CN115180736A - Coking wastewater decyanation agent and coking wastewater treatment method - Google Patents
Coking wastewater decyanation agent and coking wastewater treatment method Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 83
- 238000004939 coking Methods 0.000 title claims abstract description 65
- 238000007255 decyanation reaction Methods 0.000 title claims abstract description 27
- 238000004065 wastewater treatment Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000003463 adsorbent Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
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- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 6
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 6
- 239000011630 iodine Substances 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 239000010802 sludge Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 239000000701 coagulant Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical group O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- 230000003311 flocculating effect Effects 0.000 claims description 2
- 239000006194 liquid suspension Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 46
- 208000028659 discharge Diseases 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal cyanide Chemical class 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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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
- C02F1/28—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
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- 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
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a coking wastewater decyanation agent, which is prepared by compounding an adsorbent, a metal complexing agent and a cationic polymer auxiliary agent; comprises the following components in percentage by weight: 30% -75% of composite adsorbent; 10 to 50 percent of inorganic copper salt and 2 to 15 percent of cationic polymer additive; the composite adsorbent is prepared by mixing and compounding active carbon and diatomite, wherein the active carbon comprises the following components in percentage by weight: the diatomite specific weight ratio is 1-2; wherein the iodine value of the activated carbon is as follows: >700mg/g, methylene blue value: >105mg/g; the pH value of the diatomite is 6-9; the cationic polymer additive is cationic polyacrylamide or ammonium chloride-based cationic polymer. Also discloses a method for treating wastewater by using the cyanogen-removing medicament. The invention is a medicament treatment process which is practical and simple and does not increase processing equipment obviously.
Description
Technical Field
The invention relates to the field of coking wastewater treatment, in particular to a decyanation treatment method and a decyanation treatment process for cyanide-containing wastewater.
Background
The cyanide in the coking wastewater is generated by a series of chemical reactions in the production process of coke, N element can form various pollutants with C, H, O and S in the coking process, wherein N and C are combined to form CN-, CN-coordination capacity is strong, the cyanide can form a complex with metal ions, can form nitrile with organic matters, and can form hydrocyanic acid with H +. During the treatment process of the coking wastewater, the existence forms of cyanide are different. Hydrogen cyanide, alkali metal cyanide and metal cyanide complex with weak complexing ability are easy to remove, residual cyanide in coking wastewater after biochemical treatment mainly takes ferricyanide with high stability as a main component, and common oxidants have poor treatment effect on the cyanide. With the promulgation of emission standards for pollutants from the coking chemical industry (GB 16171-2012), the emission standards for total cyanide have increased further, which requires advanced treatment of ferricyanide in the biochemical effluent. Through investigation on related enterprises, the conventional cyanogen removal process (such as coagulating sedimentation) is difficult to achieve stable standard. With the improvement of the environmental protection requirement, once raw water cyanide fluctuates after the wastewater reuse and zero discharge device operates, the indexes of concentrated water cyanide are easily influenced, the existing physicochemical process has limited cyanide reduction capability, the discharged water cyanide is close to exceeding the standard, and the environmental protection pressure is large.
No matter the physical and chemical treatment of the coking wastewater treatment process, the wastewater recycling or the membrane concentrated water or the slag flushing water in the zero discharge stage, the cyanogen-containing component in the sewage is not only difficult to degrade, but also volatile, has strong toxicity, seriously harms the health of human beings and pollutes the environment.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a coking wastewater cyanide high-efficiency treatment agent and a method for removing wastewater cyanide in each process stage of the coking industry by using the high-efficiency cyanide removal agent, and the requirements of wastewater direct discharge standard or membrane system concentrated water cyanide treatment are met.
The technical scheme of the invention is that a cyanide removing agent for coking wastewater,
the cyanogen removing medicament is prepared by compounding an adsorbent, a metal complexing agent and a cationic polymer auxiliary agent;
the cyanogen removing medicament comprises the following components in percentage by weight: 30% -75% of composite adsorbent; 10 to 50 percent of inorganic copper salt and 2 to 15 percent of cationic polymer additive; inorganic copper salt is a metal complexing agent.
