in protein solutions containing various amino acids and peptide chains. This is because the inorganic system has a low viscosity and contains a single impurity, and the diffusion dialysis and electrodialysis are combined, so that the method is only suitable for inorganic systems or acid-base systems. The silk fibroin solution has higher viscosity, more complex impurity containing condition and more serious membrane pollution condition, and the combined technology of diffusion dialysis and electrodialysis is directly used for desalting the silk fibroin solution, so that the problems of high cost, low desalting efficiency, high membrane replacement frequency and the like exist. Therefore, in order to overcome the problem of high viscosity of the silk fibroin solution, a plurality of partition plates are arranged in the electrodialysis device, a plurality of concentration chambers and a plurality of desalination chambers are formed by the compartments formed by the partition plates, and ion exchange resin is filled in the desalination chambers, wherein the filled ion exchange resin is a mixed resin obtained according to the mass ratio of anion exchange resin to cation exchange resin of 1 (1-1.5), and the electrodialysis is called packed bed electrodialysis. Under the action of the direct current electric field of electrodialysis, salt ions in the silk fibroin solution can realize rapid migration of ions by means of ion exchange resin, because the migration speed of the ions on the resin is 2-3 orders of magnitude faster than that in the solution; the filling of the resin can play a good stirring role in the runner, so that the thickness of the liquid film is reduced, and the resistance of ion migration is greatly reduced. And the thickness of the desalting chamber partition plate is 2-3mm, the thickness of the concentrating chamber partition plate is 0.5mm, and the two ends of the electrodialysis device are provided with the grids for preventing resin leakage.
Through long-term practice and a large number of experiments, the inventor explores a set of process conditions, and applies diffusion dialysis and electrodialysis to the desalination process of protein solution, so that the desalination efficiency is improved, and the energy consumption is reduced to a great extent.
The present invention will be described more specifically with reference to the following examples, which are not intended to limit the present invention in any way.
The desalination system of the soluble silk fibroin solution comprises a diffusion dialysis module, an electrodialysis module and a raw material box 10, wherein the diffusion dialysis module and the electrodialysis module share one raw material box 10, the raw material box is provided with two inlets (a diffusion dialysis liquid inlet and an electrodialysis raw material inlet) and two outlets (a raw material outlet and an electrodialysis raw material outlet), and the inlets and the outlets are communicated inside the raw material box, so that the diffusion dialysis module and the electrodialysis module are connected.
The diffusion dialysis module, as shown in fig. 2, comprises a diffusion dialysis stock pump 2, a diffusion dialyzer 5 and a deionized water tank 9. Wherein the diffusion dialyzer 5 is provided with a raw material inlet, a diffusion dialysis liquid outlet, a diffusion water inlet and a diffusion water outlet; the raw material inlet and the diffusion dialysis fluid outlet are respectively connected with the raw material outlet and the diffusion dialysis fluid inlet of the raw material box 10; the diffusion water inlet and the diffusion water outlet are respectively connected with the water outlet and the water inlet of the deionized water tank 9. A plurality of vertically placed partition boards are arranged in the diffusion dialyzer 5, the partition boards divide the space inside the diffusion dialyzer into a plurality of compartments, and cation exchange resin is filled in the compartments; the cation exchange resin is a polystyrene gel resin. The positions of a raw material inlet and a diffusion dialysis liquid outlet in the diffusion dialyzer 5 are arranged in a diagonal manner; the positions of the diffusion water inlet and the diffusion water outlet are also arranged in a diagonal manner; the diffusion water and the raw material in the diffusion dialyzer 5 flow reversely, the contact area is increased, and the desalination efficiency and the desalination rate are improved. The raw material box 10 is filled with a soluble silk fibroin solution, a raw material outlet of the raw material box 10 is connected with a raw material inlet of the diffusion dialyzer 5 through a diffusion dialysis material pump 2, and the soluble silk fibroin solution in the raw material box 10 is pumped into the diffusion dialyzer 5 for primary desalting. A raw material flowmeter 3 and a raw material pressure gauge 4 are also arranged on the pipeline between the diffusion dialysis material pump 2 and the diffusion dialyzer 5. Meanwhile, deionized water is