CN115504605A - Process device and treatment method for anion resin chlorination mother liquor - Google Patents
Process device and treatment method for anion resin chlorination mother liquor Download PDFInfo
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- CN115504605A CN115504605A CN202211274941.5A CN202211274941A CN115504605A CN 115504605 A CN115504605 A CN 115504605A CN 202211274941 A CN202211274941 A CN 202211274941A CN 115504605 A CN115504605 A CN 115504605A
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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
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a process unit for anion resin chlorination mother liquor, which comprises the following steps: the system comprises a waste liquid storage tank, a hydrolysis reactor, a solid-liquid separator, an oxidation reactor I, an oxidation reactor II, a flocculation sedimentation tank and a plate-and-frame filter press; the invention realizes the efficient purification treatment of waste liquid generated in the process of producing the anion resin, and is beneficial to solving the problems of incomplete harmless treatment and poor treatment effect of hazardous wastes in the anion resin chlorination mother liquid.
Description
Technical Field
The invention relates to the technical field of hazardous waste treatment, in particular to a process device and a treatment method of anion resin chlorination mother liquor.
Background
With the continuous development of science and technology, the functionality of the ion exchange resin is continuously developed in different fields, particularly the application and development of the functionality of the anion exchange resin in recent years, and the total manufacturing amount of the anion exchange resin in China is suddenly ahead of the total manufacturing amount in the world; in the chlorination process of producing the anion resin, zinc chloride is only used as a catalyst and does not participate in the reaction, the content of the zinc chloride in the mother liquor is more than 45 percent, a large amount of zinc chloride can be completely dissolved in the mother liquor in acid mother liquor, and the waste liquor generated in the production of the anion resin in the chlorination process is greatly increased, wherein the chlorination mother liquor of the anion resin is generated in the chloromethylation reaction process in the production of the anion resin; the generated anion resin chlorination mother liquor contains complex organic matters such as tar and the like, and has more impurities, and the mother liquor is black viscous liquid, so that the waste liquor has complex components, and can not be directly incinerated due to the fact that the mother liquor contains a large amount of heavy metals and shows strong acidity.
In the prior art, the recovery and disposal methods of anion resin chlorination mother liquor which are disclosed at present are as follows:
for example, the Chinese patent of invention with the publication number of CN101518747A, namely a recycling system and a recycling method of chlorinated mother liquor, designs a production method of chloromethyl ether without participation of liquid formaldehyde and hydrochloric acid, and directly recycles the chlorinated mother liquor to synthesize the chloromethyl ether.
For example, the invention patent of China with the publication number of CN113955766A "method for preparing zinc borate by utilizing zinc chloride in anion resin chlorination mother liquor" is that zinc chloride slurry in the chlorination mother liquor is weighed and then placed in a reaction kettle, supersaturated borax solution is dripped, the temperature is reduced after reaction for a period of time, the zinc borate crystal is generated after standing, the method does not purify the zinc chloride, and the zinc borate preparation in the later stage involves a large amount of work of purification, impurity removal and the like, which causes a large amount of hazardous waste to be generated, and the recovery cost is high.
In conclusion, the existing method for disposing the anion resin chlorination mother liquor mainly relates to recycling of components with useful values, the recycling cost is high, and harmless disposal of such hazardous wastes is not carried out.
Disclosure of Invention
The invention aims to provide a process device and a treatment method for anion resin chlorination mother liquor, which are used for solving the problems of incomplete harmless treatment and poor treatment effect of hazardous wastes in the anion resin chlorination mother liquor.