The composite adsorbent is prepared by mixing and compounding active carbon and diatomite, wherein the active carbon comprises the following components in parts by weight: the diatomite specific weight ratio is 1-2:1; wherein the iodine value of the activated carbon is as follows: >700mg/g, methylene blue value: >105mg/g; the pH value of the diatomite is 6-9;
the cationic polymer additive is cationic polyacrylamide or ammonium chloride-based cationic polymer. The cationic polymer additive is a cationic polymer, and the ammonium chloride-based cationic polymer is one of the concentrated cationic polymers.
The adsorbent is used for adsorbing cyanide and partial organic matters by utilizing the special specific surface area and hydrophilic property of the active carbon or the diatomite; the metal complexing agent is used for utilizing metal cation and CN in solution - The method has extremely strong complexing ability to form stable complex precipitate to remove cyanide; the cationic polymer assistant is one kind of ionic reinforcer for flocculation, decolorizing and purification.
The metal complexing agent and cyanide ions form stable complex precipitates, and the removal of the cyanide is further enhanced by matching the adsorption effect of the adsorbent and the flocculation and purification effects of the high-molecular auxiliary agent.
According to the coking wastewater decyanation agent, the inorganic copper salt is preferably copper sulfate pentahydrate.
According to the coking wastewater decyanation agent, the granularity of the activated carbon is preferably as follows: the 200-mesh screen dropping rate is more than 60%; the fineness of the diatomite is within the range of 300 meshes to 1200 meshes. The indexes of the adsorbent mainly consider the size of adsorption, small granularity, large specific surface area and strong adsorption. In this particle size range, the efficiency of use of the powder is considered to be high.
The invention also provides a method for treating the coking wastewater by using the coking wastewater decyanation agent, wherein the treatment equipment comprises a pH adjusting tank, a primary decyanation tank, a primary sedimentation tank, a secondary decyanation tank, a secondary sedimentation tank and a water outlet tank, and the method comprises the following steps:
(1) Fully mixing the adsorbent, inorganic copper salt and cationic polymer additive according to a proportion, fully mixing and uniformly stirring to prepare compound powder or liquid suspension;
(2) The coking wastewater containing cyanogen to be treated enters a pH adjusting tank, alkali is added to adjust the pH, the mixture is uniformly stirred to maintain the pH at 5.0-7.0, and then the mixture enters a first-stage cyanogen removing tank;
(3) Adding a ferrous sulfate solution into the primary decyanation tank, fully stirring and reacting, then feeding the mixture into a primary sedimentation tank, feeding the supernatant into a subsequent secondary decyanation tank, and discharging sludge at the bottom into a sludge tank;
(4) Adding the cyanogen removal agent obtained in the step (1) and a coagulant polyacrylamide into a secondary cyanogen removal tank, slowly stirring and uniformly mixing, and feeding into a secondary sedimentation tank; the dosage of the cyanogen removing medicament is 150-1000mg/L (wastewater);
(5) Flocculating and precipitating in a sedimentation tank to form solid, carrying out solid-liquid separation, and feeding the treated wastewater into a water outlet tank.
The mixing and stirring temperature of the step (1) is 15-40 ℃.
According to the method for treating the coking wastewater by the decyanation agent for the coking wastewater, the coking wastewater preferably comprises wastewater of each process stage in the coking industry. Is mainly suitable for the cyanide-containing wastewater with medium and low concentration. High concentration wastewater requires pretreatment.
According to the method for treating the coking wastewater by the cyanogen removing agent for the coking wastewater, the stirring time in the step (1) is preferably 5-20 minutes; the stirring time in the step (2) is 5-20 minutes.
According to the method for treating the coking wastewater by using the coking wastewater decyanation agent, the alkali in the step (2) is preferably sodium hydroxide or a sodium hydroxide solution. More preferably, the sodium hydroxide solution has a mass concentration of 20 to 40%.
