CN111807590A - Resource treatment method for exempting dangerous waste of high ammonia nitrogen wastewater in coal chemical industry - Google Patents
Resource treatment method for exempting dangerous waste of high ammonia nitrogen wastewater in coal chemical industry Download PDFInfo
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Abstract
The invention discloses a resource treatment method for exempting dangerous wastes of high ammonia nitrogen wastewater in coal chemical industry, belonging to the field of wastewater treatment. The method comprises the following steps: 1) removing cyanide by adopting ozone aeration; 2) performing pH adjustment to remove carbonate ions; carrying out nanofiltration and/or electrodialysis treatment on the wastewater treated in the step (1), and separating organic matters and salt in the wastewater to obtain nanofiltration product water and/or electrodialysis concentrated water; 4) carrying out electrocatalytic oxidation treatment on nanofiltration water production water and/or electrodialysis concentrated water; 5) and preparing ammonium chloride crystals by using the evaporative crystallization device. The method of the invention effectively and thoroughly separates salts, organic matters, impurities and the like through pretreatment, and the ammonium chloride is recovered.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a resource treatment method for exempting dangerous wastes of high ammonia nitrogen wastewater in coal chemical industry.
Background
In the process of gasification in coal chemical industry, coal enters a gasification furnace in the form of dry powder or coal water slurry, reacts with oxygen under the conditions of high pressure and high temperature to generate crude gas, and the crude gas is washed and then sent to a conversion section. Conversion of CO to H by shift reaction2Therefore, the components are regulated, ammonia and other nitrogen-containing compounds can be generated in the side reaction of the shift reaction, and the ammonia and other nitrogen-containing compounds can enter a water phase and are removed from the shift gas in the subsequent water washing or steam condensation process, so that the method is a source of high ammonia-nitrogen wastewater. The high ammonia nitrogen wastewater produced in the coal chemical industry has the characteristics as follows: the wastewater is in a slightly alkaline state and contains a large amount of NH4 +、Cl-、CO3 2-Ions, the total salt content is about 6%; the organic matter content in the wastewater is more than 300 (represented by TOC), wherein the cyanide content is in the range of 50-70 mg/L, the content is high, and the cyanide is a highly toxic substance.
The treatment technology for the high ammonia nitrogen wastewater mainly comprises a biological method, a precipitation method, a breakpoint chlorination method and a stripping/stripping deamination method. The biological method mainly utilizes microorganisms to convert ammonia nitrogen in the wastewater into nitrate nitrogen or nitrite nitrogen through nitrification. However, when the ammonia nitrogen or the salt content in the wastewater is too high, the growth of microorganisms is easily inhibited or killed, and further the ammonia nitrogen removal is ineffective. In addition, the technology is greatly influenced by temperature, and occupies a large area; precipitation method-addition of PO mainly4 3-、Mg2+React to generate insoluble MgNH4PO4Crystallizing and precipitating so as to remove ammonia nitrogen from the wastewater. The method introduces newThe pollution factor has better removal effect only by adding excessive other two ions; the breakpoint chlorination method is that chlorine is introduced into wastewater to reach a certain point, the content of the free chlorine in the water is lowest at the point, the concentration of ammonia is reduced to zero, but the operation cost is high, and the secondary pollution problem is caused by chloramine and chlorinated organic compounds as byproducts; and (3) a stripping deamination method, namely adjusting the wastewater to be strong alkaline, blowing off ammonia gas in the wastewater under the condition of high-temperature blowing off, and recovering ammonia water or ammonium salt in a liquid receiving manner. The method is also a common technology for the existing high ammonia nitrogen wastewater in coal chemical industry. However, the technology mainly has the following problems in the operation process: (1) the recycled ammonium chloride has poor chroma, lower purity and lower added value of resource utilization. Trace chromogenic substances are contained in the high ammonia nitrogen wastewater in the coal chemical industry, so that the recycled ammonium chloride is light blue, the chromaticity can influence the resource utilization or sale of the recycled ammonium chloride, the recycled ammonium chloride possibly contains highly toxic substances, and the additional value of the recycling of the ammonium chloride is seriously reduced. (2) Decyanation treatment has not been considered in the prior art. Cyanide