The purpose of the invention can be realized by the following technical scheme:
a process unit of anion resin chlorination mother liquor comprises:
a waste liquid storage tank, wherein the inner cavity of the waste liquid storage tank is used for containing waste liquid generated in the process of producing the anion resin;
the hydrolysis reactor is connected with the waste liquid storage tank through a pipeline, a first dosing device is arranged above the hydrolysis reactor, and the first dosing device conveys recycled water into the waste liquid storage tank through a pipeline;
the solid-liquid separator is connected with the hydrolysis reactor through a pipeline, and a slag outlet on the solid-liquid separator is connected with an incineration system;
the first oxidation reactor is connected with the liquid outlet of the solid-liquid separator through a pipeline, a second dosing device is arranged above the first oxidation reactor, and the second dosing device conveys the potassium permanganate and the lime water into the first oxidation reactor through a pipeline;
the second oxidation reactor is connected with the first oxidation reactor through a pipeline, a third dosing device is arranged above the second oxidation reactor, and the third dosing device conveys hydrogen peroxide and ferrous sulfate into the second oxidation reactor through a pipeline;
the flocculation sedimentation tank is connected with the second oxidation reactor through a pipeline, a fourth dosing device is arranged above the flocculation sedimentation tank, and the fourth dosing device conveys sodium hydroxide and PAC into the flocculation sedimentation tank through a pipeline;
the plate-and-frame filter press is connected with the flocculation sedimentation tank through a pipeline;
and the outer walls of the hydrolysis reactor, the oxidation reactor I, the oxidation reactor II and the flocculation sedimentation tank are respectively wrapped with a cooling water circulation device.
As a further scheme of the invention: the hydrolysis reactor, the oxidation reactor I, the oxidation reactor II and the flocculation sedimentation tank are respectively connected with a gas disposal device through pipelines.
As a further scheme of the invention: the gas treatment device comprises a sulfuric acid absorber, a sodium hydroxide absorber, an activated carbon absorber and a vacuum pump which are sequentially arranged along the exhaust direction.
As a further scheme of the invention: and the cooling water circulating device is provided with a cooling circulating water inlet and a cooling circulating water outlet.
As a further scheme of the invention: and conveying the sludge treated by the plate and frame filter press to a solidification landfill treatment device, and conveying the treated sewage to a sewage treatment device.
As a further scheme of the invention: and the hydrolysis reactor, the oxidation reactor I, the oxidation reactor II and the flocculation sedimentation tank are respectively internally provided with a stirring device, a pH meter, a thermometer and an ORP meter.
As a further scheme of the invention: a first liquid pump is arranged on a pipeline between the waste liquid storage tank and the hydrolysis reactor; a second liquid pump is arranged on a pipeline between the hydrolysis reactor and the solid-liquid separator; a third liquid pump is arranged on a pipeline between the solid-liquid separator and the first oxidation reactor; a liquid pump IV is arranged on a pipeline between the first oxidation reactor and the second oxidation reactor; a fifth liquid pump is arranged on a pipeline between the second oxidation reactor and the flocculation sedimentation tank; and a liquid pump six is arranged on a pipeline between the flocculation sedimentation tank and the plate-and-frame filter press.
A method for processing anion resin chlorination mother liquor comprises the following steps:
step one, hydrolysis: pumping waste liquid generated in the process of producing anion resin in a waste liquid storage tank into a hydrolysis reactor, and adding recycled water through a first dosing device to perform hydrolysis reaction, so that chloromethyl ether is hydrolyzed and a flocculent precipitate mixture is formed due to the cross-linking polymerization of styrene and divinylbenzene;
step two, solid-liquid separation: carrying out solid-liquid separation on the mixture treated by the hydrolysis reaction in the step I by using a solid-liquid separator, conveying a solid phase to an incineration system through a slag outlet, and carrying out next treatment on a liquid phase;
step three, oxidation reaction: pumping the mixed liquid subjected to solid-liquid separation treatment in the step two into an oxidation reactor I, adding potassium permanganate into the mixed liquid through a second dosing device for oxidation, adding lime water into the mixed liquid through the second dosing device for adjusting the pH value of the mixed liquid in the oxidation reactor I to 3.0-4.0 after reacting for 4-5h, pumping the mixed liquid subjected to adjustment treatment in the oxidation reactor I into the oxidation reactor II, and adding ferrous sulfate and hydrogen peroxide into the mixed liquid through a third dosing device for continuing oxidation reaction for 3-4h;
step four, neutralization: pumping the mixed solution subjected to the step three-oxidation treatment into a flocculation precipitation tank, adding sodium hydroxide through a fourth dosing device to adjust the pH of the mixed solution to 9.0-10.0, and adding PAC through the fourth dosing device to further perform flocculation precipitation;
step five, filter pressing: pumping the mixed liquor treated in the step four into a plate-and-frame filter press, further treating the sewage filtrate in a sewage treatment device, recycling the filter residue as heavy metal zinc, and further treating other sludge filter residue in a curing landfill treatment device;
wherein, in the first step, the third step and the fourth step, a cooling water circulation device is adopted to control the reaction temperature not to exceed 5 ℃.
