CN114684956B - Membrane separation method for recycling sorbic acid in sorbic acid wastewater - Google Patents
Membrane separation method for recycling sorbic acid in sorbic acid wastewater Download PDFInfo
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- CN114684956B CN114684956B CN202011642328.5A CN202011642328A CN114684956B CN 114684956 B CN114684956 B CN 114684956B CN 202011642328 A CN202011642328 A CN 202011642328A CN 114684956 B CN114684956 B CN 114684956B
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
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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
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses a membrane separation method for recycling sorbic acid in sorbic acid wastewater, which comprises the following steps: regulating pH of the sorbic acid wastewater stock solution to 2-5, dissociating macromolecular tar substances, controlling pressure to 0.01-0.5 Mpa by an ultrafiltration membrane device, and filtering and intercepting solid suspended matters and macromolecular tar substances at 20-30 ℃ to obtain clear filtrate; heating the clarified filtrate after ultrafiltration to 60-95 ℃, then passing through a nanofiltration membrane concentration device, controlling the operation vacuum degree to-0.1 to-0.06 MPa, and intercepting sorbic acid to obtain concentrated water and clear liquid containing sorbic acid; cooling the concentrated water to 10-40 ℃, crystallizing and filtering; and (3) merging the obtained filtrate into a clarified liquid treated by the ultrafiltration membrane, and sending the clarified liquid into a nanofiltration membrane separation system to continuously separate sorbic acid. Compared with the resin method process, the method can better realize the recycling of resources.
Description
Technical Field
The invention relates to the technical field of separation, in particular to a membrane separation method for separating sorbic acid.
Background
Sorbic acid
Chinese alias: 2-propenyl acrylic acid; 2,4-hexadienoic acid; cool tea acid;
english name: (2E, 4E) -hexa-2,4-dienoic acid
English alias: sorbistat;2,4-Hexadienoic acid; sorbinic acid;
molecular formula and molecular weight: c6h8o2=112.13
Appearance: white needle-like or powdery crystals
Melting point (. Degree. C.): 132-135 ℃ (lit.)
Boiling point: 228 DEG C
Flash point: 127 DEG C
Water solubility: 887g/L (20 ℃ C.)
Solubility: slightly water-soluble, propylene glycol-soluble, absolute ethyl alcohol and methanol-soluble, glacial acetic acid, acetone, benzene, carbon tetrachloride, cyclohexane, dioxane, glycerol, isopropanol, isopropyl ether, methyl acetate and toluene.
Sorbic acid is a high-efficiency safe preservative and fresh-keeping agent recommended by international grain and agriculture organizations and health organizations, and is one of the food additives with highest safety accepted internationally. With the rapid development of industries such as food, feed and the like, the demand of sorbic acid is gradually increased year by year at home and abroad, and besides being used as a food additive, sorbic acid and derivatives thereof are increasingly developed in the synthesis of fine chemicals.
The synthesis process in the prior art comprises the following steps:
the prior art introduces a method for recovering sorbic acid in sorbic acid wastewater mainly comprising the following steps:
(1) patent document CN101177389 describes adsorption of sorbic acid with XDA-1G resin in the range of 0.5-1.0 mg/ml residual sorbic acid concentration in sorbic acid wastewater, and recovery of sorbic acid by ethanol desorption and distillation separation after saturation of adsorption.
(2) Patent document CN1168671C describes adsorption of sorbic acid with residual sorbic acid concentration of about 2000mg/L in sorbic acid washing wastewater by using a plurality of types of macroporous adsorption resin columns copolymerized by styrene-divinylbenzene, and recovery of sorbic acid by ethanol desorption and distillation separation after adsorption saturation.
The technology comprises the steps of adsorbing sorbic acid in the wastewater by resin, and eluting the sorbic acid adsorbed in the resin in an alcohol or alkali mode; the sorbic acid is recovered by the resin process, and although the sorbic acid has a certain effect, a small amount of high molecular tar substances are contained in the sorbic acid wastewater, so that the pore canal can be blocked by the resin after long-term use, and the service life of the resin can be reduced; and the resin equipment occupies a large area, and post-treatment after resin analysis is complicated. Compared with the method, the method has the advantages of simple whole treatment route, physical separation and recovery of sorbic acid, safe process, low production cost and high application value.
Patent documents adopting the above method are as follows:
1. xiong Chunhua, yao Caiping, han Xiaoxiang, wang Yaning. Process for separating and recovering sorbic acid from waste water of sorbic acid production [ P ]. CN101177389.
