CN111807490A - Combined medicament for removing COD (chemical oxygen demand) and decoloring coking wastewater advanced treatment and application - Google Patents
Combined medicament for removing COD (chemical oxygen demand) and decoloring coking wastewater advanced treatment and application Download PDFInfo
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- CN111807490A CN111807490A CN202010687528.6A CN202010687528A CN111807490A CN 111807490 A CN111807490 A CN 111807490A CN 202010687528 A CN202010687528 A CN 202010687528A CN 111807490 A CN111807490 A CN 111807490A
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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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
Abstract
The combined medicament is applied to advanced treatment of coking wastewater to remove COD and decolor and comprises, by weight, 100-200 parts of quaternary ammonium salt, 100-200 parts of compound iron salt, 200-400 parts of modified activated carbon and 1-2 parts of anionic polyacrylamide. The compound iron salt comprises 700-900 parts of polymeric ferric sulfate or polymeric ferric chloride and 100-300 parts of polymeric aluminum ferric silicate; the modified activated carbon comprises 7-8 parts of activated carbon, 1-1.5 parts of aluminum sulfate and 0.5-1 part of lime. Respectively preparing a quaternary ammonium salt stock solution and a compound iron salt into a 10% solution, preparing a 5% solution by using modified activated carbon, preparing 0.1% o solution by using anionic polyacrylamide, putting the solution into coking wastewater with COD (chemical oxygen demand) of 300-500 mg/L and chroma of 150-250 times after biochemical treatment in a coking plant, and measuring the COD of effluent of the coking wastewater to be less than 100mg/L after reinforced compound coagulation, so as to reach the indirect discharge standard of the coking industry. And the color intensity of the effluent is less than 20 times. Under the synergistic action of adsorption and enhanced flocculation, the method has the advantages of high COD removal efficiency, good precipitation effect and low operation cost, and can be widely applied to the advanced treatment of wastewater in coking plants of different scales.
Description
Technical Field
The invention relates to the field of industrial wastewater treatment, and particularly provides a combined medicament applied to advanced treatment of coking wastewater and application of the combined medicament in the advanced treatment of the industrial wastewater.
Background
The coking and coal gasification wastewater is wastewater generated in the process of producing coal gas, and is mainly characterized in that the concentration of pollutants is extremely high, various components in crude gas are dissolved or suspended, and the coking and coal gasification wastewater contains a large amount of phenol, ammonia, sulfide, cyanide and tar, a large amount of heterocyclic compounds, polycyclic aromatic hydrocarbon and the like.
Typical coking wastewater quality is shown in the following table:
| index (I) | In the range mg/L | Index (I) | In the range mg/L |
| COD | 3000-4000 | Volatile phenols | <300 |
| BOD | 1000-1500 | Polyhydric phenol | <500 |
| Ammonia nitrogen | ≤150 | Total alkalinity | 2000 |
| Organic nitrogen | 30-50 | Carbonate salt | 1000 |
Organic matter composition of typical coking wastewater: the proportion of the phenols and the derivatives thereof is the largest, and accounts for about 60-65% of the total mass percent, the proportion of the quinoline compounds is 10-15%, and the proportion of the phenols and the derivatives thereof is about 10% of the total mass percent, and the three main substances form main organic matters in the coking wastewater. The proportion of heterocyclic compounds represented by pyridines, naphthalenes, indoles and biphenyls and polycyclic aromatic hydrocarbons in the coking wastewater fluctuates between 0.13% and 1.26%, and the mass percentage of the residual pollutants in the coking wastewater except the main pollutants is about 15%.