contained in the deionized water tank 9, and a water outlet of the deionized water tank 9 is connected with a diffusion water inlet of the diffusion dialyzer 5 through a diffusion water pump 8 to pump the deionized water into the diffusion dialyzer 5. A diffusion water flowmeter 7 and a diffusion water pressure meter 6 are arranged on the pipeline between the deionized water tank 9 and the diffusion dialyzer 5. After the raw material silk fibroin solution in the diffusion dialyzer 5 is contacted with diffusion water, the salt in the raw material is diffused into the water to be removed, the salt concentration in the raw material is reduced to become diffusion dialysis solution, the salt concentration in deionized water is increased to become diffusion water, the diffusion dialysis solution is connected with a diffusion dialysis solution inlet of the raw material tank 10 through a diffusion dialysis solution outlet of the diffusion dialyzer 5 and returns to the raw material tank 10, and the diffusion water returns to the deionized water tank 9 through a diffusion water outlet of the diffusion dialyzer 5 to complete diffusion dialysis desalination. The diffusion dialysis cycle is completed when the salt content in the deionized water tank 9 reaches 60% -70% of the salt content before desalting the silk fibroin solution, and the diffusion dialysis solution (i.e., once desalted silk fibroin solution after desalting) is introduced into the electrodialysis module.
The electrodialysis module, as shown in fig. 2, comprises an electrodialysis pump 11, an electrodialyzer and a water tank 18. The electrodialysis raw material inlet of the raw material box 10 is connected with the electrodialysis product outlet and the diffusion dialysate outlet of the electrodialyzer 1; the electrodialysis raw material outlet of the raw material tank 10 is connected with the electrodialysis liquid inlet of the electrodialyzer 1. The electrodialysis device 1 is internally provided with a plurality of vertically placed partition boards, the partition boards divide the internal space of the electrodialysis device 1 into a plurality of compartments, anion exchange resin and cation exchange resin are alternately filled in the compartments, so that the compartments form a concentration chamber and a desalination chamber which are longitudinally and parallelly arranged, a fresh water inlet and an electrodialysis product outlet are respectively arranged at the lower right and the upper left of the electrodialysis device 1, and an electrodialysis liquid inlet and a concentrated water outlet are respectively arranged at the upper right and the lower left of the electrodialysis device 1. The anion exchange resin may be a polystyrene-based anion exchange resin, and the cation exchange resin may be a polystyrene-based cation exchange resin. The fresh water inlet and the concentrate outlet are connected to the fresh water outlet and the concentrate inlet of the tank 18, respectively. The raw material box 10 contains primary desalted silk fibroin solution after diffusion dialysis desalination, an electrodialysis raw material outlet of the raw material box 10 is connected with an electrodialysis raw material inlet of the electrodialysis device 1 through an electrodialysis material pump 11, and the primary desalted silk fibroin solution in the raw material box 10 is pumped into the electrodialysis device 1 for secondary desalination. The pipeline between the electrodialysis material pump 11 and the electrodialysis device 1 is also provided with a primary desalting solution flowmeter 12 and a primary desalting solution pressure gauge 13. Meanwhile, deionized water is contained in the water tank 18, and a fresh water outlet of the water tank 18 is connected with a fresh water inlet of the electrodialysis device 1 through the electrodialysis water pump 17, so that the deionized water is pumped into a desalting chamber of the electrodialysis device 1. An electroosmosis water flowmeter 16 and an electroosmosis water pressure meter 15 are arranged on the pipeline between the water tank 9 and the electrodialyzer 1. After the primary desalted silk fibroin solution in the electrodialyzer 1 is contacted with fresh water, the salt in the solution is diffused into water to be removed, the salt concentration in the solution is reduced to become an electrodialysis product, the salt concentration in the fresh water is increased to become concentrated water, the electrodialysis product is returned to the raw material tank 10 through an electrodialysis product outlet of the electrodialyzer 1, the concentrated water is returned to the water tank 18 through a concentrated water outlet of the electrodialyzer 1 to complete electrodialysis desalination, and when the conductivity of the solution in the raw material tank 10 is reduced to below 200 mu S/cm, the electrodialysis product (namely the secondary desalted silk fibroin solution) is led out from the electrodialysis product outlet and is freeze-dried to obtain solid silk fibroin powder.