The invention has the beneficial effects that:
(1) Purifying waste liquid storage tank, hydrolysis reactor, solid-liquid separator, oxidation reactor I, oxidation reactor II, flocculation sedimentation tank and plate-and-frame filter press which are arranged in sequence, adding reuse water into the hydrolysis reactor for hydrolysis reaction, so that waste liquid is hydrolyzed to form flocculent sedimentation mixture, the flocculent sedimentation mixture is convenient for removing solid-phase impurities through the solid-liquid separator, separated liquid-phase mixed liquid is pumped into the oxidation reactor I and the oxidation reactor II in sequence for oxidation reaction, and the mixed liquid pumped into the flocculation sedimentation tank can obtain Zn (OH) 2 The precipitate is treated by a plate-and-frame filter press to recycle heavy metal zinc, the finally treated sewage has low zinc ion content, neutral pH and low COD content, and the COD can be used as an organic matter phaseA comprehensive index of content;
(2) The invention realizes the efficient purification treatment of the waste liquid generated in the process of producing the anion resin, and is beneficial to solving the problems of incomplete harmless treatment and poor treatment effect of hazardous wastes in the anion resin chlorination mother liquid.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a schematic structural diagram of a process unit for chlorinating a mother liquor by using an anionic resin;
FIG. 2 is a schematic diagram of the gas disposal device connected with the hydrolysis reactor, the oxidation reactor I, the oxidation reactor II and the flocculation sedimentation tank in FIG. 1.
In the figure: 1. a waste liquid storage tank; 2. a hydrolysis reactor; 3. a solid-liquid separator; 4. a first oxidation reactor; 5. a second oxidation reactor; 6. a flocculation sedimentation tank; 7. a plate-and-frame filter press; 8. a first dosing device; 9. a second dosing device; 10. a third dosing device; 11. a fourth dosing device; 12. a cooling water circulating device; 13. a first liquid pump; 14. a liquid pump II; 15. a liquid pump III; 16. a liquid pump IV; 17. a liquid pump V; 18. a liquid pump six; 19. curing the landfill disposal device; 20. a sewage disposal device; 21. a stirring device; 22. a sulfuric acid absorber; 23. a sodium hydroxide absorber; 24. an activated carbon absorber; 25. a vacuum pump.