The advanced treatment method of the coking wastewater comprises the following steps: chemical coagulation-precipitation method, physical adsorption method, advanced oxidation method (O)3Fenton), biological treatment methods (biological aerated filters), and the like. The physical adsorption method can achieve higher removal efficiency by adopting active carbon and active coke as adsorbents, but has the disadvantages of limited adsorption capacity, large dosage, high operation cost and troublesome regeneration of the adsorbents. An ozone oxidation method: the equipment investment is large, the running power consumption is high, the decoloring effect is good, the COD removing capability is limited, and if a catalyst is added, the COD removing capability is improved to some extent. The Fenton method: the effect is better, but the types of the added medicaments are more in the process, the operation and management are troublesome, and a large amount of sludge is generated to form secondary pollution. The biological treatment method has higher construction cost and operation cost, is easily influenced by climatic conditions, and has good effect only by being combined with other methods.
The coagulating sedimentation method has simple equipment and convenient operation, and simultaneously, the flocculating agent and the organic colloid particles in the wastewater are quickly coagulated, adsorbed and coagulated, so that the coking wastewater can be deeply treated to obtain better effect. The current problem is how to prepare an efficient coagulating sedimentation agent to further improve the COD removal capacity and the decoloration effect of the coking wastewater biochemical tail water.
Disclosure of Invention
In order to solve the technical problems, the invention provides a combined medicament for removing COD and decoloring coking wastewater biochemical effluent and an application thereof, and the combined medicament has wide applicability. After the combined reagent is added into effluent after the biochemical treatment of the coking wastewater, the COD of the precipitated effluent can reach the indirect discharge standard in the discharge Standard of pollutants for coking chemical industry (GB16171-2012), and simultaneously, the chroma of the coagulating sedimentation effluent is greatly reduced.
The technical scheme of the invention is as follows:
a combined medicament suitable for removing COD (chemical oxygen demand) and decoloring coking wastewater in advanced treatment comprises 100-200 parts by weight of quaternary ammonium salt, 100-200 parts by weight of compound iron salt, 200-400 parts by weight of modified activated carbon and 1-2 parts by weight of anionic polyacrylamide; the compound ferric salt comprises 700-900 parts by weight of polymeric ferric sulfate or polymeric ferric chloride and 100-300 parts by weight of polymeric aluminum ferric silicate; the modified activated carbon comprises, by weight, 7-8 parts of activated carbon, 1-1.5 parts of aluminum sulfate and 0.5-1 part of lime, wherein the raw materials of quaternary ammonium salt, polymeric ferric sulfate or polymeric ferric chloride, polymeric aluminum ferric silicate, activated carbon, aluminum sulfate, lime and anionic polyacrylamide are all commercially available industrial grades.
The active carbon is in powder form.
The preparation method of the modified activated carbon comprises the following steps:
putting activated carbon into a container, adding water, stirring and blending into uniform paste, wherein the mass ratio of the activated carbon to the water is 3-4: 5-6;
secondly, sequentially adding aluminum sulfate and lime with the formula amount, and respectively stirring for 20-40 minutes to form mixed feed liquid;
thirdly, drying the mixed feed liquid at 100-105 ℃ until the water content is less than 5%;
and fourthly, grinding the mixture to 200-300 meshes by using a ball mill, and sieving the mixture to obtain modified activated carbon for later use.
The invention also provides application of the combined medicament for biochemical advanced treatment of coking wastewater to remove COD and decolor: firstly, compounding iron salt to prepare 10% solution, preparing modified active carbon to prepare 5% solution, preparing polyacrylamide to prepare 0.1% solution, and preparing quaternary ammonium salt without preparation. All percentages are by weight. Then the raw materials are added into coking wastewater which is biochemically treated in a coking plant and has COD of 300-500 mg/L and chroma of 150-250 times, and the adding amount is as follows: quaternary ammonium salts: 100-200 mg/L, compounding iron salt: 100-200 mg/L, water, modified activated carbon: 200-400 mg/L, anionic polyacrylamide: 1-2 mg/L, performing advanced treatment by adopting reinforced composite coagulation, wherein the average water temperature is more than or equal to 15 ℃, the pH value is about 7.5, and finally determining that the COD of the effluent of the coking wastewater is less than 100mg/L, so that the effluent reaches the indirect discharge standard in the discharge Standard of pollutants for the coking chemical industry (GB 16171-2012). Meanwhile, the chroma of the effluent is less than 20 times.
