CN111362359A - Method for recycling alginate through forward osmosis concentration of reverse osmosis of driving agent - Google Patents
Method for recycling alginate through forward osmosis concentration of reverse osmosis of driving agent Download PDFInfo
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- CN111362359A CN111362359A CN202010189536.8A CN202010189536A CN111362359A CN 111362359 A CN111362359 A CN 111362359A CN 202010189536 A CN202010189536 A CN 202010189536A CN 111362359 A CN111362359 A CN 111362359A
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- driving agent
- alginate
- storage device
- forward osmosis
- reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
Abstract
The invention relates to a method for recycling alginate by forward osmosis concentration of reverse osmosis of a driving agent, which comprises a driving agent storage device, a feed liquid storage device and a forward osmosis membrane assembly, wherein the driving agent storage device is used for storing the driving agent, the driving agent is a high-valence metal ion solution, the feed liquid storage device is used for storing a raw material liquid, the raw material liquid is a sodium alginate solution, the raw material liquid in the feed liquid storage device is subjected to forward osmosis through the forward osmosis membrane assembly, the driving agent in the driving agent storage device is subjected to reverse osmosis, a cake layer is formed on one side of the forward osmosis membrane assembly close to the feed liquid storage device, the cake layer is a target product for concentration and recycling, and the component of the cake layer is high-valence metal alginate. The method has the characteristics of simple operation and high recovery efficiency, and can recover the high-valence metal alginate filter cake layer formed by reverse osmosis of the driving agent, reduce membrane pollution in the forward osmosis process and improve water flux.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for recycling alginate by forward osmosis concentration of reverse osmosis of a driving agent.
Background
The sewage recycling becomes the development direction of the future sewage treatment technology. The recovery of alginate from aerobic granular sludge is a new sewage resource-changing direction. Alginate is a biopolymer with higher economic added value, and can be widely applied to agriculture, horticulture, paper industry, medical industry and building industry due to the characteristics of high gel strength, good thickening property, strong water retention capacity and the like.
The highest content of alginate in the aerobic granular sludge can reach 25% of the dry weight of the sludge, however, the water content of the recovered alginate solution is as high as more than 99.8%. To achieve concentration and dehydration of alginate, alginate in a dissolved state may be precipitated from water by adding a chemical agent such as ethanol, calcium chloride, or a mineral acid to the alginate solution to achieve concentration and dehydration. But the chemical method consumes a large amount of chemical reagents and can cause secondary pollution, and large-scale engineering application cannot be realized. The membrane separation method for concentrating the alginate does not need to add chemical reagents, does not cause secondary pollution, and can replace the traditional method. The membrane separation mode mainly comprises microfiltration, ultrafiltration, nanofiltration and reverse osmosis driven by external pressure. Researches show that microfiltration and ultrafiltration have good recovery effect on alginate, but the operation cost is high due to external pressure, and severe membrane pollution exists; nanofiltration and reverse osmosis can achieve higher alginate rejection, but under pressure driving, more serious membrane fouling phenomenon exists. Different from the traditional membrane separation method with external pressure, forward osmosis is a novel membrane separation mode which utilizes the osmotic pressure difference of solutions on two sides of a semipermeable membrane to enable water molecules to spontaneously flow from a low osmotic pressure side to a high osmotic pressure side, and is more expected to become a proper technology for concentrating alginate.
However, reverse osmosis of the draw solute during forward osmosis is one of the bottlenecks that limit its development. The driving force in the forward osmosis process is reduced due to the reverse osmosis of the solute, and the membrane flux is reduced; in addition, solute reverse osmosis can also contaminate the feed solution and increase the cost of driver replenishment. Accordingly, much research has been devoted to the development of novel draw agents and the separation of reverse osmosis solutes from feed streams. The driving agent is continuously diluted in the forward osmosis operation process, and the diluted driving agent is generally recycled by adopting methods such as reverse osmosis, nanofiltration, ultrafiltration, membrane distillation, heat treatment and the like. Based on the above problems, the search for a driving agent with high water flux, low reverse salt flux, easy recovery and disposal or direct use after dilution is still the focus of the research on the driving agent in the forward osmosis technology at present. However, the problem of reverse osmosis of the driver has not been solved at all so far.