Detailed Description
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 only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Referring to fig. 1 and 2, the present invention is a process apparatus for chlorination of mother liquor of anion resin, comprising: the system comprises a waste liquid storage tank 1, a hydrolysis reactor 2, a solid-liquid separator 3, a first oxidation reactor 4, a second oxidation reactor 5, a flocculation sedimentation tank 6 and a plate-and-frame filter press 7; waste liquid generated in the process of producing the anionic resin is contained in the inner cavity of the waste liquid storage tank 1; the hydrolysis reactor 2 is connected with the waste liquid storage tank 1 through a pipeline, a first dosing device 8 is arranged above the hydrolysis reactor 2, and the first dosing device 8 conveys the reuse water into the waste liquid storage tank 1 through a pipeline; the solid-liquid separator 3 is connected with the hydrolysis reactor 2 through a pipeline, and a slag outlet on the solid-liquid separator 3 is connected with an incineration system; the first oxidation reactor 4 is connected with a liquid outlet of the solid-liquid separator 3 through a pipeline, a second dosing device 9 is arranged above the first oxidation reactor 4, and the second dosing device 9 conveys the potassium permanganate and the lime water into the first oxidation reactor 4 through a pipeline; the second oxidation reactor 5 is connected with the first oxidation reactor 4 through a pipeline, a third dosing device 10 is arranged above the second oxidation reactor 5, and the third dosing device 10 conveys hydrogen peroxide and ferrous sulfate into the second oxidation reactor 5 through a pipeline; the flocculation sedimentation tank 6 is connected with the second oxidation reactor 5 through a pipeline, a fourth dosing device 11 is arranged above the flocculation sedimentation tank 6, and the fourth dosing device 11 conveys sodium hydroxide and PAC into the flocculation sedimentation tank 6 through a pipeline; the plate-and-frame filter press 7 is connected with the flocculation sedimentation tank 6 through a pipeline;
when waste liquid that produces anion resin in-process carries out innocent treatment in proper order, wherein, hydrolysis reactor 2, oxidation reactor 4, oxidation reactor two 5 and flocculation and precipitation pond 6 are divided to be divided the parcel respectively on the outer wall and are provided with cooling water circulating device 12, be provided with cooling circulation water inlet and cooling circulation delivery port on the cooling water circulating device 12, because contain a large amount of organic components in the waste liquid that produces anion resin in-process, for example chloromethyl ether, chloromethyl ether has special smell, the boiling point is at 55 ℃, smell escapes when handling, the handling process need be carried out through cooling water circulating device 12 control low temperature.
Further, the hydrolysis reactor 2, the oxidation reactor I4, the oxidation reactor II 5 and the flocculation sedimentation tank 6 are respectively connected with a gas treatment device through pipelines, and the gas treatment device comprises a sulfuric acid absorber 22, a sodium hydroxide absorber 23, an activated carbon absorber 24 and a vacuum pump 25 which are sequentially arranged along the exhaust direction, so that the waste gas generated in the treatment reaction process is subjected to acid removal, alkali removal and adsorption treatment, and the harm of the discharged waste gas to the atmospheric environment is reduced.
Further, the sludge treated by the plate-and-frame filter press 7 is conveyed to a solidification landfill treatment device 19, and the treated sewage is conveyed to a sewage treatment device 20, so that harmless sewage and sludge are obtained after the waste liquid generated in the process of producing the anion resin is finally treated.
Furthermore, a stirring device 21, a pH meter, a thermometer and an ORP meter are respectively arranged in the hydrolysis reactor 2, the oxidation reactor I4, the oxidation reactor II 5 and the flocculation sedimentation tank 6, the stirring device 21 is arranged to accelerate the reaction speed in each process, and the pH meter, the thermometer and the ORP meter are used for correspondingly detecting the reaction value in each process.
Further, a first liquid pump 13 is arranged on a pipeline between the waste liquid storage tank 1 and the hydrolysis reactor 2; a second liquid pump 14 is arranged on a pipeline between the hydrolysis reactor 2 and the solid-liquid separator 3; a third liquid pump 15 is arranged on a pipeline between the solid-liquid separator 3 and the first oxidation reactor 4; a liquid pump IV 16 is arranged on a pipeline between the first oxidation reactor 4 and the second oxidation reactor 5; a fifth liquid pump 17 is arranged on a pipeline between the second oxidation reactor 5 and the flocculation sedimentation tank 6; a liquid pump six 18 is arranged on a pipeline between the flocculation sedimentation tank 6 and the plate-and-frame filter press 7, so that waste liquid generated in the process of producing the anionic resin is conveniently treated and pumped by each procedure in sequence.