2. Zhang Quanxing, luo Gang, li Aimin, etc. the method for treating and recovering washing waste water in sorbic acid production [ P ]. CN1168671C.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a membrane separation method for recycling sorbic acid in sorbic acid wastewater, which overcomes the risk of easy blockage in a resin adsorption method.
The technical scheme of the invention is that the membrane separation method for recycling sorbic acid in sorbic acid wastewater comprises the following steps:
1) Regulating pH of the sorbic acid wastewater stock solution to 2-5, dissociating macromolecular tar substances, controlling pressure to 0.01-0.5 Mpa by an ultrafiltration membrane device, and filtering and intercepting solid suspended matters and macromolecular tar substances at 20-30 ℃ to obtain clear filtrate;
2) Heating the clarified filtrate after ultrafiltration to 60-95 ℃, then passing through a nanofiltration membrane concentration device, controlling the operation vacuum degree to-0.1 to-0.06 MPa, and intercepting sorbic acid to obtain concentrated water and clear liquid containing sorbic acid;
3) Cooling the concentrated water to 10-40 ℃, crystallizing and filtering;
4) And 3) merging the filtrate obtained in the step 3) into a clarified liquid treated by an ultrafiltration membrane, and sending the clarified liquid into a nanofiltration membrane separation system to continuously separate sorbic acid.
The pressure in step 1) is controlled in the range, and the main function is to maintain stable flux, and the membrane is easily damaged by high pressure.
The purpose of the step 2) of raising the temperature is to ensure that the materials of the membrane system are in a homogeneous state of the aqueous solution, and avoid the phenomenon that the membrane holes are blocked due to the rising and precipitation of sorbic acid concentration during membrane separation. The degree of vacuum influences the separation efficiency, and the higher the degree of vacuum, the higher the separation efficiency.
In the step 2), concentrated water and clear liquid containing sorbic acid are obtained; cooling and crystallizing the concentrated water; a clear liquid biochemical treatment system;
in the step 3), filtering to obtain filtrate and a wet product of sorbic acid. The obtained sorbic acid as a tide product is sent to a production system, and the filtrate is sent to be combined with the clear liquid after ultrafiltration for use.
Ultrafiltration device function: filtering and intercepting solid suspended matters and macromolecular tar matters;
nanofiltration membrane device function: separating and intercepting sorbic acid in the wastewater.
According to the membrane separation method for recycling sorbic acid in sorbic acid wastewater, preferably, the membrane adopted by the ultrafiltration membrane device in the step 1) is selected from an inorganic membrane or an organic membrane, and the molecular weight cut-off of the membrane is 1000Da to 8000Da.
According to the membrane separation method for recycling sorbic acid in sorbic acid wastewater, preferably, the membrane adopted by the nanofiltration membrane concentration device in the step 2) is selected from an inorganic membrane or an organic membrane, and the molecular weight cut-off of the membrane is 100 Da-300 Da.
According to the membrane separation method for recycling sorbic acid in sorbic acid wastewater, in the step 1), preferably, the pH is adjusted by alkali liquor.
According to the membrane separation method for recycling sorbic acid in sorbic acid wastewater, in the step 2), preferably, heat exchange of clarified filtrate after ultrafiltration is raised to 60-95 ℃.
According to the membrane separation method for recycling sorbic acid in sorbic acid wastewater, in the step 2), preferably, the clarified filtrate after ultrafiltration is heated to 70-90 ℃.
Preferably, in step 3), the cooling mode is cooling with cooling water.
Preferably, in step 3), the concentrated water is cooled to 15-35 ℃.
The technical principle of the invention is as follows:
the waste water in the sorbic acid production process contains sorbic acid, and suspended matters or macromolecular tar and other impurities in the waste water are removed through pretreatment; the pretreated water adopts a membrane separation technology, and the sorbic acid with high added value is intercepted by the difference of the molecular weight of organic matters. The invention adopts the membrane separation technology to separate and recycle the sorbic acid in the wastewater, realizes the recycling of sorbic acid resources and reduces the production cost of sorbic acid.
The ultrafiltration principle of the invention: at normal temperature, the solvent and small molecular substances pass through the microporous membrane medium with a certain pressure and flow rate by using the pressure difference at two sides of the microporous membrane as driving force, and the large molecular substances are blocked by the filter membrane.