In order to shorten the desalting time, the above desalting system may be modified, as shown in fig. 3, only that the diffusion dialysis module and the electrodialysis module no longer share the raw material tank 10, but are divided into a diffusion dialysis raw material tank 19 and an electrodialysis raw material tank 20. Wherein, the liquid outlet of the diffusion dialysis raw material box is provided with a tee joint, and is connected with the raw material inlet of the diffusion dialyzer or the electrodialysis raw material inlet of the electrodialysis raw material box. The rest of the structure and connection relationship are the same as those of the system shown in fig. 2.
Based on the desalination system of the soluble silk fibroin solution shown in the above figure 2, the invention also provides a desalination method of the soluble silk fibroin solution, comprising the following steps:
(1) Primary desalting was performed by diffusion dialysis: closing the electrodialysis module, and firstly adding silk fibroin solution (Na is used for silk 2 CO 3 Degumming, namely dissolving a calcium chloride-ethanol-water ternary system), entering the raw material from a raw material inlet of a diffusion dialyser through a diffusion dialyser pump 2 according to the liquid linear velocity of 1-5cm/s, discharging from a diffusion dialyser liquid outlet after dialyzing, circulating the circulating flow back into a raw material box, pumping deionized water in a deionized water tank into a diffusion water inlet of the diffusion dialyser through a diffusion water pump 8 according to the linear velocity of 1-5cm/s, discharging from the diffusion water outlet, and circulating and flowing back into the water tank. When the salt content in the deionized water tank reaches 60% -70% (preferably 65%) of the salt content before the silk fibroin solution is desalted, the diffusion dialysis is stopped, and the silk fibroin solution is desalted once in the raw material tank.
The linear velocity ratio of silk fibroin solution to deionized water is (1-2): 1 (preferably 2:1), and the flow rate (i.e., linear velocity) in diffusion dialysis affects the diffusion rate of ions, the faster the flow rate, the faster the calcium ions and chloride ions diffuse into deionized water.
(2) Secondary desalting by electrodialysis: at this time, the diffusion dialysis module was turned off, the electrodialysis module was turned on, and 0.1g/LNa was introduced to both sides of the electrodialyzer electrode 2 SO 4 The solution (polar water) is powered on, and the current is 0.3A or less (preferably 0.2A). With electrodialysis pumps 11 passing through hoses at liquid linear velocities of 1-5cm/s, introducing the primary desalted silk fibroin solution in the raw material box into an electrodialysis liquid inlet of the electrodialysis device 1, entering the electrodialysis device 1, desalting by electrodialysis, flowing out of an electrodialysis product outlet, circulating into the raw material box, simultaneously pumping deionized water in a water tank into the electrodialysis device 1 from a fresh water outlet according to the liquid linear velocity of 1-5cm/s, performing ion exchange with the primary desalted silk fibroin solution, flowing out of a concentrated water outlet, and circularly flowing into the water tank. When the conductivity of the silk fibroin solution in the raw material box is not higher than 200 mu S/cm, stopping electrodialysis, and leading out the silk fibroin solution which is subjected to secondary desalination in the raw material box from an electrodialysis product outlet to the next working procedure.
(3) And (3) freeze drying: pre-freezing the secondary desalted silk fibroin solution at-80 ℃ until no liquid silk fibroin exists, and then performing freeze drying under vacuum condition to obtain the solid silk fibroin.
