CN114516689A - Calcium carbide method polyvinyl chloride mercury-containing wastewater treatment and recycling method and application device thereof - Google Patents
Calcium carbide method polyvinyl chloride mercury-containing wastewater treatment and recycling method and application device thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 76
- 238000004064 recycling Methods 0.000 title claims abstract description 30
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 19
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 19
- 239000005997 Calcium carbide Substances 0.000 title claims abstract description 18
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004065 wastewater treatment Methods 0.000 title description 6
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 title 1
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 113
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
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- 239000002351 wastewater Substances 0.000 claims abstract description 56
- 238000001179 sorption measurement Methods 0.000 claims abstract description 42
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- 239000012267 brine Substances 0.000 claims abstract description 15
- 238000007670 refining Methods 0.000 claims abstract description 15
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 15
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 15
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 15
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- 238000006386 neutralization reaction Methods 0.000 claims description 14
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- 238000001914 filtration Methods 0.000 claims description 8
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000008394 flocculating agent Substances 0.000 claims description 6
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 claims description 6
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- 239000006004 Quartz sand Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
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- 241000196324 Embryophyta Species 0.000 claims description 3
- 229920001429 chelating resin Polymers 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
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- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
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- 239000002023 wood Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
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- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
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- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- SDZKFLOLROQIAK-UHFFFAOYSA-N [S-2].[Na+].[Hg+] Chemical compound [S-2].[Na+].[Hg+] SDZKFLOLROQIAK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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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
-
- 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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/52—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
-
- 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
- C02F1/5281—Installations for water purification using chemical agents
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The application discloses a method for treating and recycling mercury-containing wastewater of polyvinyl chloride by a calcium carbide method and an application device thereof, the method comprises the steps of coagulating the mercury-containing wastewater, efficiently precipitating in two stages, oxidizing ozone, coupling activated carbon adsorption processes, and efficiently removing and degrading TOC in high-salt wastewater in a gradable manner, wherein sulfate radicals, carbonate radicals and calcium ions are gradually removed through an original matched process of a brine refining treatment unit of a recycling production unit, the mercury-containing produced water can be safely recycled to an electrolytic cell, zero discharge and resource recycling of the mercury-containing wastewater are realized, and compared with electrodialysis, evaporation concentration, nanofiltration, ultrafiltration, MVR/multiple-effect evaporation and the like, the method is simple in process, low in operation cost and high in engineering degree, and the purposes of energy conservation, emission reduction, resource utilization and environment protection are effectively realized.
Description
Technical Field
The application relates to the technical field of wastewater treatment, in particular to a method for treating and recycling mercury-containing wastewater of polyvinyl chloride by using a calcium carbide method and an application device thereof.
Background
The chlor-alkali industry occupies an important position in the field of chemical production in China, and the product relates to aspects of national economy and daily life of people. At present, more than 90% of domestic polyvinyl chloride production enterprises mainly adopt a calcium carbide method. High-salt mercury-containing wastewater can be generated in the production process. After the standard of discharge standards of industrial water pollutants of caustic soda and polyvinyl chloride is put forward, the mercury content in water after mercury-containing wastewater treatment is regulated to be increased to 0.003mg/L from 0.005mg/L initially, and some domestic enterprises have strict requirements on effluent mercury indexes and require that the effluent mercury concentration is less than 0.001 mg/L.
