CN110386728B - Integrated process for treating high-salinity high-COD industrial wastewater through tubular free radical oxidation - Google Patents
Integrated process for treating high-salinity high-COD industrial wastewater through tubular free radical oxidation Download PDFInfo
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- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
Abstract
The invention provides an integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation, which realizes zero discharge of high-salinity high-concentration organic wastewater by settling, evaporative cooling crystallization, water distribution in a water distribution tank, tubular free radical oxidation, microbial degradation and reverse osmosis membrane treatment, solves the problems of high operating cost and incomplete treatment in the prior art and can treat high-salinity high-COD wastewater with salt content of more than 25 wt%; the integrated process for treating the high-salinity high-COD industrial wastewater through the tubular free radical oxidation realizes the self-sufficiency of heat energy in the system, utilizes the heat generated in the wet reaction process, maintains the self-use heat of the wet reaction, can realize the heating of the evaporator in a steam-rich mode, and saves energy.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to an integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation.
Background
In the social and economic development and urbanization process of China, water resource shortage is becoming one of the main factors restricting the sustainable development strategy of China. In recent years, with the continuous increase of industrial scale in China, the industrial water consumption is increased dramatically. Meanwhile, the amount of generated wastewater is rapidly increased, and great challenges are brought to the current wastewater treatment and recycling technology. If the industrial wastewater is directly discharged, the environmental pollution of the surrounding soil and water body can be serious. After the wastewater is qualified after treatment, if the wastewater is not recycled, water resource waste is caused, and water resource shortage is aggravated. For high-salinity wastewater, due to the lack of technical, economic feasibility and reliability, dilution discharge methods are mostly adopted. The method can not only reduce the total amount of pollutant emission really, but also cause fresh water waste, especially the discharge of salt-containing waste water, and the mineralization of fresh water resources and the alkalization of soil are caused. Compared with the desalination technical level of zero discharge or zero discharge of foreign high-salinity wastewater, China has a large gap. Therefore, how to develop an economic and effective desalination treatment process technology for high-salinity wastewater, promote the resource utilization of the high-salinity wastewater, and solve the bottleneck problem of water resource recycling.
Generally, for biochemical treatment of wastewater, high salinity wastewater refers to wastewater containing organic matter and at least a mass fraction of Total Dissolved Solids (TDS) greater than 3.5%. Because such waste water contains, in addition to organic contaminants, a large amount of soluble inorganic salts, such as Cl-、Na+、SO4 2-、Ca2+And the like. Therefore, such waste water is generally the limit of biochemical treatment. It has been reported that phenol-containing wastewater containing 15% salt has been treated abroad with specially domesticated halophilic bacteria; in China, the use of halophilic bacteria to treat wastewater containing 5% salt is reported. Besides seawater desalination, other sources of the wastewater mainly come from the following fields: chemical production, incomplete chemical reaction or by-products of chemical reaction, in particular to a large amount of high-COD and high-salt toxic wastewater generated in the production process of chemical products such as dyes, pesticides and the like; secondly, wastewater treatment, in the wastewater treatment process, mineralization caused by the addition of a water treatment agent, acid and alkali and concentrated solution generated by the recovery of most of 'light' water can increase the concentration of soluble salts to form 'high salinity wastewater' which is difficult to biochemically treat. It can be seen that the salt-containing wastewater has greater environmental pollution than the common wastewater.
At present, common treatment methods for high-salt high-concentration degradation-resistant organic wastewater comprise the following steps: incineration, evaporative desalination, membrane separation, ion exchange, electrochemical, and tubular free radical oxidation. The incineration method is characterized in that organic matters in the wastewater react violently with oxygen in the air at 800-1000 ℃, energy is released, high-temperature combustion gas and solid residues with stable properties are generated, the operation cost is high, and the incineration method can generate waste gases such as sulfur oxides, nitrogen oxides and dioxin. Moreover, the organic wastewater with high salt content seriously corrodes incineration equipment, and the service life of the equipment is influenced. Evaporative desalination is a process in which the waste water is heated with steam to evaporate most of the water and precipitate the inorganic salt. However, when the concentration of organic matters in the wastewater is high, inorganic salts and organic matters cannot be effectively separated, so that a large amount of viscous fluid is generated, and the treatment cost is high as hazardous waste. Membrane separation is a method of separating different substances by using pressure as a driving force according to the size of the particle size of the substance to be separated. But when the content of organic matters in the wastewater is higher, the membrane is polluted; meanwhile, the complex components in the wastewater can also influence the separation effect of organic matters and inorganic salts. Ion exchange is a reversible chemical reaction between ions in the liquid phase and ions in the solid phase. Because the exchange capacity of the resin is limited, the regeneration times of the resin can be greatly increased and the ion exchange effect is reduced due to the overhigh salt concentration, and the method is not suitable for treating the wastewater with the overhigh salt concentration. The electrochemical method is to apply current to generate an electric field, so that anions and cations in the solution move directionally, inorganic salt is separated out at two electrodes, and meanwhile, a certain effect of removing organic matters is achieved. However, the electrochemical method is not suitable for treating high-concentration organic wastewater because the cost for treating wastewater by the electrochemical method is greatly increased along with the increase of organic matters and salt content.