The invention has the following advantages and effects:
1. in the product of the invention, the quaternary ammonium salt is used as a cationic organic high-molecular coagulant, and the quaternary ammonium salt can neutralize negative charges attached to chromogenic group molecules of partial organic matters in wastewater by providing a large amount of cations so as to destabilize, finally generate a large amount of floccules, can adsorb, flocculate and destabilize so as to achieve the aim of decoloring, and has the advantages of high flocculation speed, small using amount, small influence by coexisting salts, PH and temperature and the like.
2. The addition of the modified activated carbon further carries out net capture and adsorption on some soluble organic matters with the molecular weight of 500-1000 and organic matters with low solubility and weak polarity, such as benzene and phenols, which are remained in the wastewater, so that the adsorption and flocculation capabilities of the modified activated carbon are enhanced. Meanwhile, the alkalinity consumed in the coagulation process can be supplemented, and the pH application range and the chemical phosphorus removal effect of the medicament are improved.
3. The polysilicate added in the compound ferric salt is used as a novel inorganic polymeric flocculant, has strong binding and aggregation capabilities, generates thick floc and has good precipitation performance, and can obviously improve the low-temperature adaptability of the flocculation process.
4. The combined addition of the modified activated carbon and the compound ferric salt has a physical adsorption process and a chemical strong flocculation process, and the removal rate of COD and the removal rate of chroma can be obviously improved due to the synergistic effect of the physical adsorption process and the chemical strong flocculation process.
5. The combined medicament has efficient adsorption and flocculation effects, has good adaptability to different coking plant wastewater by optimizing and adjusting the adding amount of various medicaments, meets the indirect discharge standard in the discharge Standard of pollutants for coking chemical industry (GB16171-2012), and is efficiently suitable for the treatment of other colored wastewater, such as printing and dyeing, pigment dye, coal chemical industry and other industries. After treatment, the effluent can meet the first-grade discharge requirement of Integrated wastewater discharge Standard (GB 8978-1996).
Drawings
FIG. 1 is a schematic flow chart of the combined agent for COD removal and decolorization in the advanced treatment of coking wastewater.
Detailed Description
Example 1
The preparation method of the combined medicament for removing COD and decoloring coking wastewater by advanced treatment comprises the following steps:
firstly, industrial-grade calcium oxide, powdered activated carbon, aluminum sulfate, polymeric ferric sulfate, polymeric aluminum ferric silicate, quaternary ammonium salt and anionic polyacrylamide are purchased.
A combined reagent suitable for deep treatment of coking wastewater to remove COD and decolor is prepared by firstly weighing 700 parts of polymeric ferric sulfate and 300 parts of polymeric aluminum ferric silicate, and mixing to prepare a compound ferric salt; secondly, putting 80g of activated carbon into a container, adding water, stirring (the mass ratio of the activated carbon to the water is 3:5), and blending into uniform paste; sequentially adding 10g of aluminum sulfate and 10g of lime, respectively stirring for 30 minutes, drying at 100 ℃ until the water content is less than 5%, grinding to 200-300 meshes by using a ball mill, and sieving to obtain the modified activated carbon.
Weighing 10g of compound iron salt, 5g of modified activated carbon and 0.1g of anionic polyacrylamide, and adding water to prepare solutions (wt%) of 10%, 5% and 0.1% respectively for later use, wherein the quaternary ammonium salt is not required to be prepared and is directly used. Measuring quaternary ammonium salt: compounding iron salt: modified activated carbon: polyacrylamide 100: 100: 200: 2 parts by weight of the raw materials form a combined agent for removing COD and decoloring coking wastewater by advanced treatment. The preparation flow of the combined medicament for removing COD and decoloring by advanced treatment of coking wastewater is shown in figure 1.