The mercury-containing wastewater has high salinity, the content is 8% -10%, and the wastewater mainly comprises NaCl, TOC: 70-120 mg/L, a small amount of carbonate, sulfate radicals, iron ions, calcium ions, aluminum ions and a small amount of organic matters. At present, the mercury-containing wastewater treatment technology mainly comprises a sulfide precipitation method, a zinc reduction method, an activated carbon adsorption method, an ion exchange mercury removal method, an electrolysis method and a microorganism treatment method. The direct sulfide precipitation method has poor operability, is easy to cause the insufficient or excessive addition of sulfides, and when the sulfide is excessive, sulfide ions and mercury sulfide generate a complex to be dissolved again, and the mercury concentration of effluent is generally higher than 0.005 mg/L. A zinc reduction method: zinc is a very active metal, the consumption is high, the mercury elementary substance is difficult to collect and treat after reduction, and multi-stage combination is needed. Meanwhile, zinc ions are introduced into the water, so that later recycling is not facilitated. The activated carbon adsorption process is limited by adsorption capacity and does not provide high removal rates for soluble mercury in water. Resin adsorption is not suitable for removing high-concentration mercury in wastewater. The microbiological method is not suitable for treating mercury-containing wastewater in a high-salt environment, and the treatment effect cannot meet the industrial requirements.
For the recycling of mercury-containing wastewater after treatment, the domestic chemical industry unit mostly recycles the mercury-containing wastewater to an acetylene generator or a conversion section foam absorption tower, but the recycling has many problems. Because the concentration of chloride ions in water is high, the chloride ions are recycled to the acetylene generator, the concentration of the chloride ions in the acetylene sludge slurry exceeds the standard, and the technical indexes of the subsequent cement production by carbide slag exceed the standard. When the salt is reused in the foam tower, the salt in water can be separated out and crystallized, the foam tower is blocked, and the chemical production is influenced. The methods reported in the literature for recycling are high-energy-consumption processes such as reverse osmosis, electrodialysis, evaporative crystallization and the like. As the water content of the mercury-containing wastewater in industrial production is small and is only 3-6 m3/h, the concentration of chloride ions is as high as 60000-80000 mg/, the investment per ton of water is huge, the energy consumption is high, the operation requirement is strict, and the processes or the methods only stay in the test stage, only have academic value and cannot realize industrial application. Therefore, the recycling method and the process which are economic, do not influence chemical production, are convenient to operate and can be engineered for the mercury concentration of the mercury-containing wastewater after treatment is less than 0.001mg/L are found at present, and the method and the process have important significance for the sustainable development of enterprises.
In view of the characteristics of the mercury-containing wastewater, the recycling of the treated wastewater to the electrolytic cell for salt dissolution is an economic and environment-friendly treatment scheme, on one hand, the salinity resource in water is fully utilized, and the problem of high-salt water treatment is solved. However, organic pollutants in water can cause the cell voltage to rise, the power consumption to rise and the service life of the ionic membrane to be reduced.
Disclosure of Invention
The application mainly aims to provide a method for treating and recycling mercury-containing wastewater of polyvinyl chloride by using a calcium carbide method and an application device thereof, so as to solve the current problem.
In order to achieve the above object, the present application provides the following techniques:
the invention provides a method for treating and recycling mercury-containing wastewater of polyvinyl chloride by using a calcium carbide method, which comprises the following steps:
s1, pretreating the mercury-containing wastewater to remove impurities and precipitates in the water to obtain a first mixed solution;
s2, carrying out acid-base neutralization adjustment on the first mixed solution, and adjusting the pH value to 7.5-9.5 to obtain a second mixed solution;
s3, adding a mercury removing agent and sodium sulfide into the second mixed solution, performing precipitation after reaction, and removing mercury ion precipitates to obtain a third mixed solution;
s4, adding an inorganic flocculant and/or a coagulant aid into the third mixed solution, coagulating and then precipitating to obtain a fourth mixed solution;
S5, lifting the fourth mixed solution into a filter, and performing ozone oxidation on the produced water through the filter to remove TOC to obtain a fifth mixed solution;
and S6, sequentially carrying out activated carbon adsorption and two-stage deep adsorption on the fifth mixed solution, removing partial TOC and dissolved mercury in the water, keeping the concentration of the mercury in the effluent to be less than 0.001mg/L, and lifting the produced water to a brine refining plant for salt dissolving.