Wherein the mass percentage of silk fibroin in the silk fibroin solution in the raw material tank before desalination is started is selected below 6wt% in order to ensure good solution flow and migration and diffusion of salt ions while reducing pressure on the membrane. The thickness of the separator in the diffusion dialyzer is between 2mm and 3mm, and the cation exchange membrane can be homogeneous or heterogeneous. The desalination rate in the diffusion dialysis process can be flexibly controlled and regulated through the operation time, when the primary desalination rate reaches 60% -70%, the primary desalination silk fibroin solution is introduced into the electrodialysis module to carry out secondary desalination until the salt content is no longer reduced, and in a certain range, the time of electrodialysis secondary desalination is shorter (0.2A is optimal) when the current is larger.
Example 1
1) According to Na 2 CO 3 The concentration is 5g/L, and the bath ratio is 1:40, degumming the silk.
Adding 20g of sodium carbonate into 4000ml of tap water, boiling silk in water for 30min, changing the liquid, boiling again for 30min, boiling with deionized water added with sodium carbonate for 30min for the third time, and checking whether sericin is stripped off with picric acid carmine solution after every 30 min. Then cleaning with deionized water, drying at 50 ℃, and cutting into small sections for standby.
2) The molar ratio is 1:2:8, preparing a calcium chloride-ethanol-water ternary system solution, and dissolving silk.
490ml deionized water was added to a three-necked flask followed by slow addition of 377.4g CaCl 2 Adding CaCl into water 2 A large amount of heat is generated, when the temperature is reduced to about 60 ℃, the three-neck flask is placed into a water bath kettle with the temperature of 60 ℃, 395ml of absolute ethyl alcohol is measured by a measuring cylinder and slowly poured into the flask, then the cut silk segments are added into the dissolving liquid, and after the silk is completely dissolved, stirring and heating are continued for dissolving for 4 hours. After dissolution, the silk fibroin solution is cooled to room temperature, and then centrifuged for 10min by a centrifuge at 8000r/min, and the supernatant is taken and bottled for later use.
Technical parameters of diffusion dialysis module
External dimensions: 100mm by 200mm; effective dimensions: 70mm by 120mm; thickness of the separator: 2-3mm; diffusion dialysis cation membrane: compact homogeneous cation exchange membranes; membrane pair number 10 pairs
Technical parameters of electrodialysis Membrane stacks
External dimensions: 100mm by 200mm; effective dimensions: 70mm by 120mm; concentration chamber separator thickness: 0.5mm, and the thickness of the partition plate of the desalting chamber is 2-3mm; homogeneous anion-cation exchange membrane: compact homogeneous anion-cation exchange membrane; the number of membrane pairs is 10.
120g of the silk fibroin solution prepared in the step 2) is taken in a raw material box, 100ml of water is added, the concentration is diluted to 4%, 2000ml of deionized water is added in a deionized water box, the flow rate of the silk fibroin solution is regulated to 40L/h, the flow rate of the water is regulated to 20L/h, cyclic desalination is carried out, and the operation is stopped after 6.8h until the desalination rate is 65%.
Taking a silk fibroin solution subjected to primary desalination, adding 2000ml of deionized water into a water tank to carry out electrodialysis secondary desalination, regulating the flow of the silk fibroin solution to 40L/h, regulating the flow of water to 20L/h, introducing polar water, regulating the flow of the polar water to 3L/h, switching on a direct current power supply after the water flow is stable, regulating the current to 0.2A, stopping desalination when the conductivity of an electrodialysis product reaches about 200 mu S/cm (namely TDS is 0.1 g/L), wherein the desalination time is 3.5h, the final desalination rate is 99.98%, the silk fibroin recovery rate is 91.35%, and the calculated power consumption is lower than 0.0175KWh.
The silk fibroin solutions in the following examples were prepared using steps 1) and 2) of example 1; the technical parameters of the diffusion dialysis module and the electrodialysis module are also the same as in example 1.
Example 2
120g of silk fibroin solution is taken in a raw material box, 100ml of deionized water is added, the concentration is diluted to 4%, 2000ml of deionized water is added in the deionized water box, the flow rate of the silk fibroin solution is controlled to be 40L/h, the flow rate of water is controlled to be 20L/h, diffusion dialysis is carried out for once desalting, and the operation is stopped after 6h until the desalting rate is 60%.