is a highly toxic substance, the content of the cyanide in the high ammonia nitrogen wastewater in the coal chemical industry is as high as 60mg/L, and if the cyanide is not treated, the cyanide can be diffused and transferred in the subsequent process, so that the recovered ammonia water and the kettle residue contain a large amount of cyanide, and the worse influence is caused; and (3) the ammonia distillation process has high alkali consumption and poor economy. The ammonia distillation blow-off process is adopted to treat the high ammonia nitrogen wastewater, the pH value of the wastewater needs to be adjusted to be strong alkaline, but ammonia nitrogen is taken as a buffer ion, the pH value can be adjusted to be high only by consuming a large amount of alkali, the preliminary estimation shows that the ammonia distillation blow-off process only consumes the alkali with the cost of more than 200 yuan/ton, and the economical efficiency is poor. (4) The difficulty of the treatment of the residue after ammonia distillation is increased, and the resource utilization degree is obviously reduced. The still residue of the ammonia distillation after the addition of alkali is a salt mixed system, mainly ammonium chloride and sodium chloride, and a large amount of organic matters exist, the separation difficulty of mixed salt is increased, the existence of high chloride ions can greatly reduce the effect of advanced catalytic oxidation, and finally the still residue cost is difficult to be used as a resource.
Therefore, the existing ammonia distillation process can not only cause the diffusion transfer of pollutants, but also has higher alkali regulation cost, higher kettle residue treatment cost, lower resource utilization degree and lower economic benefit.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that the prior ammonia distillation process can not completely and effectively separate salts, organic matters, impurities and the like, so that the chroma of the recovered ammonium chloride salt is poor, the purity is low, the ammonia distillation process has high alkali consumption and high cost, the invention provides the resource treatment method exempting from the dangerous waste of the high ammonia nitrogen wastewater in the coal chemical industry.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a resource treatment method for exempting dangerous wastes of high ammonia nitrogen wastewater in coal chemical industry, which comprises the following steps:
step (1): carrying out ozone aeration on the wastewater, strictly controlling the concentration of ozone and the aeration time, removing cyanide, avoiding organic matters in the wastewater from being damaged and increasing the consumption of ozone;
step (2): adjusting the pH value of the wastewater treated in the step (1) to 3.5-6 by using hydrochloric acid, and removing carbonate in the wastewater;
and (3): carrying out nanofiltration and/or electrodialysis treatment on the wastewater treated in the step (2), and separating organic matters and salt in the wastewater to obtain nanofiltration product water and/or electrodialysis concentrated water;
adopts a nanofiltration device and utilizes pressure to drive monovalent NH4 +、Cl-The organic matters in the wastewater are trapped in the concentrated water through the nanofiltration membrane, so that the separation effect of the organic matters and the salt is achieved; an electrodialysis device is adopted, and the charged ions are separated from the organic matters by mainly utilizing the charge driving principle, so that the separation of the salt and the organic matters in the wastewater is realized.
By adopting the nanofiltration and electrodialysis device, on one hand, the ammonium chloride to be recovered can pass through the nanofiltration membrane, so that the aim of efficiently separating the ammonium chloride salt from organic matters is fulfilled, on the other hand, the salinity concentration can be improved through electrodialysis, the separation effect of the salt and the organic matters is further enhanced, and the purity of the recovered ammonium chloride salt is ensured.
And (4): enabling the nanofiltration water production water and/or the electrodialysis concentrated water treated in the step (3) to enter an electrocatalytic oxidation device for treatment;
the electrocatalytic oxidation device can deeply remove trace impurity components such as chromogenic substances, cyanides, organic matters and the like, and improve the crystal chromaticity and purity of the recovered ammonium chloride;
and (5): the water sample treated in the step (4) enters an evaporative crystallization device, when the volume of evaporative condensate is 60-90% of the original evaporative volume, the evaporative crystallization process is completed, and the solid-liquid mixture enters a solid-liquid separation device;
and (6): and (5) drying the crystals obtained by solid-liquid separation in the step (5) to obtain ammonium chloride crystals, and recycling the supernatant obtained by solid-liquid separation to the ozone oxidation stage.