As an alternative embodiment of the present application, optionally, the weight ratio of sodium sulfide to mercury removing agent is 1: 1 to 1.5; and the weight ratio of the mercury-containing wastewater to the total amount of the added sodium sulfide and mercury removing agent is 20000-50000: 1.
as an optional embodiment of the application, the mercury removing agent is a compound formed by aluminum, iron and calcium ions and activated carbon according to the weight ratio of 1: 0.7-1.2: 0.3-0.5: 3.8-5.0.
As an alternative embodiment of the present application, optionally, the flocculant is an inorganic salt of aluminum or iron or a polymeric flocculant, the coagulant aid is polyacrylamide; and, the adding amount of the flocculating agent is as follows: 200-500 mg/L, and the adding concentration of the coagulant aid is 1-2 mg/L.
As an optional embodiment of the application, optionally, the ozone oxidation time is 1-3 h, the ozone adding concentration is 100-300 mg/L, and the TOC concentration in effluent is less than 20 mg/L.
The second aspect of the invention provides an application device for implementing the method for treating and recycling mercury-containing wastewater of calcium carbide process polyvinyl chloride, which comprises the following steps:
the pretreatment equipment is used for pretreating mercury-containing wastewater and comprises a grating and a primary sedimentation tank, wherein the mercury-containing wastewater sequentially passes through the grating and the primary sedimentation tank, impurities and precipitates in the water are removed to obtain a first mixed solution, and the first mixed solution is discharged into a neutralization tank;
the neutralization tank is used for carrying out acid-base neutralization adjustment on the first mixed solution, adjusting the pH value to 7.5-9.5 to obtain a second mixed solution, and discharging the second mixed solution into the reaction tank;
the reaction tank is internally provided with a mercury removing agent and sodium sulfide and is used for converting mercury ions into solid mercury after reacting with the second mixed solution and discharging a reaction compound into a first-stage efficient sedimentation tank;
the first-stage efficient sedimentation tank is used for performing first-stage sedimentation and removing mercury ion sediments to obtain a third mixed solution, and the third mixed solution is discharged into the coagulation tank;
a coagulation tank, wherein an inorganic flocculant and/or a coagulant aid are added into the coagulation tank and are used for coagulating with the third mixed solution to obtain a coagulated liquid and discharging the coagulated liquid into a secondary efficient sedimentation tank;
the second-stage efficient sedimentation tank is used for carrying out second-stage sedimentation, and precipitating the coagulation liquid to obtain a fourth mixed liquid, and the fourth mixed liquid enters the intermediate water tank and is lifted to the filter;
The filter is used for filtering the fourth mixed solution;
the ozone oxidation equipment is arranged in the filter and used for carrying out ozone oxidation on the filtered mixed solution, removing TOC to obtain a fifth mixed solution and discharging the fifth mixed solution into the activated carbon adsorption filter;
the activated carbon adsorption filter is used for further adsorbing and removing part of TOC and mercury in the water, and the mixed solution after adsorption and filtration is discharged into the grade deep adsorption filter;
the two-stage deep adsorption filter is used for deeply removing dissolved mercury in water to obtain clear water, keeping the mercury concentration of the clear water to be less than 0.001mg/L, and discharging outlet water meeting the mercury concentration condition into a brine refining unit;
and the brine refining unit is used for utilizing the effluent to carry out salt dissolving.
As an alternative embodiment of the present application, optionally, the filter is a quartz sand filter or a multi-media filter.
As an alternative embodiment of the present application, optionally, the filler in the activated carbon adsorption filter is one of shell activated carbon, coconut shell gold activated carbon or wood-like activated carbon; the filler in the two-stage depth adsorption filter is Tulsion CH 97/95 series filler of mercury-removing chelating resin.
As an optional embodiment of the present application, optionally, the diameter of the ozone bubbles is 5 to 50 μm.
Compared with the prior art, this application can bring following technological effect:
1. the characteristics of simple process, convenient operation and low operation cost of the sodium sulfide mercury removal are kept, meanwhile, the mercury removal agent is added, the effect of efficiently and stably removing mercury in water can be achieved, deep adsorption treatment is arranged subsequently, and the concentration of the effluent is guaranteed to be less than 0.001 mg/L.