Taking primary desalted silk fibroin solution, adding 2000ml deionized water into a water tank for electrodialysis secondary desalting, regulating the flow of the silk fibroin solution to 40L/h, regulating the flow of water to 20L/h, introducing polar water, regulating the flow of the polar water to 3L/h, switching on a direct current power supply after the circulating water flow is stable, controlling the current to be 0.2A, stopping desalting when the conductivity of the silk fibroin solution reaches about 200 mu S/cm (namely TDS is 0.1 g/L), and measuring the desalting time to be 3.8h. The final desalination rate is 99.92%, the recovery rate of silk fibroin is 91.0%, and the power consumption is lower than 0.02KWh.
Example 3
120g of silk fibroin solution is taken in a raw material box, 100ml of deionized water is added, the concentration is diluted to 4%, 2000ml of deionized water is added in the deionized water box, the flow rate of the silk fibroin solution is controlled to be 40L/h, the flow rate of water is controlled to be 20L/h, diffusion dialysis is carried out for one-time desalination, and the operation is stopped after 8h until the desalination rate is 70%.
Taking primary desalted silk fibroin solution, adding 2000ml deionized water into a water tank for electrodialysis secondary desalting, regulating the flow of the silk fibroin solution to 40L/h, regulating the flow of water to 20L/h, introducing polar water, regulating the flow of the polar water to 3L/h, switching on a direct current power supply after the circulating water flow is stable, controlling the current to be 0.2A, stopping desalting when the conductivity of the silk fibroin solution reaches about 200 mu S/cm (namely TDS is 0.1 g/L), and measuring the desalting time to be 3h. The final desalination rate is 99.89%, the recovery rate of silk fibroin is 88.24%, and the power consumption is lower than 0.015KWh.
Example 4
120g of silk fibroin solution is taken in a raw material box, 100ml of deionized water is added, the concentration is diluted to 4%, 2000ml of deionized water is added in the deionized water box, the flow rate of the silk fibroin solution is controlled to be 20L/h, the flow rate of water is controlled to be 40L/h, diffusion dialysis is carried out for once desalting, and the operation is stopped after 11.5h until the desalting rate is 65%.
Taking primary desalted silk fibroin solution, adding 2000ml deionized water into a water tank for electrodialysis secondary desalting, regulating the flow of the silk fibroin solution to 20L/h, regulating the flow of water to 40L/h, introducing polar water, regulating the flow of the polar water to 3L/h, switching on a direct current power supply after the circulating water flow is stable, controlling the voltage to 25V and the current to 0.2A, stopping desalting when the conductivity of the silk fibroin solution reaches about 200 mu S/cm (namely TDS is 0.1 g/L), and measuring the desalting time to 4.5h. The final desalination rate is 99.90%, the recovery rate of silk fibroin is 83.74%, and the power consumption is lower than 0.225KWh.
Example 5
120g of silk fibroin solution is taken in a raw material box, 100ml of deionized water is added, the concentration is diluted to 4%, 2000ml of deionized water is added in the deionized water box, the flow rate of the silk fibroin solution is controlled to be 20L/h, diffusion dialysis is carried out for one time for desalination, and the operation is stopped after 8 hours until the desalination rate is 65%.
Taking primary desalted silk fibroin solution, adding 2000ml deionized water into a water tank for electrodialysis secondary desalting, regulating the flow of the silk fibroin solution to 20L/h, regulating the flow of water to 20L/h, introducing polar water, regulating the flow of the polar water to 3L/h, switching on a direct current power supply after the circulating water flow is stable, controlling the voltage to 25V and the current to 0.2A, stopping desalting when the conductivity of the silk fibroin solution reaches about 200 mu S/cm (namely TDS is 0.1 g/L), and measuring the desalting time to 4h. The final desalination rate is 99.94%, the recovery rate of silk fibroin is 90.42%, and the power consumption is lower than 0.2KWh.