Disclosure of Invention
In view of the above problems in the prior art, the main object of the present invention is to provide a method for recovering alginate by forward osmosis concentration using reverse osmosis of a driving agent, which has the characteristics of simple operation and high recovery efficiency, and can recover a high-price metal alginate cake layer formed by reverse osmosis, thereby reducing membrane pollution during forward osmosis and improving water flux.
The technical scheme of the invention is as follows:
the utility model provides a method for utilize concentrated alginate of retrieving of positive osmosis of driving agent reverse osmosis, includes driving agent storage device, feed liquid storage device and forward osmosis membrane module, driving agent storage device is used for storing the driving agent, just the driving agent is high valence metal ion solution, feed liquid storage device is used for storing raw materials liquid, just raw materials liquid is sodium alginate solution, raw materials liquid in the feed liquid storage device carries out forward osmosis through forward osmosis membrane module, simultaneously the driving agent in the driving agent storage device carries out reverse osmosis, just raw materials liquid is in forward osmosis membrane module is close to one side of feed liquid storage device forms the filter cake layer, the filter cake layer is the target product of concentrated recovery promptly, just the composition of filter cake layer is high valence metal alginate.
Feed liquid storage device through first conveyer pipe with the forward osmosis membrane subassembly is linked together, the forward osmosis membrane subassembly pass through the second conveyer pipe with drive agent storage device is linked together, drive agent storage device still pass through the third conveyer pipe with the forward osmosis membrane subassembly is linked together, just the forward osmosis membrane subassembly pass through the fourth conveyer pipe with feed liquid storage device is linked together.
And a first gear pump is arranged on the third conveying pipe, and a second gear pump is arranged on the fourth conveying pipe.
The high-valence metal ion solution is CaCl2Solutions or MgCl2One or two of the solutions.
The high-valence metal ion solution is CaCl2And (3) solution.
The raw material liquid forms a filter cake layer on one side of the forward osmosis membrane component close to the liquid material storage device, the filter cake layer is a concentrated and recovered target product, and the filter cake layer is calcium alginate or magnesium alginate.
The invention has the following advantages and beneficial effects: the device comprises a driving agent storage device, a feed liquid storage device and a forward osmosis membrane assembly, wherein the driving agent storage device is used for storing a driving agent, the driving agent is a high-valence metal ion solution, the feed liquid storage device is used for storing a raw material liquid, the raw material liquid is a sodium alginate solution, the raw material liquid in the feed liquid storage device is subjected to forward osmosis through the forward osmosis membrane assembly, meanwhile, the driving agent in the driving agent storage device is subjected to reverse osmosis, a cake layer is formed on one side, close to the feed liquid storage device, of the raw material liquid, the cake layer is a target product for concentration and recovery, and the components of the cake layer are high-valence metal alginate; the invention utilizes the reverse osmosis phenomenon of the driving agent in the forward osmosis process to achieve the dual purposes of resource recovery and water flux increase, and converts the disadvantage of reverse osmosis of the driving agent into advantage.
Drawings
FIG. 1 is a schematic diagram of the structure of the apparatus used in forward osmosis experiments in the method for recovering alginate by forward osmosis concentration using reverse osmosis of a driving agent according to the embodiment of the present invention.
FIG. 2 is a Fourier infrared spectrum of sodium alginate with a cake layer in an example of the invention.
FIG. 3 is an X-ray photoelectron spectrum of sodium alginate in an example of the present invention.
FIG. 4 is an X-ray photoelectron spectrum of a filter cake layer according to an embodiment of the present invention.
FIG. 5 is a graph showing the water flux change for different drivers during forward osmosis in an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should also be noted that, unless otherwise explicitly specified or limited, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The invention will be further described with reference to the drawings and specific examples.