As a further improvement of the invention, the treatment time of the electrocatalytic oxidation device is 10-120 min.
As a further improvement of the invention, the nanofiltration treatment device has the volume ratio of nanofiltration inlet water to nanofiltration produced water of 1: (0.70-0.95);
as a further improvement of the invention, the nanofiltration treatment device adopts two-stage nanofiltration, and salt and organic matters are fully separated;
as a further improvement of the invention, the ratio of the volume of the receiving liquid to the volume of the inlet water in the electrodialysis device is (0.2-2): 1, when the salt concentration ratio of inlet water to concentrated water is 1: (0.5-5), completing the electrodialysis treatment.
As a further improvement of the invention, two or more stages are adopted in the treatment of the electrodialysis device.
As a further improvement of the invention, activated carbon is added in the ozone aeration process, and the adding amount of the activated carbon is 1-20% of the volume of the wastewater;
the activated carbon can play a role in adsorbing color development substances on one hand, can be used as a catalytic filler to improve the effect of ozone oxidation on the other hand, and can be automatically regenerated in the adsorption-catalysis-oxidation process without adding a regeneration process;
as a further improvement of the invention, the ozone aeration time is 30-60 min.
As a further improvement of the invention, hydrogen peroxide is added during ozone aeration to improve the cyanogen breaking effect by synergistic oxidation, and the adding amount of the hydrogen peroxide accounts for 0.1-1% of the volume ratio of the wastewater.
As a further improvement of the present invention, the solid-liquid separation device is a centrifugal separation device.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the resource treatment method exempting from hazardous waste of high ammonia nitrogen wastewater in coal chemical industry recycles high-purity ammonium chloride crystals, and evaporates residual liquid to solve the problem in a system without generating any hazardous waste. According to the process, according to the characteristics of the wastewater, impurity components such as cyanide, organic matters and the like in the wastewater are removed by adopting ozone for breaking cyanogen, a nanofiltration membrane and/or electrodialysis, and then ammonium chloride is recovered through evaporation crystallization, the purity of the ammonium chloride can reach the standard of first-class products in the industrial ammonium chloride standard (GB/T2946-. Therefore, the invention does not produce any hazardous waste, realizes the exemption of the hazardous waste in the treatment process, and greatly reduces the treatment cost of the hazardous waste for enterprises.
(2) The resource treatment method exempts from hazardous waste of high ammonia nitrogen wastewater in coal chemical industry solves the problem of chromaticity in the prior treatment technology. The method comprises the steps of firstly utilizing membrane separation (nanofiltration) interception and/electrodialysis to realize separation of organic matters and salt, simultaneously realizing concentration of salt, then further utilizing a series of physical, chemical and electrochemical reactions in an electrolysis process by an electro-catalytic oxidation technology to remove refractory chromogenic organic matters which are difficult to separate from salt and still exist after nanofiltration and/or electrodialysis treatment, and combining membrane separation and/or electrodialysis with electro-catalysis to ensure that the TOC concentration can be reduced to 0.01mg/L at the lowest before ammonium chloride is evaporated, crystallized and recovered, and the color of a solution is changed from light blue to colorless (the chroma is effectively removed); cyanide reaches the undetected standard, and high-purity recovery of ammonium chloride is guaranteed.
(3) The resource treatment method exempting from hazardous waste of high ammonia nitrogen wastewater in coal chemical industry removes cyanide and organic matters in two steps, and reduces the cost for removing and separating the organic matters. Ozone catalytic oxidation is used as an advanced oxidation means, and the operation cost is high. In the invention, ozone reacts preferentially with cyanide, and the dosage and reaction time of the oxidant are strictly controlled, so that ozone and cyanide react efficiently while other organic matters are prevented from being oxidized. Most of organic matters in the wastewater are mainly separated from salt by using a nanofiltration membrane and/or interception, and meanwhile, the concentration of the salt is realized, and the removal cost of the organic matters is reduced. The invention creatively adopts a two-step method to remove cyanide and organic matters, fully exerts the respective advantages of ozone oxidation and membrane separation technologies, improves the organic matter removal effect and reduces the treatment cost.