Example 2
A combined reagent suitable for deep treatment of coking wastewater to remove COD and decolor is prepared by firstly weighing 800 parts of polymeric ferric chloride and 200 parts of polymeric aluminum ferric silicate, and mixing to prepare a compound ferric salt; secondly, putting 75g of activated carbon into a container, adding water, stirring (the mass ratio of the activated carbon to the water is 3:5), and blending into uniform paste; and sequentially adding 13g of aluminum sulfate and 8g of lime, respectively stirring for 30 minutes, drying at 100 ℃ until the water content is less than 5%, grinding to 200-300 meshes by using a ball mill, and sieving to obtain the modified activated carbon.
Weighing 10g of compound iron salt, 5g of modified activated carbon and 0.1g of anionic polyacrylamide, and adding water to prepare solutions (wt%) of 10%, 5% and 0.1% respectively for later use, wherein the quaternary ammonium salt is not required to be prepared and is directly used. Measuring quaternary ammonium salt: compounding iron salt: modified activated carbon: polyacrylamide 150: 150: 300: 1.5 parts by weight of the raw materials form a combined agent for removing COD (chemical oxygen demand) and decoloring in the advanced treatment of the coking wastewater.
Example 3
A combined reagent suitable for deep treatment of coking wastewater to remove COD and decolor is prepared by firstly weighing 900 parts of polymeric ferric chloride and 100 parts of polymeric ferric aluminum silicate, and mixing to prepare a compound ferric salt; secondly, putting 70g of activated carbon into a container, adding water, stirring (the mass ratio of the activated carbon to the water is 3:5), and blending into uniform paste; adding 15g of aluminum sulfate and 5g of lime in sequence, stirring for 30 minutes respectively, drying at 100 ℃ until the water content is less than 5%, grinding to 200-300 meshes by using a ball mill, and sieving to obtain the modified activated carbon.
Weighing 10g of compound iron salt, 5g of modified activated carbon and 0.1g of anionic polyacrylamide, and adding water to prepare solutions (wt%) of 10%, 5% and 0.1% respectively for later use, wherein the quaternary ammonium salt is not required to be prepared and is directly used. Measuring quaternary ammonium salt: compounding iron salt: modified activated carbon: polyacrylamide 200: 200: 400: 1 part by weight, to form a combined medicament for removing COD and decoloring coking wastewater by advanced treatment.
Comparative example 1
The same as example 1, but without the addition of quaternary ammonium salt.
Comparative example 2
The same as example 1, but the modified activated carbon was replaced with activated carbon.
Comparative example 3
The same as example 1, but the compound iron salt is replaced by polymeric ferric sulfate and the modified activated carbon is replaced by activated carbon.
Comparative example 4
The same as example 1, but the compounded iron salt was replaced with polymeric iron sulfate.
Example 4
The combined medicament prepared in the embodiments 1 to 3 of the invention is suitable for the advanced treatment of coking wastewater to remove COD and decolor, and has the effect of carrying out the advanced treatment on the coking wastewater of a certain coking plant.
The coking wastewater of a certain coking plant is measured, and the water quality condition of the coking wastewater after biochemical treatment is as follows: COD is 250-350 mg/L, and chroma is 120-200 times. The combined reagent suitable for removing COD and decoloring in the advanced treatment of the coking wastewater in the embodiments 1 to 3 is added into the coking wastewater, and the adding amount of the embodiment 1 is as follows: 100mg/L of quaternary ammonium salt, 100mg/L of compound iron salt, 200mg/L of modification activity and 2mg/L of anionic polyacrylamide, wherein the adding amount of the embodiment 2 is 150mg/L of quaternary ammonium salt, 150mg/L of compound iron salt, 300mg/L of modification activity and 1.5mg/L of anionic polyacrylamide; the dosage of the embodiment 3 is as follows: 200mg/L of quaternary ammonium salt, 200mg/L of compound iron salt, 400mg/L of modification activity and 1mg/L of anionic polyacrylamide; carrying out advanced treatment (the average water temperature is 15 ℃, the pH value of the water sample is about 7.2), and finally respectively measuring the COD and the chroma of the water sample.