2. The method combines the universality characteristics of brine refining processes of downstream recycling units in industrial production, and aims at reasonably combining the processes to remove key TOC pollutants, so that high-concentration salt in water is recycled, the environmental protection problem is solved, and certain economic benefit is generated. The method comprises the steps of coagulation, two-stage efficient precipitation, ozone oxidation and activated carbon adsorption process coupling in the mercury-containing wastewater, and can be used for grading, efficiently removing and degrading TOC in the high-salinity wastewater. Sulfate radicals, carbonate ions and calcium ions are gradually removed through an original matched process of a brine refining treatment unit of a recycling production unit, the mercury-containing produced water can be safely recycled to an electrolytic cell, zero emission and resource recycling of the mercury-containing wastewater are realized, and compared with electrodialysis, evaporation concentration, nanofiltration, ultrafiltration, MVR/multi-effect evaporation and the like, the process is simple, low in operation cost and high in engineering degree, and the purposes of energy conservation, emission reduction, resource utilization and environment protection are effectively realized.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the application and to enable other features, objects, and advantages of the application to be more apparent. The drawings and the description of the exemplary embodiments of the present application are provided for explaining the present application and do not constitute an undue limitation on the present application. In the drawings:
FIG. 1 is a schematic view of the process for treating and recycling mercury-containing wastewater of polyvinyl chloride produced by calcium carbide process according to the present invention;
FIG. 2 is a schematic diagram showing the composition of the apparatus for applying the present invention.
Detailed Description
In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, but not all 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 application.
It should be noted that the terms "first," "second," and the like in the description and claims of this application and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It should be understood that the data so used may be interchanged under appropriate circumstances such that embodiments of the application described herein may be used. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
In addition, the term "plurality" shall mean two as well as more than two.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
Example 1
As shown in fig. 1, a first aspect of the present invention provides a method for treating and recycling mercury-containing wastewater of polyvinyl chloride by a calcium carbide process, comprising the following steps:
s1, pretreating the mercury-containing wastewater to remove impurities and precipitates in the water to obtain a first mixed solution;
in this embodiment, the mercury-containing wastewater of the calcium carbide process polyvinyl chloride is selected for wastewater treatment and recycling. Firstly, pretreating mercury-containing wastewater, and removing impurities and precipitates in the wastewater through a grating and a primary sedimentation tank in sequence; the raw water is pretreated by a grating and precipitation, aiming at removing impurities and precipitates in the water.
S2, carrying out acid-base neutralization adjustment on the first mixed solution, and adjusting the pH value to 7.5-9.5 to obtain a second mixed solution;
acid-base neutralization regulation is carried out, so that alkaline conditions Na are conveniently ensured2The removal effect of S and mercury can reduce the dosage of flocculating agent and coagulant aid in the coagulating sedimentation tank, and the coagulation effect can be ensured.
S3, adding a mercury removing agent and sodium sulfide into the second mixed solution, performing precipitation after reaction, and removing mercury ion precipitates to obtain a third mixed solution;
And adding a mercury removing agent and sodium sulfide to convert mercury ions in the mixed solution into solid mercury precipitates, so that the precipitates are convenient to precipitate, and continuously removing impurities.
The mercury removing agent can effectively prevent HgS and excessive S2-And touch, the generation of soluble HgS complex is avoided, and the concentration of the mercury in the effluent is ensured to be less than 0.005 mg/L. When the engineering operation control level is higher, the mercury concentration can be less than 0.003mg/L
S4, adding an inorganic flocculant and/or a coagulant aid into the third mixed solution, coagulating and then precipitating to obtain a fourth mixed solution;
and (3) adding an inorganic flocculant and/or a coagulant aid alternatively for coagulating sedimentation, further removing impurities and the like in the mixed solution. When the method is implemented, the inorganic flocculant and/or the coagulant aid can be firstly put into a coagulation tank, the mixed liquid of the previous procedure can be stirred and coagulated after entering the coagulation tank, and then the mixed liquid is discharged into a sedimentation tank to be sedimentated and filtered by a steering engine, so that clear liquid is obtained.