(4) According to the resource treatment method for exempting the dangerous waste of the high ammonia nitrogen wastewater in the coal chemical industry, other impurity ions are not introduced in the whole process. In the whole treatment process, CO in the wastewater is treated in an acid adjusting stage3 2-、HCO3 -Conversion to CO2And meanwhile, the organic matters and other impurities in the wastewater are removed by adopting the processes of ozone oxidation, membrane method recovery and the like, and no other impurity ions are introduced in the whole process, so that the main component in the solution is the ammonium chloride solution, and the recovery of high-purity ammonium chloride crystals is guaranteed.
(5) The resource treatment method exempted from hazardous wastes of the high ammonia nitrogen wastewater in the coal chemical industry has higher purity of the evaporation residual liquid and can be solved in a system. The evaporation mother liquor generated in the evaporation crystallization process is mainly a saturated ammonium chloride solution, has less impurity ions and organic matter content, can be directly recycled to the oxidation process of the front section, does not generate independent mother liquor hazardous waste, and greatly reduces the wastewater treatment cost.
Drawings
FIG. 1 is a process flow diagram of the treatment method in example 1;
FIG. 2 is a process flow diagram of the treatment method in example 2.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The detection indexes of the high ammonia nitrogen wastewater in the coal chemical industry are shown in table 1.
TABLE 1 raw water quality index of high ammonia nitrogen wastewater from coal chemical industry
As can be seen from the data in the table, the wastewater is alkaline and contains a large amount of NH4 +、Cl-、CO3 2-Ions, the total salt content is about 6%; the content of organic matters in the wastewater is more than 300 (represented by TOC), wherein the content of cyanide is 56.3mg/L, and the content is higher; the heavy metal content in the wastewater is low, so that the influence of the heavy metal does not need to be considered in the treatment process.
In the embodiment, a process flow diagram of a nanofiltration, electrodialysis and electrocatalytic oxidation method is shown in fig. 1, and the method comprises the following specific steps:
(1) taking 2L of coal chemical industry high ammonia nitrogen wastewater, adopting ozone aeration for 60min, and adding powdered activated carbon with wastewater volume ratio of 1% in the ozone aeration. After ozone aeration, the cyanide content in the solution is reduced to 1.3mg/L, the removal rate reaches 97.7 percent, the TOC content is reduced to 200.6mg/L, and the removal rate is 36.2 percent;
in the step, the activated carbon can play a role in adsorbing color development substances on one hand, and can be used as a catalytic filler to improve the effect of ozone oxidation on the other hand, and meanwhile, the activated carbon can be automatically regenerated in the adsorption-catalysis-oxidation process without adding a regeneration process;
(2) adding HCl into a water sample subjected to ozone aeration to adjust the pH value of the wastewater to 4, and fully stirring until bubbles are not generated any more, so as to ensure that carbonate in the water body is completely removed;
(3) taking the wastewater after acid adjustment to enter a nanofiltration device, wherein nanofiltration produced water mainly is an ammonium chloride solution, nanofiltration concentrated water mainly comprises impurities such as ammonium chloride, organic matters and the like, and the volume ratio of nanofiltration inlet water to produced water is 1: and 0.7, finishing nanofiltration treatment. At the moment, the salt content of nanofiltration produced water is 64230mg/L, the TOC content is 15.4mg/L, and the removal rate of organic matters reaches 95.1%; the salinity content in the nanofiltration concentrated water is consistent with that of produced water, but the TOC content is 187.2mg/L, and the concentrated water can be recycled to the ozone oxidation stage;
adopting a nanofiltration device, mainly using monovalent NH4 +、Cl-Organic matters in the wastewater can be trapped in the concentrated water through the nanofiltration membrane, so that the separation effect of the organic matters and salt is achieved;
(4) taking nanofiltration product water, allowing the nanofiltration product water to enter an electrodialysis device for salinity concentration, receiving by adopting pure water, wherein the volume ratio of receiving liquid to electrodialysis inlet water is 0.5:1, and when the salinity ratio of the electrodialysis inlet water to the concentrated water is 1: 2, completing electrodialysis, and concentrating the salt content by 1 time, wherein the salt content in electrodialysis concentrated water is 106980mg/L, and the TOC content is 1.44 mg/L;
an electrodialysis device is adopted, and the principle of separating organic matters from charged ions by mainly utilizing the charge driving principle is utilized to separate the salt and the organic matters in the wastewater.