According to the method for treating the coking wastewater by using the coking wastewater decyanation agent, the stirring time in the step (3) is preferably 10-30 minutes.
According to the method for treating the coking wastewater by using the coking wastewater decyanation agent, the dosage of the ferrous sulfate in the step (3) is preferably 50-600mg/L. The ferrous sulfate is mainly used for initially reducing the concentration of cyanide in water to below 5 mg/L.
According to the method for treating the coking wastewater by using the coking wastewater decyanation agent, the polyacrylamide mass concentration in the step (4) is preferably 0.5-2%, and the addition amount is 1-3 per mill. The adding amount is 1-3 per mill calculated according to the ratio of the mass of the polyacrylamide solute to the waste water.
The invention has the beneficial effects that:
compared with the prior art, the coking wastewater cyanide high-efficiency treatment agent, the high-efficiency cyanide removal agent and the cyanide removal process provided by the invention are used for removing the cyanide in wastewater in each process stage in the coking industry, and are suitable for removing low-concentration cyanide in wastewater. Aiming at the requirements of removing cyanide in the effluent of biochemical treatment of common coking wastewater, membrane system concentrated water and cyanide-containing slag flushing water, the agent treatment process is practical and simple and does not increase processing equipment remarkably. Taking biochemical effluent of coking wastewater as an example, the total cyanogen in the wastewater before treatment is less than 10mg/L, the volatile cyanogen in the wastewater is less than 2mg/L, and the effluent cyanide is less than 0.2mg/L after the high-efficiency cyanogen removing agent is added.
Drawings
FIG. 1 is a flow chart of a cyanide-containing wastewater removal process.
Detailed Description
Example 1:
in the first-stage and second-stage treatment engineering of coking wastewater of a certain company, treated water is from solvent dephenolization, wastewater after ammonia water distillation, coal refining process drainage, chemical product process drainage, COG condensed water and various accident drainage, and mainly comprises three parts of biological anoxic and aerobic treatment, coagulation filtration treatment, sludge dehydration treatment and the like. Design processing scale of 5800m 3 And d, treating and directly discharging.
The COD content of biochemical effluent is 150-500mg/L, and the cyanide content is 1-2mg/L. The chroma is within the range of 128-256 times, the fluoride is within the range of 30-60mg/L, and the wastewater discharge requirement reaches the discharge limit value of the pollutant discharge standard of the coking chemical industry (GB 16171-2012) and the discharge limit value of the pollutant discharge concentration of the water of the new enterprises is shown in the table 2.
In the physicochemical treatment stage of biochemical effluent, 3 physicochemical reaction tanks, a sedimentation tank and a water outlet tank are originally designed to mainly remove refractory organic matters, cyanides, fluorides and chroma. Because the cyanide content in water is not high, ferrous sulfate is not needed, sodium hydroxide is added into the first reaction tank after adjustment to adjust the PH value to be neutral, a high-efficiency cyanide removing medicament of 350mg/L is added, the mixture is stirred and reacted for 20min, and then the mixture enters a second chemical reaction tank; adding 3500mg/L calcium chloride solution and 2500mg/L aluminum sulfate solution into a second reaction tank, and removing fluoride ions and organic matters in a matching manner; adding 3 thousandths of polyacrylamide into a coagulation reaction tank after reaction, slowly stirring and uniformly mixing, and feeding into a sedimentation tank; then forming solid by flocculation and precipitation in a sedimentation tank, separating solid from liquid, and feeding the treated wastewater into a drainage tank. In the embodiment, according to the water quality condition and the cyanogen removal requirement, the efficient cyanogen removal agent is adopted, and the composition ratio of the medium composite adsorbent is 70 percent; 20 percent of inorganic copper salt, 10 percent of cationic polymer additive and water are prepared into 10 percent mixed solution. In the composite adsorbent, the specific gravity of the activated carbon and the diatomite is 1:1, the iodine value of the activated carbon is 750mg/g, the methylene blue value is 110mg/g, the pH value of the diatomite is 7.5, and the cationic polymer auxiliary agent is cationic polyacrylamide. The total cyanide and cyanide in the wastewater biochemical effluent are both less than or equal to 0.2mg/L, and the requirements of the discharge standard of pollutants in the coking chemical industry are met.