Example 6
120g of silk fibroin solution is taken in a raw material box, 100ml of deionized water is added, the concentration is diluted to 4%, 2000ml of deionized water is added in the deionized water box, the flow rate of the silk fibroin solution is controlled to be 40L/h, the flow rate of water is controlled to be 20L/h, diffusion dialysis is carried out for one-time desalination, and the operation is stopped after 6.8h until the desalination rate is 65%.
Taking primary desalted silk fibroin solution, adding 2000ml deionized water into a water tank for electrodialysis secondary desalting, regulating the flow of the silk fibroin solution to 40L/h, regulating the flow of water to 20L/h, introducing polar water, regulating the flow of the polar water to 3L/h, switching on a direct current power supply after the circulating water flow is stable, controlling the current to be 0.1A, stopping desalting when the conductivity of the silk fibroin solution reaches about 200 mu S/cm (namely TDS is 0.1 g/L), and measuring the desalting time to be 7h. The final desalination rate is 99.98%, the recovery rate of silk fibroin is 91.0%, and the power consumption is lower than 0.0175KWh.
Example 7
120g of silk fibroin solution is taken in a raw material box, 100ml of deionized water is added, the concentration is diluted to 4%, 2000ml of deionized water is added in the deionized water box, the flow rate of the silk fibroin solution is controlled to be 40L/h, the flow rate of water is controlled to be 20L/h, diffusion dialysis is carried out for one-time desalination, and the operation is stopped after 6.8h until the desalination rate is 65%.
Taking primary desalted silk fibroin solution, adding 2000ml deionized water into a water tank for electrodialysis secondary desalting, regulating the flow of the silk fibroin solution to 40L/h, regulating the flow of water to 20L/h, introducing polar water, regulating the flow of the polar water to 3L/h, switching on a direct current power supply after the circulating water flow is stable, controlling the current to be 0.3A, stopping desalting when the conductivity of the silk fibroin solution reaches about 200 mu S/cm (namely TDS is 0.1 g/L), and measuring the desalting time to be 3.2h. The final desalination rate is 99.98%, the recovery rate of silk fibroin is 91.3%, and the power consumption is lower than 0.024KWh.
Comparative example 1
120g of silk fibroin solution is taken in a raw material box, 100ml of deionized water is added, the concentration is diluted to 4%, 2000ml of deionized water is added in the deionized water box, the flow rate of the silk fibroin solution is controlled to be 40L/h, the flow rate of water is controlled to be 20L/h, diffusion dialysis is carried out for once desalting, and the operation is stopped after 5.2h until the desalting rate is 40%.
Taking primary desalted silk fibroin solution, adding 2000ml deionized water into a water tank for electrodialysis secondary desalting, regulating the flow of the silk fibroin solution to 40L/h, regulating the flow of water to 20L/h, introducing polar water, regulating the flow of the polar water to 3L/h, switching on a direct current power supply after the circulating water flow is stable, controlling the current to be 0.2A, stopping desalting when the conductivity of the silk fibroin solution reaches about 200 mu S/cm (namely TDS is 0.1 g/L), and measuring the desalting time to be 5.7h. The final desalination rate was 99.96%, the recovery rate of silk fibroin was 94.04%, and the power consumption was 0.071KWh.
Comparative example 2
120g of silk fibroin solution is taken in a raw material box, 100ml of deionized water is added, the concentration is diluted to 4%, 2000ml of deionized water is added in the deionized water box, the flow rate of the silk fibroin solution is controlled to be 40L/h, the flow rate of water is controlled to be 20L/h, diffusion dialysis is carried out for once desalting, and the operation is stopped after 26h until the desalting rate is 90%.
Taking primary desalted silk fibroin solution, adding 2000ml deionized water into a water tank for electrodialysis secondary desalting, regulating the flow of the silk fibroin solution to 40L/h, regulating the flow of water to 20L/h, introducing polar water, regulating the flow of the polar water to 3L/h, switching on a direct current power supply after the circulating water flow is stable, controlling the current to be 0.2A, stopping desalting when the conductivity of the silk fibroin solution reaches about 200 mu S/cm (namely TDS is 0.1 g/L), and measuring the desalting time to be 1h. The final desalination rate is 99.90%, the recovery rate of silk fibroin is 83.74%, and the power consumption is lower than 0.005KWh.