After the addition of the flocculant and/or coagulant aid, the majority of the colloids in the water and also part of the TOC by the action of the net-trap can be removed and the turbidity reduced.
S5, lifting the fourth mixed solution into a filter, and performing ozone oxidation on the produced water through the filter to remove TOC to obtain a fifth mixed solution;
The clear liquid firstly enters an intermediate water tank, and enters a filter through lifting for primary filtration. Then, oxidation treatment is carried out, in the embodiment, ozone is generated by generating water in the filter, and ozone oxidation is carried out to remove TOC.
And S6, sequentially carrying out activated carbon adsorption and two-stage deep adsorption on the fifth mixed solution, removing part of TOC and dissolved mercury in the water, keeping the concentration of the mercury in the effluent to be less than 0.001mg/L, and lifting the produced water to a brine refining factory for use as salt dissolving.
And purifying and filtering the clear liquid after ozone oxidation treatment again, firstly further adsorbing and removing part of TOC and mercury in the water by adopting activated carbon adsorption, finally deeply removing dissolved mercury in the water by two-stage deep adsorption, and finally keeping the concentration of the mercury in the outlet water to be less than 0.001mg/L so as to meet the requirement of industrial salt production.
As a preferable embodiment of this embodiment, it is preferable that the diameter of ozone bubbles used is 5 to 50 μm.
Deeply adsorbing produced water to primary salt hydrate salt in a plant area, and quickly hydrolyzing trace aluminum ions and iron ions in raw water in a two-stage high-efficiency sedimentation tank to form sediment which can be quickly removed. Two-stage efficient precipitation adopts activated carbon adsorption and deep adsorption, can make mixed solution deposit by the absorption get rid of, and is pure gradually, improves purification efficiency, will specifically follow in the follow-up detail.
After adsorption, a small amount of calcium ions, sulfate ions and carbonate ions enter a salt dissolving pool, and on one hand, the calcium ions, the sulfate ions and the carbonate ions are mixed with other process salt water, and the concentration is reduced after dilution. Simultaneously, the saline water refinement units are all matched with hardness removal (adding NaOH + Na)2CO3) And removing sulfate radical (adding BaCl)2) And the carbonate removal (HCl addition) equipment, a small amount of inorganic impurities in produced water can be removed in the brine refining unit, equipment does not need to be added in the mercury-containing wastewater treatment unit, the process is simple, and the cost is reduced. After the TOC in the raw water is coagulated, oxidized by ozone and adsorbed by activated carbon, the TOC is reduced to be below 20mg/L, and the TOC concentration requirement of the inlet water of the ionic membrane is met. And (4) introducing the effluent into a brine refining unit of a salt manufacturing factory, and using the effluent as salt to obtain waste water for utilization.
As an alternative embodiment of the present application, optionally, the weight ratio of sodium sulfide to mercury removing agent is 1: 1 to 1.5; and the weight ratio of the mercury-containing wastewater to the total amount of the added sodium sulfide and mercury removing agent is 20000-50000: 1.
as an optional embodiment of the application, the mercury removing agent is a compound formed by aluminum, iron and calcium ions and activated carbon according to the weight ratio of 1: 0.7-1.2: 0.3-0.5: 3.8-5.0.
As an alternative embodiment of the present application, optionally, the flocculant is an inorganic salt of aluminum or iron or a polymeric flocculant, the coagulant aid is polyacrylamide (anionic); and, the adding amount of the flocculating agent is as follows: 200-500 mg/L, and the adding concentration of the coagulant aid is 1-2 mg/L.
As an optional embodiment of the present application, optionally, the ozone oxidation time is 1 h-3 h, the ozone adding concentration is 100-300 mg/L, and the TOC concentration in effluent is less than 20 mg/L.