As shown in fig. 1 to 5: the method for recycling alginate through forward osmosis concentration by reverse osmosis of a driving agent provided by the embodiment of the invention comprises a driving agent storage device 100, a feed liquid storage device 200 and a forward osmosis membrane assembly 300, wherein the driving agent storage device 100 is used for storing the driving agent, the driving agent is a high-valence metal ion solution, the feed liquid storage device 200 is used for storing a raw material liquid, the raw material liquid is a sodium alginate solution, the raw material liquid in the feed liquid storage device 200 is subjected to forward osmosis through the forward osmosis membrane assembly 300, meanwhile, the driving agent in the driving agent storage device 100 is subjected to reverse osmosis, and the raw material liquid forms a cake layer on one side of the forward osmosis membrane assembly 300 close to the feed liquid storage device 200, the cake layer is a target product for concentration and recycling, and the component of the cake layer is high-valence metal alginate.
The feed liquid storage device 200 is communicated with the forward osmosis membrane component 300 through a first conveying pipe 201, the forward osmosis membrane component 300 is communicated with the driving agent storage device 100 through a second conveying pipe 202, the driving agent storage device 100 is further communicated with the forward osmosis membrane component 300 through a third conveying pipe 203, and the forward osmosis membrane component 300 is communicated with the feed liquid storage device 200 through a fourth conveying pipe 204.
The third conveying pipe 203 is provided with a first gear pump 101, and the fourth conveying pipe 204 is provided with a second gear pump 102.
The high-valence metal ion solution is CaCl2Solutions or MgCl2One or two of the solutions.
The high-valence metal ion solution may be CaCl preferentially2And (3) solution.
The raw material liquid forms a filter cake layer on one side of the forward osmosis membrane component 300 close to the liquid material storage device 200, the filter cake layer is a concentrated and recovered target product, and the filter cake layer is calcium alginate or magnesium alginate.
The embodiment of the invention provides a method for recovering alginate by forward osmosis concentration of reverse osmosis of a driving agent, wherein reverse osmosis metal ions interact with alginate to form corresponding metal alginate such as calcium alginate and magnesium alginate, and the generated metal alginate is a target product to be concentrated and recovered, and meanwhile, the target product has lower membrane pollution to a forward osmosis membrane. The invention is based on the reverse thinking mode, and is operated against the reverse thinking mode, the reverse osmosis problem of the driving agent is not avoided, and the driving agent with reverse osmosis is further utilized to react with the alginate to generate the target metal alginate to be concentrated and recovered.
For example, using sodium alginate as the starting solution, CaCl2The solution is a driving agent, calcium ion reverse osmosis occurs in the forward osmosis process, and a filter cake layer is formed on the raw material liquid side. The filter cake layer is made of calcium alginate, which is a recovered product and has less membrane pollution and can reduce the water flux decline in the forward osmosis process. FIG. 1 is a schematic structural diagram of an apparatus used in forward osmosis experiments.
By analyzing the components of the filter cake formed on the feed liquid side during the forward osmosis process, fig. 2 is a fourier infrared spectrogram of sodium alginate and the filter cake layer material, indicating that the carboxylate signal peak of the filter cake layer material is shifted, possibly due to the presence of calcium ions; further, fig. 3 and 4 are X-ray photoelectron spectra of alginate and cake material, respectively, and comparing the two results confirms that the cake material is indeed calcium alginate. FIG. 5 shows the water flux change for different drivers in forward osmosis process, where the drivers are 2mol/L NaCl solution and 1mol/L CaCl solution2Solution, 2mol/L CaCl2The solution was 1g/L sodium alginate solution. As can be seen from the figure, 2mol/L NaCl solution is mixed with 1mol/L CaCl2The osmotic pressures of the solutions are similar, so the total water flux is not greatly different, and the trends are similar; and 2mol/L CaCl2When the solution is used as a driving agentThe overall water flux increases due to the increase in osmotic pressure, while the trend of the water flux rising appears in the first two hours. Namely, the initial stage of forward osmosis provided by the invention is shown, calcium ions reversely permeate along with the progress of the experiment, a calcium alginate filter cake layer is formed on the raw material liquid side, and the water flux rather shows a rising trend, namely, 2mol/L CaCl is proved2Membrane fouling is instead reduced in the early stages of forward osmosis when the solution is used as a driving agent.
The embodiment of the invention provides a method for recycling alginate by forward osmosis concentration through reverse osmosis of a driving agent, which solves the core problems in the forward osmosis technology: driver reverse osmosis, driver consumption, and water flux decline (greater membrane fouling).