Example 2:
the coking wastewater treatment engineering of a certain company adopts a pretreatment, O/A/O and advanced treatment process. Design treatment Scale 4000m 3 And d, directly discharging the treated product. The content of cyanide in biochemical effluent is 3-10mg/L. The wastewater discharge requirement reaches the discharge limit of the pollutant discharge standard of the coking chemical industry (GB 16171-2012) and the discharge concentration limit of the pollutant of the newly-built enterprises in the table 2.
The physicochemical treatment stage of the treated effluent adopts the arrangement of a secondary reaction tank, a sedimentation tank and a water outlet tank at present, and is matched with the removal of fluoride, COD and chroma. Adjusting the pH value to be within the range of 5.0-7.0 before entering a first-stage reaction tank, adding 150mg/L of ferrous sulfate medicament into the first-stage reaction tank, stirring for reacting for 30min, and then entering a second-stage reaction tank; adding 800mg/L of high-efficiency decyanation agent (liquid) into the secondary reaction tank, adding 3 per mill of polyacrylamide into the water outlet end, slowly stirring and uniformly mixing, and feeding into a sedimentation tank; then forming solid by flocculation and precipitation in a sedimentation tank, separating solid from liquid, and feeding the treated wastewater into a drainage tank. In the embodiment, the efficient cyanogen removing agent is adopted, and the component ratio of the medium-density composite adsorbent is 60%; 35% of inorganic copper salt, 5% of cationic polymer additive and water are prepared into a 10% mixed solution. In the composite adsorbent, the specific gravity of the activated carbon and the diatomite is 2:1, the iodine value of the activated carbon is 780mg/g, the methylene blue value is 121mg/g, the pH value of the diatomite is 7.8, and the cationic polymer auxiliary agent is ammonium chloride-based cationic polymer. The total cyanide of the biochemical effluent of the wastewater is 8-15mg/L, and the cyanide of the effluent after the reaction is less than or equal to 0.2mg/L.
Example 3
The production quantity of the waste liquid generated by the coke oven desulfurization of a certain iron and steel enterprise is 2.5m 3 And h, all the waste water enters the phenol-cyanogen wastewater treatment system, because the cyanide content in the desulfurization waste liquid is high, the cyanide content reaches 1000-2000mg/L, the high cyanide content can cause great influence on the phenol-cyanogen wastewater biochemical treatment system, and the deep transformation of the phenol-cyanogen wastewater system is planned.
The improved treatment process comprises two-stage decyanation, wherein the effluent of a regulating reservoir enters a desulfurization and decyanation reactor, 3% ferrous sulfate is added for desulfurization and decyanation reaction, then solid-liquid separation is carried out, the effluent enters a second-stage decyanation tank, 1000mg/L of high-efficiency decyanation agent is added, then cationic PAM is added for precipitation separation, the concentration of the total cyanogen (CN-) of the treated wastewater is less than 150mg/L, and the wastewater enters a subsequent biochemical reaction tank. In the embodiment, the efficient cyanogen removing agent is adopted for preparing 40% of the composite adsorbent; 50% of inorganic copper salt, 10% of cationic polymer additive and water are prepared into 10% mixed solution. In the composite adsorbent, the specific gravity of the activated carbon and the diatomite is 1:1, the iodine value of the activated carbon is 812mg/g, the methylene blue value is 135mg/g, the pH value of the diatomite is 7.3, and the cationic polymer auxiliary agent is ammonium chloride-based cationic polymer.
The coking wastewater cyanide high-efficiency treatment agent, the high-efficiency cyanide removal agent and the cyanide removal process provided by the invention are used for removing wastewater cyanides in various process stages in the coking industry, and are practical and simple medicament treatment processes without obviously increasing process equipment.