In a preferred embodiment, one of the specific embodiments is:
collect the mercury-containing waste water after foam absorption tower acid water, alkaline washing tower drainage, towards catalyst waste water mixture, will contain mercury waste water and get into grille, preliminary sedimentation tank in proper order, get rid of aquatic debris and precipitate, get into neutralization pond and adjust waste water PH to 8.5, then get into the reaction tank, sodium sulfide and demercuration agent weight ratio 1 in the pond: 1.2, the weight ratio of the mercury-containing wastewater to the total amount of the added sodium sulfide and the mercury removing agent is 30000: 1, enabling effluent of a reaction tank to enter a primary efficient sedimentation tank, adopting an inclined tube for sedimentation in the efficient sedimentation tank, enabling supernatant of the primary efficient sedimentation tank to flow into a coagulation tank, and adding polyaluminium chloride and polyacrylamide (negative), wherein the adding concentrations are 260mg/L and 1.5mg/L respectively; thoughtlessly congeal pond exit linkage second grade high-efficient sedimentation tank, it produces the floc and obtains subsiding fast to congeal, second grade high-efficient sedimentation tank form is the pipe chute sediment, the supernatant gets into the filter, the filter form is quartz sand filter, the filter produces water and carries out ozone oxidation, ozone addition concentration 250mg/L, ozone oxidation produces water and connects active carbon adsorption filter in order, two-stage degree of depth adsorbs, finally produce water and recycle in salt solution essence to the unit, wherein adsorption resin chooses for use Tulsion CH 97, each unit is handled the back pollutant index and is seen in table 1:
Watch (A)
TABLE 1 pollutant index after treatment of each unit
By adopting the process, the TOC in the high-salinity wastewater can be removed and degraded in a grading and high-efficiency manner through the coupling of the processes of coagulation, two-stage high-efficiency precipitation, ozone oxidation and activated carbon adsorption in the mercury-containing wastewater. Sulfate radicals, carbonate ions and calcium ions are gradually removed through an original matched process of a brine refining treatment unit of a recycling production unit, the mercury-containing produced water can be safely recycled to an electrolytic cell, zero emission and resource recycling of the mercury-containing wastewater are realized, and compared with electrodialysis, evaporation concentration, nanofiltration, ultrafiltration, MVR/multi-effect evaporation and the like, the process is simple, low in operation cost and high in engineering degree, and the purposes of energy conservation, emission reduction, resource utilization and environment protection are effectively realized.
Example 2
The second aspect of the invention provides an application device for implementing the method for treating and recycling the mercury-containing wastewater of polyvinyl chloride by using the calcium carbide process, which comprises the following steps:
the pretreatment equipment is used for pretreating mercury-containing wastewater and comprises a grating and a primary sedimentation tank, wherein the mercury-containing wastewater sequentially passes through the grating and the primary sedimentation tank, impurities and precipitates in the water are removed to obtain a first mixed solution, and the first mixed solution is discharged into a neutralization tank;
the neutralization tank is used for carrying out acid-base neutralization adjustment on the first mixed solution, adjusting the pH value to 7.5-9.5 to obtain a second mixed solution, and discharging the second mixed solution into the reaction tank;
A reaction tank, in which a mercury removing agent and sodium sulfide are added for reacting with the second mixed solution to convert mercury ions into solid mercury and discharging a reaction compound into a first-stage efficient sedimentation tank;
the first-stage efficient sedimentation tank is used for performing first-stage sedimentation and removing mercury ion sediments to obtain a third mixed solution, and the third mixed solution is discharged into the coagulation tank;
a coagulation tank, wherein an inorganic flocculant and/or a coagulant aid are added into the coagulation tank and are used for coagulating with the third mixed solution to obtain a coagulated liquid and discharging the coagulated liquid into a secondary efficient sedimentation tank;
the second-stage efficient sedimentation tank is used for carrying out second-stage sedimentation, and precipitating the coagulation liquid to obtain a fourth mixed liquid, and the fourth mixed liquid enters the intermediate water tank and is lifted to the filter;
the filter is used for filtering the fourth mixed solution;
the ozone oxidation equipment is arranged in the filter and used for carrying out ozone oxidation on the filtered mixed solution, removing TOC to obtain a fifth mixed solution and discharging the fifth mixed solution into the activated carbon adsorption filter;
the activated carbon adsorption filter is used for further adsorbing and removing part of TOC and mercury in the water, and the mixed solution after adsorption and filtration is discharged into the grade deep adsorption filter;
the two-stage deep adsorption filter is used for deeply removing dissolved mercury in water to obtain clear water, keeping the mercury concentration of the clear water to be less than 0.001mg/L, and discharging outlet water meeting the mercury concentration condition into a brine refining unit;
And the brine refining unit is used for utilizing the effluent to carry out salt dissolving.