(5) The electrodialysis concentrated water enters an electrocatalytic oxidation device, the electrocatalytic oxidation reaction time is 10min, cyanide in the wastewater is reduced to undetected concentration, the TOC concentration is reduced to 0.03mg/L, and the color of the solution is changed from light blue to colorless;
the electrocatalytic oxidation treatment in the step can deeply remove trace impurity components such as chromogenic substances, cyanides, organic matters and the like, and improve the crystal chromaticity and purity of the recovered ammonium chloride;
(6) the effluent after electrocatalytic oxidation enters an evaporation crystallization device, when evaporation condensate is 60% of the original evaporation volume, the evaporation crystallization process is completed, a solid-liquid mixture enters a centrifugal separation device, the TOC concentration in centrifugal supernatant is reduced to 0.9mg/L, the TOC concentration can be directly recycled to an ozone oxidation process, the obtained crystals are dried, and the purity is detected;
(7) 5g of dried ammonium chloride crystals are weighed and dissolved in 100mL of pure water, the purity of the ammonium chloride crystals is detected, and the detection result indexes are shown in Table 2.
TABLE 2 recovered ammonium chloride Crystal purity
The statistics of wastewater indexes at each treatment stage are shown in Table 3.
TABLE 3 statistics of wastewater indexes at various treatment stages
Example 2
The process flow chart of the resource treatment method for realizing exemption of dangerous wastes of high ammonia nitrogen wastewater in coal chemical industry by adopting the nanofiltration and electrocatalytic oxidation process is shown in figure 2, and the concrete steps are as follows:
(1) taking 2L of coal chemical industry high ammonia nitrogen wastewater, adding 1% hydrogen peroxide into the wastewater, simultaneously adding powdered activated carbon with the wastewater volume ratio of 10%, aerating with ozone for 40min, reducing the cyanide content in the solution to 1.2mg/L after the ozone aeration, wherein the removal rate reaches 97.8%, the TOC content is reduced to 221.1mg/L, and the removal rate is 29.7%;
(2) adding HCl into a water sample subjected to ozone aeration to adjust the pH value of the wastewater to 3.5, and fully stirring until bubbles are not generated any more;
(3) and (3) taking the wastewater after acid adjustment to enter a nanofiltration device, wherein nanofiltration water production is mainly ammonium chloride solution, nanofiltration concentrated water is mainly ammonium chloride and organic matters, and the water volume ratio of the nanofiltration water inlet to the water production is 1:0.95, so as to finish nanofiltration treatment. At the moment, the salt content of nanofiltration produced water is 63720mg/L, the TOC content is 18.3mg/L, and the removal rate of organic matters reaches 94.2%; the salinity content in the nanofiltration concentrated water is consistent with that of produced water, but the TOC content is 204.5mg/L, and the concentrated water can be recycled to an ozone oxidation stage;
(4) the nanofiltration water product enters an electrocatalytic oxidation device, the electrocatalytic oxidation reaction time is 30min, the cyanide in the wastewater is reduced to the undetected concentration, the TOC concentration is reduced to 0.08mg/L, and the color of the solution is changed from light blue to colorless;
(5) the electrocatalytic oxidation effluent enters an evaporation crystallization device, when evaporation condensate is 70% of the original evaporation volume, the evaporation crystallization process is completed, a solid-liquid mixture enters a centrifugal separation device, the TOC content in centrifugal supernatant is 0.8mg/L, the centrifugal supernatant can be recycled to an ozone oxidation process, crystals obtained by centrifugation are dried, and the purity is detected;
(6) 5g of dried ammonium chloride crystals are weighed and dissolved in 100mL of pure water, the purity of the ammonium chloride crystals is detected, and the detection result indexes are shown in Table 4.