The desalination time and energy consumption (water consumption and electricity consumption) of the present invention were compared with those of other methods based on the desalination time and energy consumption (water consumption and electricity consumption) of example 1 of the present invention, respectively, as shown in table 1:
TABLE 1 comparison of desalination effects of various desalination methods
| Desalination method | Desalination time | Desalination rate/% | Consumption of water | Desalination electricity consumption |
| The |
1 | 99.98 | 1 | 1 |
| Dialysis bag | 6.3 | 99.79 | 8.6 | 0 |
| Nanofiltration | 1.2 | 98 | 4 | 48 |
| Electrodialysis | 0.9 | 99.5 | 3.2 | 2.9 |
Table 1 shows that deionized water in the invention is recycled, electrodialysis depth desalting time is shorter, consumption of extreme water is also reduced, and therefore water consumption is far smaller than other processes. In addition, the process has similar desalination time, higher desalination rate and the greatest advantage of lower electricity consumption compared with the electrodialysis only desalination. Therefore, the process shortens the desalination time and reduces the energy consumption under the condition of achieving higher desalination rate.
The specific parameters of the other examples and comparative examples are shown in Table 2, and the parameters not listed are the same as those of example 1.
TABLE 2 parameters in other examples desalination processes
The foregoing is merely a preferred embodiment of the invention, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended by the present invention.
Claims (6)
1. The desalting system for the soluble silk fibroin solution is characterized by comprising a raw material box, a diffusion dialysis module and an electrodialysis module, wherein the raw material box is provided with two inlets of a diffusion dialysis liquid inlet and an electrodialysis raw material inlet and two outlets of a raw material outlet and an electrodialysis raw material outlet, the diffusion dialysis liquid inlet and the raw material outlet of the raw material box are connected with the diffusion dialysis module, and the electrodialysis raw material inlet and the electrodialysis raw material outlet of the raw material box are connected with the electrodialysis module;
the diffusion dialysis module comprises a diffusion dialysis material pump, a diffusion water pump, a diffusion dialyzer and a deionized water tank; the diffusion dialyzer is connected with the raw material box through a diffusion dialysis material pump, and the deionized water box is connected with the diffusion dialyzer through a diffusion water pump;
the diffusion dialyzer is provided with a raw material inlet, a diffusion dialysis liquid outlet, a diffusion water inlet and a diffusion water outlet; the raw material inlet and the diffusion dialysis liquid outlet are respectively connected with the raw material outlet and the diffusion dialysis liquid inlet of the raw material box; the diffusion water inlet and the diffusion water outlet are respectively connected with the water outlet and the water inlet of the deionized water tank; the positions of the raw material inlet and the diffusion dialysis liquid outlet of the diffusion dialysis device are arranged in a diagonal manner; the positions of the diffusion water inlet and the diffusion water outlet are also arranged in a diagonal manner;
the electrodialysis module comprises an electrodialysis material pump, an electrodialysis water pump, an electrodialyzer and a water tank; the electrodialysis device is connected with a raw material box through an electrodialysis material pump, and the water box is connected with the electrodialysis device through an electrodialysis water pump; the electrodialysis device comprises a concentration chamber and a desalination chamber which are longitudinally and alternately arranged in parallel, and an electrodialysis raw material inlet of the raw material box is connected with an outlet of the desalination chamber; the electrodialysis raw material outlet of the raw material box is connected with the inlet of the concentration chamber; the inlet of the desalination chamber and the outlet of the concentration chamber are respectively connected with the fresh water outlet and the concentrated water inlet of the water tank;
the thickness of a baffle plate in the diffusion dialyzer is 2mm-3mm, the thickness of a baffle plate of a desalting chamber in the dialyzer is 2mm-3mm, and the thickness of a baffle plate of a concentrating chamber is 0.5mm; the ion exchange resin filled in the desalting chamber is a mixed resin obtained by the mass ratio of the anion exchange resin to the cation exchange resin being 1:1-1:1.5.