Claims (10)
1. The utility model provides a coking wastewater removes cyanogen medicament which characterized in that:
the cyanogen removing medicament is prepared by compounding an adsorbent, a metal complexing agent and a cationic polymer auxiliary agent;
the cyanogen removing medicament comprises the following components in percentage by weight: 30% -75% of composite adsorbent; 10 to 50 percent of inorganic copper salt and 2 to 15 percent of cationic polymer additive;
the composite adsorbent is prepared by mixing and compounding active carbon and diatomite, wherein the active carbon comprises the following components in parts by weight: the diatomite specific weight ratio is 1-2:1; wherein the iodine value of the activated carbon is as follows: >700mg/g, methylene blue value: >105mg/g; the pH value of the diatomite is 6-9;
the cationic polymer additive is cationic polyacrylamide or ammonium chloride-based cationic polymer.
2. The coking wastewater decyanation agent according to claim 1, characterized in that: the inorganic copper salt is copper sulfate pentahydrate.
3. The coking wastewater decyanation agent according to claim 1, characterized in that: the granularity of the activated carbon is as follows: the mesh screen dropping rate of 200 is more than 60%; the fineness of the diatomite is within the range of 300 meshes to 1200 meshes.
4. The method for treating the coking wastewater by using the coking wastewater decyanation agent of claim 1 is characterized in that: the treatment facility includes pH equalizing basin, one-level cyanogen removal pond, one-level sedimentation tank, second grade cyanogen removal pond, second grade sedimentation tank and play water pool, includes the following step:
(1) Fully mixing the adsorbent, inorganic copper salt and cationic polymer additive according to a proportion, fully mixing and uniformly stirring to prepare compound powder or liquid suspension;
(2) The coking wastewater containing cyanogen to be treated enters a pH adjusting tank, alkali is added to adjust the pH, the mixture is uniformly stirred to maintain the pH at 5.0-7.0, and then the mixture enters a first-stage cyanogen removing tank;
(3) Adding a ferrous sulfate solution into the primary decyanation tank, fully stirring and reacting, then feeding the mixture into a primary sedimentation tank, feeding the supernatant into a subsequent secondary decyanation tank, and discharging sludge at the bottom into a sludge tank;
(4) Adding the cyanogen removal agent obtained in the step (1) and a coagulant polyacrylamide into a secondary cyanogen removal tank, slowly stirring and uniformly mixing, and feeding into a secondary sedimentation tank; the dosage of the cyanogen removing medicament is 150-1000mg/L;
(5) Flocculating and precipitating in a sedimentation tank to form solid, carrying out solid-liquid separation, and feeding the treated wastewater into a water outlet tank.
5. The method for treating the coking wastewater by the cyanogen-removing agent for the coking wastewater as claimed in claim 4, which is characterized in that: the coking wastewater comprises wastewater of each process stage in the coking industry.
6. The method for treating the coking wastewater by the cyanogen removal agent for the coking wastewater according to claim 4, which is characterized in that: the stirring time in the step (1) is 5-20 minutes; the stirring time in the step (2) is 5-20 minutes.
7. The method for treating the coking wastewater by the cyanogen removal agent for the coking wastewater according to claim 4, which is characterized in that: and (3) the alkali in the step (2) is sodium hydroxide or sodium hydroxide solution.
8. The method for treating the coking wastewater by the cyanogen removal agent for the coking wastewater according to claim 4, which is characterized in that: the stirring time in the step (3) is 10-30 minutes.
9. The method for treating the coking wastewater by the cyanogen-removing agent for the coking wastewater as claimed in claim 4, which is characterized in that: the dosage of the ferrous sulfate in the step (3) is 50-600mg/L.
10. The method for treating the coking wastewater by the cyanogen-removing agent for the coking wastewater as claimed in claim 4, which is characterized in that: in the step (4), the mass concentration of the polyacrylamide is 0.5-2%, and the addition amount is 1-3 per mill.
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