TABLE 4 recovered ammonium chloride Crystal purity
Example 3
The method for realizing the exemption of the dangerous waste of the high ammonia nitrogen wastewater in the coal chemical industry by adopting the method of electrodialysis and electrocatalytic oxidation comprises the following specific steps:
(1) taking 2L of coal chemical industry high ammonia nitrogen wastewater, adding 0.5% hydrogen peroxide into the wastewater, simultaneously adding powdered activated carbon with the wastewater volume ratio of 10%, aerating with ozone for 45min, reducing the cyanide content in the solution to 0.75mg/L after the ozone aeration, wherein the removal rate reaches 98.7%, the TOC content is reduced to 218.6mg/L, and the removal rate is 30.5%;
(2) adding HCl into a water sample subjected to ozone aeration to adjust the pH value of the wastewater to 6, and fully stirring until bubbles are not generated any more;
(3) taking the wastewater after acid adjustment to enter an electrodialysis device, wherein pure water is adopted for electrodialysis, and the volume ratio of receiving liquid to electrodialysis inlet water is 0.2:1, when the salt ratio of electrodialysis inflow water to concentrated water is 1: and 1, completing electrodialysis. At the moment, the salt content in the electrodialysis concentrated water is 63822mg/L, and the TOC content is 12.9 mg/L; the content of salt in the electrodialytic fresh water is 63560mg/L, and the TOC content is 205.3 mg/L.
(4) The electrodialysis concentrated water enters an electrocatalytic oxidation device, the electrocatalytic oxidation reaction time is 60min, cyanide in the wastewater is reduced to undetected concentration, the TOC concentration is reduced to 0.03mg/L, and the color of the solution is changed from light blue to colorless;
(5) the electrodialysis concentrated water enters an evaporation crystallization device, when the evaporation condensate is 80% of the original evaporation volume, the evaporation crystallization process is completed, the solid-liquid mixture enters a centrifugal separation device, the TOC content in the centrifugal supernatant is 0.6mg/L, the TOC content can be directly recycled to the ozone oxidation process, the obtained crystals are dried, and the purity is detected;
(6) 5g of dried ammonium chloride crystals are weighed and dissolved in 100mL of pure water, the purity of the ammonium chloride crystals is detected, and the detection result indexes are shown in Table 5.
TABLE 5 recovered ammonium chloride Crystal purity
Example 4
The resource treatment method for realizing exemption of dangerous wastes of the high ammonia nitrogen wastewater in the coal chemical industry by adopting the nanofiltration and electrocatalytic oxidation method comprises the following specific steps:
(1) taking 2L of coal chemical industry high ammonia nitrogen wastewater, adding 0.1% of hydrogen peroxide into the wastewater, simultaneously adding 20% of powdered activated carbon by volume of the wastewater, and carrying out ozone aeration for 50 min. After ozone aeration, the cyanide content in the solution is reduced to 0.5mg/L, the removal rate reaches 98.6 percent, the TOC content is reduced to 207.8mg/L, and the removal rate is 33.9 percent;
(2) adding HCl into a water sample subjected to ozone aeration to adjust the pH value of the wastewater to 5, and fully stirring until bubbles are not generated any more;
(3) and (3) taking the wastewater after acid adjustment to enter a nanofiltration device, wherein nanofiltration produced water mainly comprises an ammonium chloride solution, and nanofiltration concentrated water mainly comprises ammonium chloride and organic matters. When the volume ratio of the water quantity of the nanofiltration inlet water to the water yield is 1:0.7, primary nanofiltration is completed, the salt content of the water produced by the primary nanofiltration is 63750mg/L, the TOC content is 10.8mg/L, and the removal rate of organic matters reaches 96.6%; the salinity content in the first-stage nanofiltration concentrated water is consistent with that of produced water, the TOC content is 198.1mg/L, and the concentrated water can be recycled to an ozone oxidation stage; in the secondary nanofiltration, the water produced by the primary nanofiltration is taken as inlet water, and when the volume ratio of the water produced by the primary nanofiltration to the water produced by the secondary nanofiltration is 1:0.9, the nanofiltration treatment is completed. The salt content of the water produced by the secondary nanofiltration is 63850mg/L, the TOC content is 3.6mg/L, and the removal rate of organic matters reaches 98.8%; the TOC content in the secondary nanofiltration concentrated water is 12.0mg/L, and the secondary nanofiltration concentrated water is recycled to the ozone oxidation stage;