2. The desalination system of claim 1, wherein a feed flow meter and a feed pressure meter are further provided on the piping between the feed tank and the diffusion dialyzer; and a diffusion water flowmeter and a diffusion water pressure meter are further arranged on a pipeline between the deionized water tank and the diffusion dialyzer.
3. The desalination system of claim 1 or 2, wherein a primary desalination solution flow meter and a primary desalination solution pressure meter are further provided on the line between the feed tank and the electrodialyzer; and an electroosmosis water flowmeter and an electroosmosis water pressure meter are further arranged on a pipeline between the water tank and the electrodialyzer.
4. A desalination method of a soluble silk fibroin solution, which is characterized in that the desalination system of any one of claims 1-3 is used, the silk fibroin solution is led into a diffusion dialysis module from a raw material box for diffusion dialysis, and primary desalted silk fibroin solution is obtained; introducing the primary desalted silk fibroin solution into a raw material box of an electrodialysis module for electrodialysis to obtain a secondary desalted silk fibroin solution, namely a desalted silk fibroin solution;
the desalination method comprises the following steps:
(1) Primary desalting was performed by diffusion dialysis: opening a diffusion dialysis module quickly, closing an electrodialysis module, enabling silk fibroin solution in a raw material box to enter from a raw material inlet of a diffusion dialyzer through a diffusion dialysis material pump according to the liquid linear velocity of 1-5cm/s, enabling the silk fibroin solution to come out from a diffusion dialysis liquid outlet after diffusion dialysis, enabling a circulating flow to return into the raw material box, enabling deionized water in a deionized water box to be pumped into the diffusion dialyzer from a diffusion water inlet at the linear velocity of 1-5cm/s by the diffusion water pump, enabling the deionized water to flow out from the diffusion water outlet, and enabling the circulating flow to return into a deionized water box; stopping diffusion dialysis when the salt content of deionized water in the deionized water tank reaches 60-70% of the salt content of the silk fibroin solution before desalination, so as to obtain a primary desalted silk fibroin solution; the linear velocity ratio of the silk fibroin solution to deionized water is (1-2): 1, a step of;
(2) Secondary desalting by electrodialysis: closing a diffusion dialysis module quickly, opening an electrodialysis module, switching on a power supply to enable the current not to exceed 0.3A, pumping primary desalted silk fibroin solution in a raw material box into a desalting chamber of an electrodialysis device through an electrodialysis liquid inlet at the liquid linear speed of 1-5cm/s by an electrodialysis material pump, desalting by electrodialysis, flowing out of an electrodialysis product outlet of the desalting chamber, circulating into the raw material box, enabling deionized water in a water tank to enter a concentration chamber from a fresh water outlet of the electrodialysis device at the liquid linear speed of 1-5cm/s, performing ion exchange with the primary desalted silk fibroin solution, and flowing out of the concentration chamber outlet and circulating into the water tank; when the conductivity of the silk fibroin solution in the raw material box is below 200 mu S/cm, stopping electrodialysis to obtain a secondary desalted silk fibroin solution, namely the desalted silk fibroin solution, and leading out from an electrodialysis product outlet.
5. The desalination method of claim 4, wherein the silk fibroin solution is prepared from silk through Na 2 CO 3 Degumming, dissolving a calcium chloride-ethanol-water ternary system to obtain the silk fibroin solution with the concentration of less than 6wt% before diffusion dialysis in a raw material box.
6. A process for preparing the soluble silk fibroin features that Na is used for silk 2 CO 3 Degumming, dissolving a calcium chloride-ethanol-water ternary system to obtain a silk fibroin solution, desalting the silk fibroin solution by the desalting method according to claim 4 or 5 to obtain a secondary desalted silk fibroin solution, and finally freeze-drying to obtain silk fibroin.
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