The invention adopts a technical scheme of a disposal method.
The principle of the treatment method is as follows: the waste liquid (acidity: 1.0-4.0 mol/L, COD content: 100000-500000mg/L, zinc content: 150000-200000 mg/L) generated in the process of producing anion resin is taken as a main disposal object, firstly, the waste liquid is diluted by adding back water and then hydrolyzed to form solid precipitate, and the reaction system belongs to a dispersion system of suspension polymerization and is an unstable system, and monomer liquid drops have the tendency of mutual agglomeration under the action of liquid boundary tension; after reaction, solid-liquid separation is carried out, the solid phase can be treated by an incineration system, the liquid phase adopts potassium permanganate to oxidize and decompose residual organic matters, a Fenton oxidation system (hydrogen peroxide and ferrous sulfate) is adopted to further oxidize the organic matters, sodium hydroxide is used for adjusting the pH value to be about 8.0, hydroxyl ions and heavy metal zinc ions form zinc hydroxide precipitate, a macromolecular precipitate is formed by utilizing the flocculation effect of the zinc hydroxide precipitate, finally, after the solid-liquid mixed liquid is subjected to plate and frame filter pressing, the filter residue is subjected to resource recycling of heavy metal zinc, the filter liquid enters a sewage treatment device for treatment, and the treated effluent can flow back to a hydrolysis device for use.
The reaction mechanism in the process of the treatment method is as follows:
the suspension polymerization dispersion system is an unstable system, monomer liquid drops have a tendency of mutual agglomeration under the action of liquid interfacial tension, and after the conversion rate reaches 20% -30%, a part of high polymer is swelled in the monomer liquid drops, so that the liquid drops become sticky, and the collision between the liquid drops can cause a bonding phenomenon, and the crosslinked polymer generated by styrene and divinylbenzene in the waste liquid of the ion exchange resin production.
Hydrolysis mechanism of chloromethyl ether:
the oxidation mechanism is as follows:
H 2 O+Fe 2+ →·OH+Fe 3+ +OH -
H 2 O 2 +Fe 3+ →·O 2 H+Fe 2+ +H +
Fe 2+ +·OH→Fe 3+ +OH -
Fe 3+ +·O 2 H→Fe 2+ +H + +O 2
·OH+H 2 O 2 →H2O + ·O 2 H
Fe 2+ +·O 2 H→HO 2 - +Fe 3+
the precipitation mechanism is as follows:
Zn 2+ +2OH - →Zn(OH) 2 ↓
a method for processing anion resin chlorination mother liquor comprises the following steps:
step one, hydrolysis: pumping waste liquid generated in the process of producing the anionic resin in the waste liquid storage tank 1 into a hydrolysis reactor 2, and adding recycled water through a first dosing device 8 to perform hydrolysis reaction, so that chloromethyl ether is hydrolyzed and a flocculent precipitate mixture is formed due to the cross-linking polymerization of styrene and divinylbenzene;
step two, solid-liquid separation: carrying out solid-liquid separation on the mixture treated by the hydrolysis reaction in the step I by using a solid-liquid separator 3, conveying a solid phase to an incineration system through a slag outlet, and carrying out next treatment on a liquid phase;
step three, oxidation reaction: pumping the mixed liquid subjected to solid-liquid separation treatment in the step two into an oxidation reactor I4, adding potassium permanganate into the mixed liquid through a second dosing device 9 for oxidation, after reacting for 4-5 hours, adding lime water into the mixed liquid through a second dosing device 9 to adjust the pH value of the mixed liquid in the oxidation reactor I4 to 3.0-4.0, pumping the mixed liquid subjected to adjustment treatment in the oxidation reactor I4 into a second oxidation reactor 5, and adding ferrous sulfate and hydrogen peroxide into the mixed liquid through a third dosing device 10 for continuous oxidation reaction for 3-4 hours;
step four, neutralization: pumping the mixed solution subjected to the triple oxidation treatment into a flocculation sedimentation tank 6, adding sodium hydroxide through a fourth dosing device 11 to adjust the pH of the mixed solution to 9.0-10.0, and adding PAC through the fourth dosing device 11 to further perform flocculation sedimentation;
step five, filter pressing: pumping the mixed liquor treated in the step four into a plate-and-frame filter press 7, further treating the sewage filtrate in a sewage treatment device 20, recycling the heavy metal zinc from the filter residue, and further treating other sludge filter residue in a curing and landfill treatment device 19;
wherein, in the first step, the third step and the fourth step, a cooling water circulation device 12 is adopted to control the reaction temperature not to exceed 5 ℃.