The results are shown in table 1, and the removal effect of the combined reagent for removing COD and decoloring in advanced treatment of coking wastewater on COD and chromaticity of effluent of biochemical treatment can be seen from table 1, and the indirect discharge standard in the discharge standard of pollutants for coking chemical industry (GB16171-2012) is satisfied.
TABLE 1 Effect of the combination preparations prepared in examples 1 to 3 on the advanced treatment of coking wastewater from a certain coking plant
Example 5
The combined medicament prepared in example 1 and suitable for advanced treatment of coking wastewater to remove COD and decolor is used for advanced treatment of coking wastewater of a certain coking plant and is compared with other common coagulants in effect.
The coking wastewater of a certain coking plant is measured, and the water quality condition of the coking wastewater after biochemical treatment is as follows: COD is 250-350 mg/L, and chroma is 120-200 times. The combined reagent which is suitable for removing COD and decoloring in the advanced treatment of the coking wastewater in the embodiment 1 is added into the coking wastewater, and the adding amount is as follows: the method comprises the following steps of preparing 100mg/L quaternary ammonium salt, 100mg/L compound iron salt, 200mg/L modified activity and 2mg/L anionic polyacrylamide, performing advanced treatment (the average water temperature is 15 ℃, and the pH value of a water sample is about 7.2) by using a combined reagent suitable for removing COD and decoloring coking wastewater, and finally respectively determining the COD and the chromaticity of the water sample.
The results of comparing the treatment effects of the combined agent for advanced treatment of coking wastewater with those of other common coagulants are shown in Table 2. The adding amount of other coagulants is 400mg/L, and the adding amount of anionic polyacrylamide is 5 mg/L.
From table 2, it can be seen that the combined reagent suitable for advanced treatment of coking wastewater to remove COD and decolor has better removal effects on COD and chroma of effluent from biochemical treatment than other coagulants, the COD removal rate is not less than 70%, the chroma removal rate is not less than 90%, and the indirect discharge standard in the discharge standard of pollutants for coking chemical industry (GB16171-2012) is satisfied.
Table 2 comparison of the effect of the combination agent prepared in example 1 and other common coagulants on advanced treatment of coking wastewater of a certain coking plant
Example 6
The combined medicament prepared in example 1 and the medicaments prepared in comparative examples 1 to 4 are used for carrying out advanced treatment on coking wastewater of a certain coking plant.
The coking wastewater of a certain coking plant is measured, and the water quality condition of the coking wastewater after biochemical treatment is as follows: COD is 250-350 mg/L, and chroma is 120-200 times. The coking wastewater was treated by using the prepared combination agents and the agents prepared in comparative examples 1 to 4 in amounts shown in Table 3, with the average water temperature of 15 ℃ or 25 ℃ and the pH of the water sample of about 7.2, and as a result, as shown in Table 3, the following conclusions were obtained: the synergistic effect of the modified activated carbon and the compound ferric salt can improve the removal rate of COD and the removal rate of chroma to a certain extent, and enhance the low-temperature adaptability of the combined medicament; ② the addition of quaternary ammonium salt further enhances the synergistic effect of other two compound and modified medicaments, and obviously improves the use effect of the combined medicament.
TABLE 3 comparison of effects of the combination preparations prepared in example 1 and the combination preparations prepared in comparative examples 1 to 4 on the advanced treatment of coking wastewater of a certain coke-oven plant
Claims (3)
1. The utility model provides a be applied to coking wastewater advanced treatment and get rid of COD and decoloration's combination medicament which characterized in that: the modified activated carbon comprises, by weight, 100-200 parts of quaternary ammonium salt, 100-200 parts of compound iron salt, 200-400 parts of modified activated carbon and 1-2 parts of anionic polyacrylamide; the compound ferric salt comprises 700-900 parts by weight of polymeric ferric sulfate or polymeric ferric chloride and 100-300 parts by weight of polymeric aluminum ferric silicate; the modified activated carbon comprises, by weight, 7-8 parts of activated carbon, 1-1.5 parts of aluminum sulfate and 0.5-1 part of lime.