Nanofiltration principle: chemical equilibrium of permeate between the surface forming phases of the membrane by the principle of dissolution-diffusion and electrical effect of the membrane surface; electrostatic interaction is formed between the membrane and the electrolyte ions, and corresponding substances are trapped according to the charge intensity.
After the ultrafiltration membrane operates for a period of time and the water yield is reduced, the tar substances on the surface of the membrane are required to be circularly cleaned by alkali liquor, and the flux is recovered. The concentration of the lye may be chosen to be 1-20wt%, more preferably 2-6wt%.
The beneficial effects are that:
1. compared with the resin method process, the method can better realize the recycling of resources.
2. The sorbic acid (the sorbic acid recovery rate is more than 95%) remained in the wastewater can be recovered, waste materials are changed into valuable materials, and the utilization rate of sorbic acid resources is improved.
3. The process is simple, no special equipment is needed, the technology is easy to master, the operation is convenient, and the operation cost is low.
4. The biodegradability of the wastewater is effectively improved while the sorbic acid in the wastewater is recovered.
Drawings
Fig. 1 is a flow chart of the present invention.
Detailed Description
The following provides a specific embodiment of a membrane separation method for recycling sorbic acid in sorbic acid wastewater.
Example 1
Firstly, regulating the pH value of the wastewater stock solution to be=2 by liquid alkali, controlling the pressure to be 0.1Mpa by an ultrafiltration membrane device (the inorganic membrane interception precision is 1000 Da), and filtering and intercepting solid suspended matters and macromolecular tar matters at the temperature of 20-30 ℃ to obtain clear filtrate; heat exchanging and heating the clarified filtrate after ultrafiltration to 90-95 ℃, then passing through a nanofiltration membrane concentration device (the interception precision of an organic membrane is 100 Da), controlling the vacuum degree to minus 0.1-minus 0.095MPa, and intercepting sorbic acid to obtain concentrated water and clear liquid containing sorbic acid; a clear liquid biochemical treatment system; cooling concentrated water containing sorbic acid to 10-15 ℃ through cooling water, crystallizing, filtering, removing sorbic acid tide products to a production system, and merging filtrate into clear liquid after ultrafiltration; the recovery rate of sorbic acid is 97.5%.
Example 2
Firstly, regulating the pH value of the wastewater stock solution to be=3 by liquid alkali, controlling the pressure to be 0.25Mpa and the temperature to be 20-30 ℃ by an ultrafiltration membrane device (inorganic membrane interception precision is 1000 Da), and filtering and intercepting solid suspended matters and macromolecular tar matters to obtain clear filtrate; heat exchanging and heating the clarified filtrate after ultrafiltration to 80-85 ℃, then passing through a nanofiltration membrane concentration device (the interception precision of an organic membrane is 100 Da), controlling the vacuum degree to minus 0.095-minus 0.09MPa, and intercepting sorbic acid to obtain concentrated water and clear liquid containing sorbic acid; a clear liquid biochemical treatment system; cooling concentrated water containing sorbic acid to 20-25 ℃ through cooling water, crystallizing, filtering, removing sorbic acid tide products to a production system, and merging filtrate into clear liquid after ultrafiltration; the recovery rate of sorbic acid is 97.5%.
Example 3
Firstly, regulating the pH value of the wastewater stock solution to be=4 by liquid alkali, controlling the pressure to be 0.5Mpa by an ultrafiltration membrane device (the interception precision of an organic membrane is 2000 Da), and filtering and intercepting solid suspended matters and macromolecular tar matters at the temperature of 20-30 ℃ to obtain clear filtrate; heat exchanging and heating the clarified filtrate after ultrafiltration to 70-75 ℃, then passing through a nanofiltration membrane concentration device (inorganic membrane interception precision is 200 Da), controlling vacuum degree to minus 0.085-minus 0.08MPa, intercepting sorbic acid, and obtaining concentrated water and clear liquid containing sorbic acid; a clear liquid biochemical treatment system; cooling concentrated water containing sorbic acid to 35-40 ℃ through cooling water, crystallizing, filtering, removing sorbic acid tide products to a production system, and merging filtrate into clear liquid after ultrafiltration; the recovery rate of sorbic acid is 95.6%.