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
Starting a cooling water circulating device 12, controlling the reaction temperature to be not more than 5 ℃, pumping 100L of waste liquid (faint yellow liquid, acidity: 4.54 mo/L, COD:20700mg/L and zinc ion: 35130 mg/L) generated in the process of producing the anionic resin into a hydrolysis reactor 2, adding 100L of recycled water for dilution, pumping flocculent precipitate mixture generated in the hydrolysis reaction into a solid-liquid separator 3, removing solid phase, pumping separated liquid phase mixed liquid into an oxidation reactor I4, adding 50g of potassium permanganate, after reacting for 5 hours, adding 40L of lime water to adjust the pH to 2.0-3.0, pumping the mixed liquid into an oxidation reactor II 5, adding 100g of ferrous sulfate, after stirring and dissolving, adding 1L of 30% hydrogen peroxide, stirring for reacting for 4 hours, pumping the mixed liquid into a flocculation sedimentation tank 6, adding 60g of sodium hydroxide to adjust the pH of the system to 9.0-10.0, adding 100g of PAC, polymerizing for 120 h, stirring for 1h, pumping the mixed liquid into a filter press, pumping the mixed liquid into a filter for further treating, treating the waste water, performing recycling treatment, and recovering the filter residue by using other heavy metals, namely recycling the filter residue, and recycling the filter residue by using the filter water of the filter residue, and recycling wastewater, and recovering the filter residue by using the sodium hydroxide, wherein the filter residue, and recycling water.
After the treatment process:
detecting the final effluent of the sewage treatment device, wherein the detection data is as follows: pH:8.8, heavy metal zinc less than 0.5mg/L, COD:42mg/L.
Example 2:
starting a cooling water circulating device 12, controlling the reaction temperature to be not more than 5 ℃, pumping 100L of waste liquid (viscous, acidity: 3.54mo L/L, zinc content: 83200mg/L, COD:213000 mg/L) generated in the process of producing the anionic resin into a hydrolysis reactor 2, adding 100L of recycled water into the waste liquid for hydrolysis, fully stirring for about 1h, pumping flocculent precipitate mixture generated by the hydrolysis reaction into a solid-liquid separator 3, removing solid phase, pumping separated liquid phase mixed liquid into an oxidation reactor I4, adding 100g of potassium permanganate, after 5h of reaction, pumping the mixed liquid into an oxidation reactor II 5, adding 35L of lime milk to adjust the pH to 2.0-3.0, adding 200g of ferrous sulfate, after stirring and dissolving, adding 2L of 30% hydrogen peroxide, stirring for reaction for 4h, pumping the mixed liquid into a precipitation device, adding 60g of caustic soda flakes to adjust the pH to 9.0-10.0, adding 100g of PAC, pumping 100g of the mixed liquid into a flocculation device, performing further flocculation treatment on the mixed liquid by using a flocculation treatment device, performing further recycling treatment on the waste water by using a flocculation treatment device after 1 g of water, and recovering the waste water, and recycling the filter residue, and performing the sludge by using a flocculation treatment device after the sludge recycling treatment device.
After the treatment process:
detecting the final effluent of the sewage treatment device, wherein the detection data is as follows: pH:8.4, heavy metal zinc is less than 0.5mg/L, COD:73mg/L.