The method for recycling alginate by forward osmosis concentration of reverse osmosis of the driving agent provided by the embodiment of the invention is a reverse osmosis alginate forward osmosis concentration recycling method by taking a solution of high-valence metal ions such as calcium ions and the like as the driving agent, and CaCl is used2The solution is used as a driving agent, which can not only recover the calcium alginate filter cake layer formed by reverse osmosis, but also reduce membrane pollution in the forward osmosis process and improve water flux.
The method for recycling alginate by forward osmosis concentration of reverse osmosis of the driving agent is not only suitable for CTA-ES membranes, but also suitable for other types of forward osmosis membranes.
The method for concentrating and recovering the alginate by forward osmosis and reverse osmosis of the driving agent is not only suitable for concentrating and dehydrating the alginate, but also suitable for concentrating and dehydrating other similar high molecular substances, such as polysaccharide, extracellular polymers and the like.
The embodiment of the invention provides a method for recycling alginate by forward osmosis concentration of reverse osmosis of a driving agent, and the driving agent in the method is not limited to CaCl2The solution can also be used as other drivers of the same type, e.g. MgCl2And (3) solution.
The embodiment of the invention provides a method for recovering alginate by forward osmosis concentration of driving agent reverse osmosis, the above embodiment is not limited to the illustrated example, and other processes with the same principle also belong to the protection scope.
According to the method for recycling alginate by forward osmosis concentration through reverse osmosis of the driving agent, high-valence metal ions in reverse osmosis interact with alginate to form corresponding metal alginate such as calcium alginate, and the generated corresponding metal alginate is a target product to be concentrated and recycled; meanwhile, the high-valence metal ions which are permeated reversely interact with the alginate to form alginate target products of corresponding metals, so that the alginate target products have lower membrane pollution to the permeable membrane; the driving agent in the embodiment of the invention is a raw material of a target product, so that the consumption problem is avoided; the invention is based on the reverse thinking mode, and can avoid the reverse osmosis problem of the driving agent, and further utilize the reverse osmosis driving agent to react with the alginate to generate the target metal alginate to be concentrated and recovered.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. A method for recovering alginate by forward osmosis concentration using reverse osmosis of a driving agent, characterized in that: including driving agent storage device, feed liquid storage device and just permeate membrane module, driving agent storage device is used for storing the driving agent, just the driving agent is high valence metal ion solution, feed liquid storage device is used for storing raw materials liquid, just raw materials liquid is sodium alginate solution, raw materials liquid in the feed liquid storage device carries out just permeating through the just permeate membrane module, simultaneously driving agent in the driving agent storage device carries out reverse osmosis, just raw materials liquid is in the just permeate membrane module is close to one side formation filter cake layer of feed liquid storage device, the filter cake layer is the target product of concentrated recovery promptly, just the composition on filter cake layer is high valence metal alginate.
2. The method for recovering alginate through forward osmosis concentration using reverse osmosis of a driving agent according to claim 1, wherein the feed liquid storage device is in communication with the forward osmosis membrane module through a first delivery pipe, the forward osmosis membrane module is in communication with the driving agent storage device through a second delivery pipe, the driving agent storage device is also in communication with the forward osmosis membrane module through a third delivery pipe, and the forward osmosis membrane module is in communication with the feed liquid storage device through a fourth delivery pipe.
3. The method for recovering alginate through forward osmosis concentration using reverse osmosis of a driving agent according to claim 2, wherein a first gear pump is provided on the third delivery pipe and a second gear pump is provided on the fourth delivery pipe.
4. The method for recovery of alginate by forward osmosis concentration using reverse osmosis with a driving agent according to any one of claims 1-3, wherein the high valence metal ion solution is CaCl2Solutions or MgCl2One or two of the solutions.
5. The method for recovery of alginate by forward osmosis concentration with reverse osmosis of a driving agent according to claim 4, wherein said high valence metal ion solution is CaCl2And (3) solution.
6. The method for recovering alginate through forward osmosis concentration using reverse osmosis of a driving agent according to claim 4, wherein the raw material solution forms a cake layer on the side of the forward osmosis membrane module close to the feed solution storage device, the cake layer is a target product of concentration recovery, and the cake layer is calcium alginate or magnesium alginate.
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