2. The combined reagent for removing COD and decoloring applied to the advanced treatment of coking wastewater in claim 1 is characterized in that: the preparation method of the modified activated carbon comprises the following steps:
putting activated carbon into a container, adding water, stirring and blending into uniform paste, wherein the mass ratio of the activated carbon to the water is 3-4: 5-6;
adding aluminum sulfate and lime in sequence, and stirring for 20-40 minutes respectively to obtain mixed feed liquid;
thirdly, drying the mixed feed liquid at 100-105 ℃ until the water content is less than 5%;
and fourthly, grinding the mixture to 200-300 meshes by using a ball mill, and sieving the ground mixture to obtain the modified activated carbon.
3. The application of the combined reagent for removing COD and decoloring in the advanced treatment of coking wastewater as claimed in claim 1, wherein: firstly, preparing a compound iron salt into a 10% solution, preparing modified activated carbon into a 5% solution, preparing anionic polyacrylamide into a 0.1% solution, preparing quaternary ammonium salt without preparing, then adding the quaternary ammonium salt into coking wastewater which is biochemically treated in a coking plant and has COD of 300-500 mg/L and chroma of 150-250 times, and adding the quaternary ammonium salt: 100-200 mg/L, adding amount of the compound iron salt: 100-200 mg/L, adding amount of modified activated carbon: 200-400 mg/L, and the adding amount of anionic polyacrylamide is as follows: 1-2 mg/L, and determining that the COD of the effluent of the coking wastewater is less than 100mg/L after composite coagulation, so that the effluent reaches the indirect discharge standard in the discharge Standard of pollutants for coking chemical industry (GB16171-2012), and the chromaticity of the effluent is less than 20 times; all the above percentages are by weight.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113716635A (en) * | 2021-10-15 | 2021-11-30 | 辽宁同筑环保设施运营有限公司 | Phosphorus removing agent for industrial sewage treatment and use method thereof |
| CN113772779A (en) * | 2021-09-18 | 2021-12-10 | 鞍钢栗田(鞍山)水处理有限公司 | Medicament for realizing reduction of low-concentration cyanide-containing coking wastewater sludge and preparation method thereof |
| CN113788568A (en) * | 2021-10-14 | 2021-12-14 | 上海宝汇环境科技有限公司 | Coking wastewater advanced treatment and coupling fluoride ion removal process |
| CN114149100A (en) * | 2021-11-10 | 2022-03-08 | 中冶南方都市环保工程技术股份有限公司 | Coking wastewater advanced treatment composite reagent and application thereof |
| CN115038671A (en) * | 2021-05-28 | 2022-09-09 | 麦王环境技术股份有限公司 | Deep purification device and process for strong brine |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115038671A (en) * | 2021-05-28 | 2022-09-09 | 麦王环境技术股份有限公司 | Deep purification device and process for strong brine |
| CN113772779A (en) * | 2021-09-18 | 2021-12-10 | 鞍钢栗田(鞍山)水处理有限公司 | Medicament for realizing reduction of low-concentration cyanide-containing coking wastewater sludge and preparation method thereof |
| CN113788568A (en) * | 2021-10-14 | 2021-12-14 | 上海宝汇环境科技有限公司 | Coking wastewater advanced treatment and coupling fluoride ion removal process |
| CN113716635A (en) * | 2021-10-15 | 2021-11-30 | 辽宁同筑环保设施运营有限公司 | Phosphorus removing agent for industrial sewage treatment and use method thereof |
| CN114149100A (en) * | 2021-11-10 | 2022-03-08 | 中冶南方都市环保工程技术股份有限公司 | Coking wastewater advanced treatment composite reagent and application thereof |
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Application publication date: 20201023 |
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