Example 3:
starting a cooling water circulating device 12, controlling the reaction temperature to be not more than 5 ℃, pumping 100L of waste liquid (viscous, acidity: 3.0 mo/L, zinc content: 53200mg/L, COD:198000 mg/L) generated in the process of producing the anionic resin into a hydrolysis reactor 2, adding 100L of reuse water into the waste liquid for hydrolysis, fully stirring for about 1h, pumping a flocculent precipitate mixture generated by the hydrolysis reaction into a solid-liquid separator 3, removing a solid phase, pumping a separated liquid phase mixed liquid into an oxidation reactor I4, adding 80g of potassium permanganate, reacting for 5h, pumping the mixed liquid into an oxidation reactor II 5, adding 30L of lime milk to adjust the pH to 2.0-3.0, adding 200g of ferrous sulfate, adding 30% of hydrogen peroxide solution after stirring and dissolving, stirring for 4h, pumping the mixed liquid into a mixed precipitator, adding 60g of caustic soda flakes to adjust the pH to 9.0-10.0, adding 100g of ferrous sulfate, adding 100g of filtrate, pumping 100g of filtrate into a polymerization tank, pumping 1h of dissolved hydrogen peroxide solution, performing further recycling treatment on the mixed liquid, performing polymerization treatment on the waste water, performing further recycling treatment by a sewage by using a filter press, and recycling treatment by using a sewage plate, and recycling sludge treatment device after recycling the mixed liquid, and recycling the waste water.
After the treatment process:
detecting the final effluent of the sewage treatment device, wherein the detection data is as follows: pH:9.0, zinc content: not detected, COD:23mg/L.
While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (8)
1. A process unit of anion resin chlorination mother liquor is characterized by comprising the following steps:
a waste liquid storage tank (1), wherein the inner cavity of the waste liquid storage tank is used for containing waste liquid generated in the process of producing anion resin;
the hydrolysis reactor (2) is connected with the waste liquid storage tank (1) through a pipeline, a first dosing device (8) is arranged above the hydrolysis reactor (2), and the first dosing device (8) conveys recycled water into the waste liquid storage tank (1) through a pipeline;
the solid-liquid separator (3) is connected with the hydrolysis reactor (2) through a pipeline, and a slag outlet on the solid-liquid separator (3) is connected with an incineration system;
the first oxidation reactor (4) is connected with the liquid outlet of the solid-liquid separator (3) through a pipeline, a second dosing device (9) is arranged above the first oxidation reactor (4), and the second dosing device (9) conveys potassium permanganate and lime water into the first oxidation reactor (4) through a pipeline;
the second oxidation reactor (5) is connected with the first oxidation reactor (4) through a pipeline, a third dosing device (10) is arranged above the second oxidation reactor (5), and the third dosing device (10) conveys hydrogen peroxide and ferrous sulfate into the second oxidation reactor (5) through a pipeline;
the flocculation sedimentation tank (6) is connected with the second oxidation reactor (5) through a pipeline, a fourth dosing device (11) is arranged above the flocculation sedimentation tank (6), and the fourth dosing device (11) conveys sodium hydroxide and PAC into the flocculation sedimentation tank (6) through a pipeline;
the plate-and-frame filter press (7) is connected with the flocculation sedimentation tank (6) through a pipeline;
and the outer walls of the hydrolysis reactor (2), the oxidation reactor I (4), the oxidation reactor II (5) and the flocculation sedimentation tank (6) are respectively wrapped with a cooling water circulation device (12).
2. The process unit for the chlorination mother liquor of anion resin according to claim 1, wherein the hydrolysis reactor (2), the first oxidation reactor (4), the second oxidation reactor (5) and the flocculation sedimentation tank (6) are respectively connected with a gas disposal device through pipelines.