Among the above-mentioned sedimentation tank, the high-efficient sedimentation tank of one-level and second grade can adopt swash plate, down tube sedimentation tank, and the normal steady operation of protection pump, grid specification select to be thin grid, and clearance 1.5 ~ 10mm, the primary sedimentation tank can be selected to be one kind of vertical flow formula, down tube, swash plate formula. And the supernatant of the first-stage high-efficiency sedimentation tank enters a coagulation tank.
As shown in fig. 2, the connection mode between the above facilities is not limited to the use of auxiliary facilities such as pump pipes or general water pipes, and the specific technical solutions of the above facilities such as the intake, discharge, and lifting are not limited in this embodiment.
As an alternative embodiment of the present application, optionally, the filter is a quartz sand filter or a multi-media filter.
As an alternative embodiment of the present application, optionally, the filler in the activated carbon adsorption filter is one of shell activated carbon, coconut shell gold activated carbon or wood-like activated carbon; the filler in the two-stage depth adsorption filter is Tulsion CH 97/95 series filler of mercury-removing chelating resin.
As an alternative embodiment of the present application, optionally, the ozone oxidation device is a micro-porous aeration disc. The microporous aeration disc is a titanium material, corundum or SS316L stainless steel shell, and the diameter of ozone bubbles is 5-50 μm.
Example 3
On the basis of embodiment 2, this embodiment prefers micro-nano ozone bubble generator as ozone oxidation equipment.
As an optional implementation scheme of the application, optionally, the ozone oxidation device is a micro-nano ozone bubble generator, and the diameter of ozone bubbles is 5-50 μm.
The micro-nano ozone bubble generator has the advantages that the diameter of ozone bubbles is 5-50 mu m, the contact area of the ozone bubbles and a water body can be increased, the retention time of ozone in water is prolonged, and the oxidation effect is further guaranteed.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (9)
1. A method for treating and recycling mercury-containing wastewater of polyvinyl chloride by a calcium carbide method is characterized by comprising the following steps:
s1, pretreating the mercury-containing wastewater to remove impurities and precipitates in the water to obtain a first mixed solution;
s2, carrying out acid-base neutralization adjustment on the first mixed solution, and adjusting the pH value to 7.5-9.5 to obtain a second mixed solution;
S3, adding a mercury removing agent and sodium sulfide into the second mixed solution, carrying out precipitation after reaction, and removing mercury ion precipitates to obtain a third mixed solution;
s4, adding an inorganic flocculant and/or a coagulant aid into the third mixed solution, coagulating and then precipitating to obtain a fourth mixed solution;
s5, lifting the fourth mixed solution into a filter, and performing ozone oxidation on the produced water through the filter to remove TOC to obtain a fifth mixed solution;
and S6, sequentially carrying out activated carbon adsorption and two-stage deep adsorption on the fifth mixed solution, removing partial TOC and dissolved mercury in the water, keeping the concentration of the mercury in the effluent to be less than 0.001mg/L, and lifting the produced water to a brine refining plant for salt dissolving.
2. The method for treating and recycling mercury-containing wastewater of calcium carbide process polyvinyl chloride as claimed in claim 1, wherein the weight ratio of sodium sulfide to mercury removing agent is 1: 1 to 1.5; and the weight ratio of the mercury-containing wastewater to the total amount of the added sodium sulfide and mercury removing agent is 20000-50000: 1.