Example 4
Firstly, regulating the pH value of the wastewater stock solution to be=5 by liquid alkali, controlling the pressure to be 0.05Mpa and the temperature to be 20-30 ℃ by an ultrafiltration membrane device (the interception precision of an organic membrane is 2000 Da), and filtering and intercepting solid suspended matters and macromolecular tar matters to obtain clear filtrate; heat exchanging and heating the clarified filtrate after ultrafiltration to 60-65 ℃, then passing through a nanofiltration membrane concentration device (the interception precision of an organic membrane is 300 Da), controlling the vacuum degree to minus 0.065-minus 0.06MPa, and intercepting sorbic acid to obtain concentrated water and clear liquid containing sorbic acid; a clear liquid biochemical treatment system; cooling concentrated water containing sorbic acid to 10-15 ℃ through cooling water, crystallizing, filtering, removing sorbic acid tide products to a production system, and merging filtrate into clear liquid after ultrafiltration; the recovery rate of sorbic acid is 95.2%.
Compared with the resin method process, the method can better realize the recycling of resources. The process is simple and the cost is reduced.
Claims (7)
1. A membrane separation method for recycling sorbic acid in sorbic acid wastewater is characterized by comprising the following steps of: the method comprises the following steps:
1) Regulating pH of the sorbic acid wastewater stock solution to 2-5, dissociating macromolecular tar substances, controlling pressure to 0.01-0.5 Mpa by an ultrafiltration membrane device, and filtering and intercepting solid suspended matters and macromolecular tar substances at 20-30 ℃ to obtain clear filtrate; the membrane adopted by the ultrafiltration membrane device is selected from an inorganic membrane or an organic membrane, and the molecular weight cut-off of the membrane is 1000Da to 8000Da;
2) Heating the clarified filtrate after ultrafiltration to 60-95 ℃, then passing through a nanofiltration membrane concentration device, controlling the operation vacuum degree to-0.1 to-0.06 MPa, and intercepting sorbic acid to obtain concentrated water and clear liquid containing sorbic acid;
3) Cooling the concentrated water to 10-40 ℃, crystallizing and filtering; filtering to obtain filtrate and sorbic acid; the obtained sorbic acid as a tide product is sent to a production system, and the filtrate is sent to be combined with clear liquid after ultrafiltration for use;
4) And 3) merging the filtrate obtained in the step 3) into a clarified liquid treated by an ultrafiltration membrane, and sending the clarified liquid into a nanofiltration membrane separation system to continuously separate sorbic acid.
2. The membrane separation method for recycling sorbic acid in sorbic acid wastewater according to claim 1, wherein the method comprises the following steps: the membrane adopted by the nanofiltration membrane concentration device in the step 2) is selected from an inorganic membrane or an organic membrane, and the molecular weight cut-off of the membrane is 100Da to 300Da.
3. The membrane separation method for recycling sorbic acid in sorbic acid wastewater according to claim 1, wherein the method comprises the following steps: in step 1), the pH is adjusted with an alkaline solution.
4. The membrane separation method for recycling sorbic acid in sorbic acid wastewater according to claim 1, wherein the method comprises the following steps: in the step 2), the clarified filtrate after ultrafiltration is subjected to heat exchange and is heated to 60-95 ℃.
5. The membrane separation method for recycling sorbic acid in sorbic acid wastewater according to claim 1, wherein the method comprises the following steps: in the step 2), the clarified filtrate after ultrafiltration is heated to 70-90 ℃.
6. The membrane separation method for recycling sorbic acid in sorbic acid wastewater according to claim 1, wherein the method comprises the following steps: in the step 3), the cooling mode is cooling by cooling water.
7. The membrane separation method for recycling sorbic acid in sorbic acid wastewater according to claim 1, wherein the method comprises the following steps: in the step 3), the temperature of the concentrated water is reduced to 15-35 ℃.
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| JPH11188358A (en) * | 1997-12-26 | 1999-07-13 | Daicel Chem Ind Ltd | Treating method for waste water containing sorbic acid or its salt, and waste water treatment equipment |
| CN101058586B (en) * | 2007-04-06 | 2013-04-24 | 杭州天创环境科技股份有限公司 | Method of concentrating and separating glyphosate in high salt content glyphosate mother liquor by film technique |
| CN102381959B (en) * | 2011-09-05 | 2014-09-03 | 南通奥凯生物技术开发有限公司 | Method for preparing potassium sorbate with membrane chemical reactor |
| CN109499369B (en) * | 2018-12-04 | 2021-08-13 | 云南中烟新材料科技有限公司 | Tobacco extract concentrating process |
| CN111875090A (en) * | 2020-06-30 | 2020-11-03 | 成都泓润科技有限公司 | Waste water treatment method |
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