3. The process unit of the anion resin chlorination mother liquor according to claim 2, wherein the gas treatment device comprises a sulfuric acid absorber (22), a sodium hydroxide absorber (23), an activated carbon absorber (24) and a vacuum pump (25) which are arranged in sequence along an exhaust direction.
4. The process unit for the anion resin chlorination mother liquor according to the claim 1, wherein the cooling water circulation device (12) is provided with a cooling circulation water inlet and a cooling circulation water outlet.
5. The process unit for the anion resin chlorination mother liquor according to the claim 1, wherein the sludge treated by the plate and frame filter press (7) is transported to a solidification landfill disposal device (19), and the treated sewage is transported to a sewage disposal device (20).
6. The process unit for the anion resin chlorination mother liquor according to the claim 1, wherein the hydrolysis reactor (2), the oxidation reactor I (4), the oxidation reactor II (5) and the flocculation sedimentation tank (6) are respectively provided with a stirring device (21), a pH meter, a thermometer and an ORP meter.
7. The process unit for the chlorination mother liquor of the anion resin according to the claim 1, wherein a first liquid pump (13) is arranged on a pipeline between the waste liquor storage tank (1) and the hydrolysis reactor (2); a second liquid pump (14) is arranged on a pipeline between the hydrolysis reactor (2) and the solid-liquid separator (3); a third liquid pump (15) is arranged on a pipeline between the solid-liquid separator (3) and the first oxidation reactor (4); a liquid pump IV (16) is arranged on a pipeline between the first oxidation reactor (4) and the second oxidation reactor (5); a fifth liquid pump (17) is arranged on a pipeline between the second oxidation reactor (5) and the flocculation sedimentation tank (6); and a liquid pump six (18) is arranged on a pipeline between the flocculation sedimentation tank (6) and the plate-and-frame filter press (7).
8. The method for treating the anion resin chlorination mother liquor is characterized by comprising the following steps of:
step one, hydrolysis: pumping waste liquid generated in the process of producing the anion resin in the waste liquid storage tank (1) into a hydrolysis reactor (2), and adding recycled water through a first dosing device (8) to perform hydrolysis reaction, so that chloromethyl ether is hydrolyzed and a flocculent precipitate mixture is formed due to the cross-linking polymerization of styrene and divinylbenzene;
step two, solid-liquid separation: carrying out solid-liquid separation on the mixture treated by the hydrolysis reaction in the step I by using a solid-liquid separator (3), conveying a solid phase to an incineration system through a slag outlet, and carrying out next treatment on a liquid phase;
step three, oxidation reaction: pumping the mixed liquid subjected to solid-liquid separation treatment in the step two into an oxidation reactor I (4), adding potassium permanganate into the mixed liquid through a medicine adding device II (9) for oxidation, after reacting for 4-5h, adding lime water into the medicine adding device II (9) to adjust the pH value of the mixed liquid in the oxidation reactor I (4) to 3.0-4.0, pumping the mixed liquid subjected to adjustment treatment in the oxidation reactor I (4) into the oxidation reactor II (5), and adding ferrous sulfate and hydrogen peroxide into the mixed liquid through a medicine adding device III (10) to continue oxidation reaction for 3-4h;
step four, neutralization: pumping the mixed solution subjected to the triple oxidation treatment into a flocculation sedimentation tank (6), adding sodium hydroxide through a fourth dosing device (11) to adjust the pH of the mixed solution to 9.0-10.0, adding PAC through the fourth dosing device (11), and further performing flocculation sedimentation;
step five, filter pressing: pumping the mixed liquor treated in the fourth step into a plate-and-frame filter press (7), further treating the sewage filtrate in a sewage treatment device (20), recycling the filter residue as heavy metal zinc, and further treating other sludge filter residue in a curing and landfill treatment device (19);
wherein, in the first step, the third step and the fourth step, a cooling water circulation device (12) is adopted to control the reaction temperature not to exceed 5 ℃.
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