3. the method for treating and recycling mercury-containing wastewater of polyvinyl chloride by using calcium carbide process as claimed in claim 1, wherein the mercury removing agent is a compound formed by aluminum, iron, calcium ions and activated carbon according to the weight ratio of 1: 0.7-1.2: 0.3-0.5: 3.8-5.0.
4. The method for treating and recycling mercury-containing wastewater of polyvinyl chloride by using calcium carbide process according to claim 1, wherein the flocculating agent is an inorganic salt of aluminum or iron or a polymer flocculating agent, and the coagulant aid is polyacrylamide; and the addition amount of the flocculating agent is as follows: 200-500 mg/L, and the adding concentration of the coagulant aid is 1-2 mg/L.
5. The method for treating and recycling mercury-containing wastewater of polyvinyl chloride by using calcium carbide process as claimed in claim 1, wherein the ozone oxidation time is 1-3 h, the ozone adding concentration is 100-300 mg/L, and the TOC concentration in effluent is less than 20 mg/L.
6. An application device for implementing the method for treating and recycling mercury-containing wastewater of calcium carbide process polyvinyl chloride according to any one of claims 1 to 5, which is characterized by comprising the following steps:
the pretreatment equipment is used for pretreating mercury-containing wastewater and comprises a grating and a primary sedimentation tank, wherein the mercury-containing wastewater sequentially passes through the grating and the primary sedimentation tank, impurities and precipitates in the water are removed to obtain a first mixed solution, and the first mixed solution is discharged into a neutralization tank;
the neutralization tank is used for carrying out acid-base neutralization adjustment on the first mixed solution, adjusting the pH value to 7.5-9.5 to obtain a second mixed solution, and discharging the second mixed solution into the reaction tank;
the reaction tank is internally provided with a mercury removing agent and sodium sulfide and is used for converting mercury ions into solid mercury after reacting with the second mixed solution and discharging a reaction compound into a first-stage efficient sedimentation tank;
The first-stage efficient sedimentation tank is used for performing first-stage sedimentation and removing mercury ion sediments to obtain a third mixed solution, and the third mixed solution is discharged into the coagulation tank;
the coagulation tank is internally provided with an inorganic flocculant and/or a coagulant aid and is used for coagulating with the third mixed solution to obtain a coagulation liquid and discharging the coagulation liquid into the second-stage efficient sedimentation tank;
the second-stage efficient sedimentation tank is used for carrying out second-stage sedimentation, and precipitating the coagulation liquid to obtain a fourth mixed liquid, and the fourth mixed liquid enters the intermediate water tank and is lifted to the filter;
the filter is used for filtering the fourth mixed solution;
the ozone oxidation equipment is arranged in the filter and used for carrying out ozone oxidation on the filtered mixed solution, removing TOC to obtain a fifth mixed solution and discharging the fifth mixed solution into the activated carbon adsorption filter;
the activated carbon adsorption filter is used for further adsorbing and removing part of TOC and mercury in the water, and the mixed solution after adsorption and filtration is discharged into the grade deep adsorption filter;
the two-stage deep adsorption filter is used for deeply removing dissolved mercury in water to obtain clear water, keeping the mercury concentration of the clear water to be less than 0.001mg/L, and discharging outlet water meeting the mercury concentration condition into a brine refining unit;
and the brine refining unit is used for utilizing the effluent to carry out salt dissolving.
7. The use of a device according to claim 6, wherein the filter is a quartz sand filter or a multi-media filter.
8. The use device as claimed in claim 6, wherein the filler in the activated carbon adsorption filter is one of shell activated carbon, coconut gold activated carbon or wood activated carbon; the filler in the two-stage depth adsorption filter is Tulsion CH 97/95 series filler of mercury-removing chelating resin.
9. The use device according to claim 6, wherein the ozone bubbles have a diameter of 5 to 50 μm.
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