(4) the nanofiltration water product enters an electrocatalytic oxidation device, the electrocatalytic oxidation reaction time is 120min, the cyanide in the wastewater is reduced to the undetected concentration, the TOC concentration is reduced to 0.01mg/L, and the color of the solution is changed from light blue to colorless;
(5) the electrocatalytic oxidation effluent enters an evaporation crystallization device, when evaporation condensate is 90% of the original evaporation volume, the evaporation crystallization process is completed, a solid-liquid mixture enters a centrifugal separation device, the TOC content in centrifugal supernatant is 0.8mg/L, the centrifugal supernatant can be recycled to an ozone oxidation process, crystals obtained by centrifugation are dried, and the purity is detected;
(6) 5g of dried ammonium chloride crystals are weighed and dissolved in 100ml of pure water, the purity of the ammonium chloride crystals is detected, and the detection result indexes are shown in Table 6.
TABLE 6 recovered ammonium chloride Crystal purity
Example 5
The method for realizing the exemption of the dangerous waste of the high ammonia nitrogen wastewater in the coal chemical industry by adopting the method of the multistage electrodialysis device and the electrocatalytic oxidation comprises the following specific steps:
(1) taking 2L of coal chemical high ammonia nitrogen wastewater, adding 15% powdered activated carbon into the wastewater, and performing ozone aeration for 20 min. After ozone aeration, the cyanide content in the solution is reduced to 0.9mg/L, the removal rate reaches 98.4 percent, the TOC content is reduced to 223.4mg/L, and the removal rate is 29.0 percent;
(2) adding HCl into a water sample subjected to ozone aeration to adjust the pH value of the wastewater to 4.2, and fully stirring until bubbles are not generated any more;
(3) taking the wastewater after acid adjustment to enter an electrodialysis device, wherein pure water is adopted for primary electrodialysis, the volume ratio of receiving liquid to electrodialysis inlet water is 0.2:1, and when the salt ratio of the electrodialysis inlet water to the salt in the concentrated water is 1:0.5, primary electrodialysis work is completed, wherein the salt content in the electrodialysis concentrated water is 67792mg/L, and the TOC content is 17.2 mg/L; the content of salt in the electrodialytic fresh water is 33296mg/L, and the TOC content is 207.2 mg/L; and (3) enabling the fresh water of the first-stage electrodialysis to enter a second-stage electrodialysis device, receiving by adopting pure water, wherein the volume ratio of receiving liquid to electrodialysis inflow water is 2:1, and when the salt ratio of the second-stage electrodialysis inflow water to the salt ratio of the second-stage electrodialysis concentrated water is 1: 5, completing the work of the second-stage electrodialysis, wherein the salt in the fresh water of the second-stage electrodialysis is 200mg/L, the TOC content is 201.6mg/L, and the fresh water of the second-stage electrodialysis can be directly discharged; 2L of raw water is taken again, secondary electrodialysis concentrated water is adopted as receiving liquid, and the volume ratio of the receiving liquid to electrodialysis inflow water is 1:0.5, when the salt ratio of the inlet water of the three-stage electrodialysis to the concentrated water of the three-stage electrodialysis is 1:1.8, completing the three-stage electrodialysis, wherein the salt content of the concentrated water of the three-stage electrodialysis is 119000mg/L, and the TOC content is 14.6 mg/L;
(4) the concentrated water of the third-stage electrodialysis enters an electrocatalytic oxidation device, the electrocatalytic oxidation reaction time is 20min, cyanide in the wastewater is reduced to the undetected concentration, the TOC concentration is reduced to 0.04mg/L, and the color of the solution is changed from light blue to colorless;
(5) the electrocatalytic oxidation effluent enters an evaporation crystallization device, when the evaporation condensate is 85% of the original evaporation volume, the evaporation crystallization process is completed, the solid-liquid mixture enters a centrifugal separation device, the TOC content in the centrifugal supernatant is 0.5mg/L, the centrifugal supernatant can be recycled to an ozone oxidation process, crystals obtained by centrifugation are dried, and the purity is detected;
(6) 5g of dried ammonium chloride crystals are weighed and dissolved in 100mL of pure water, the purity of the ammonium chloride crystals is detected, and the detection result indexes are shown in Table 7.
TABLE 7 recovered ammonium chloride Crystal purity
Claims (10)
1. A resource treatment method for exempting hazardous wastes of high ammonia nitrogen wastewater in coal chemical industry is characterized by comprising the following steps: the method comprises the following steps:
1) carrying out ozone aeration on the wastewater to remove cyanide;
2) adjusting the pH of the wastewater treated in the step 1) to remove carbonate ions;
3) carrying out nanofiltration and/or electrodialysis treatment on the wastewater treated in the step 2), and separating organic matters and salt in the wastewater to obtain nanofiltration product water and/or electrodialysis concentrated water;
4) carrying out electrocatalytic oxidation treatment on the nanofiltration water production water and/or the electrodialysis concentrated water treated in the step 3);
5) evaporating and crystallizing the water sample treated in the step 4) to prepare ammonium chloride crystals.
2. The exemption resource treatment method for the dangerous waste of the high ammonia nitrogen wastewater in the coal chemical industry according to the claim 1, which is characterized in that: activated carbon is added in the ozone aeration process, and the adding amount of the activated carbon is 1-20% of the volume of the water sample.
3. The exemption resource treatment method for the dangerous waste of the high ammonia nitrogen wastewater in the coal chemical industry according to the claim 1 or 2, which is characterized in that: the ozone aeration time is 20-60 min.
4. The exemption resource treatment method for the dangerous waste of the high ammonia nitrogen wastewater in the coal chemical industry according to the claim 3, which is characterized in that: adding hydrogen peroxide during ozone aeration, wherein the adding volume of the double oxidation accounts for 0.1-1% of the volume of the wastewater.
5. The method for exempting resource treatment of dangerous waste of high ammonia nitrogen wastewater in coal chemical industry according to claim 4, characterized in that: in the nanofiltration treatment process, the volume ratio of nanofiltration inlet water to nanofiltration produced water is 1: (0.70-0.95).
6. The method for exempting resource treatment of dangerous waste of high ammonia nitrogen wastewater in coal chemical industry according to claim 5, characterized in that: the time of the electrocatalytic oxidation treatment is 10-120 min.
7. The exemption resource treatment method for the dangerous waste of the high ammonia nitrogen wastewater in the coal chemical industry according to the claim 1 or 2, which is characterized in that: the nanofiltration and/or electrodialysis treatment is two-stage or more.
8. The exemption resource treatment method for the dangerous waste of the high ammonia nitrogen wastewater in the coal chemical industry according to the claim 7, which is characterized in that: the volume ratio of the receiving liquid to the water inlet in the electrodialysis treatment process is (0.2-2): 1.
9. the method for exempting resource treatment of hazardous waste of high ammonia nitrogen wastewater in coal chemical industry according to claim 8, characterized in that: in the electrodialysis treatment process, when the salt concentration ratio of the electrodialysis inflow water to the electrodialysis concentrated water is 1 (0.5-5), the electrodialysis treatment is completed.
10. The exemption resource treatment method for the dangerous waste of the high ammonia nitrogen wastewater in the coal chemical industry according to the claim 1, which is characterized in that: in the evaporation crystallization process, when the volume of the evaporation condensate is 60-90% of the original evaporation volume, the evaporation crystallization process is completed.
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