The tubular radical oxidation process was developed on the basis of the wet air oxidation process. The wet air oxidation method was developed by Zimmer to man in the united states in 1994, and is also called the WAO method. The treatment method of adding the catalyst in the WAO method is called a tubular free radical oxidation method, which is called a WACO method for short. The method is characterized in that under the conditions of high temperature (200-280 ℃) and high pressure (2-8 MPa), oxygen-enriched gas or oxygen is used as an oxidant, the catalytic action of a catalyst is utilized to accelerate the respiratory reaction between organic matters in the wastewater and the oxidant, so that the organic matters in the wastewater and poisons containing N, S and the like are oxidized into CO2、N2、SO2、H2O, achieving the purpose of purification. For various industrial organic wastewater with high chemical oxygen content or containing compounds which can not be degraded by a biochemical method, the COD removal rate reaches more than 99 percent, no post-treatment is needed, and the emission standard can be reached only by one-time treatment. However, the existing industrialized tubular free radical oxidation catalysts are not salt-tolerant (halogen salt, sulfate, phosphate, etc.), wherein the catalyst in high-chlorine wastewater can generate the phenomena of loss of active components and irreversible poisoning, and the activity of the catalyst is seriously influenced. Therefore, the development of a salt-tolerant catalyst is very important for treating high-salt high-concentration organic wastewater, and the industrial application range of tubular free radical oxidation can be expanded.
In conclusion, no process method with low cost and good treatment effect exists for the high-salt degradation-resistant organic wastewater at present. The traditional method has the problems of high treatment cost, secondary pollution (generation of hazardous waste and waste gas), incapability of meeting the requirement of environmental protection and the like.
Disclosure of Invention
Aiming at the problems of high treatment cost and poor treatment effect of the existing high-salt refractory organic wastewater, the invention provides an integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation, and the high-COD wastewater with the salinity of more than 25 wt% can realize zero discharge of wastewater treatment after treatment.
In order to achieve the purpose, the invention adopts the technical scheme that: a treatment process of high-salt degradation-resistant wastewater comprises the following steps:
s1, introducing the high-salt and high-COD wastewater into a wastewater buffer tank for sedimentation and desanding, and separating large-particle sand and other substances to avoid the abrasion of the pump and the blockage of a pipe network caused by the sand in the wastewater, and even the interference and the damage of the biochemical treatment process;
s2, introducing the wastewater in the wastewater buffer into an evaporator by using a sewage pump, evaporating, cooling and crystallizing, concentrating the high-salt wastewater by evaporation to obtain condensed water and a concentrated solution, cooling the concentrated solution to separate out soluble salt substances in the high-salt wastewater by crystallization, and filtering to obtain a crystallized salt compound and a crystallized mother solution;
s3, adding the crystallization mother liquor into a water distribution tank, and adjusting the salinity in the water distribution tank to 10-15 wt% by using the condensed water in the evaporator;
s4, introducing the sewage in the water distribution tank into a wet oxidation reactor, carrying out wet oxidation at a certain temperature, carrying out oxidative decomposition on macromolecular organic matters in the wastewater by a strong oxidant, breaking double bonds in the organic matter structure, oxidizing the macromolecules into micromolecules, further oxidizing the micromolecules into carbon dioxide and water, and greatly reducing the COD (chemical oxygen demand) and greatly improving the BOD/COD value;
s4, directly introducing the wastewater discharged from the wet oxidation reactor into a microbial degradation pool for microbial degradation;
and S5, filtering the degradation liquid by a biochar filter bed, introducing the degradation liquid into a reverse osmosis membrane treatment device for output rate, using the degradation liquid after reverse osmosis, and carrying out low-temperature evaporation and crystallization on the reverse osmosis high-salt concentrated water to generate industrial salt which can be reused.
Preferably, the heating source in the evaporator in step S2 is derived from the wet oxidation reactor in step S4;
preferably, the evaporation amount of the wastewater in the step S2 is preferably 15-35% of the total amount of the wastewater;
preferably, a wastewater salinity detecting device is arranged in the distribution tank in the step S3, and the wastewater salinity detecting device is connected with the microcomputer controller, and the microcomputer controller is used for controlling the amount of the added condensed water.
Preferably, the wet oxidation reactor in step S4 is a radical generator, and the radical generator is loaded with a composite catalyst; further preferably, the free radical generator comprises a high-pressure air feeding device, and the high-pressure air feeding device comprises an air compressor, a high-pressure buffer tank and an air flow meter.
Preferably, the composite catalyst is LaMnxCo1-xO3A perovskite catalyst, wherein the value of x is in the range of 0.01 to 0.2;
the preparation method comprises the following steps:
1) weighing lanthanum soluble salt, manganese soluble salt and cobalt soluble salt according to a stoichiometric ratio, dissolving the lanthanum soluble salt, the manganese soluble salt and the cobalt soluble salt in a certain amount of deionized water to prepare a mixed metal salt solution, adding a certain amount of citric acid, and stirring until the mixed metal salt solution is completely dissolved to form sol;
2) drying the sol, cooling to room temperature, fully grinding and sieving;
3) adding the sieved powder into a calcining device, and carrying out microwave heating calcination under an air atmosphere to obtain the powder with LaMnxCo1-xO3A perovskite-type catalyst.
Preferably, the halophilic bacteria in the step S5 are halophilic bacteria with high tolerance, which are screened and cultured by using high-salinity wastewater with the concentration of 10-15 wt%.
Preferably, the reverse osmosis membrane in step S5 is made of cellulose acetate, polyamide, polyimide, etc., and the operating pressure is preferably 1.5 to 2.5 Mpa.
Compared with the prior art, the invention has the beneficial effects that:
1) by utilizing the integrated process, the zero discharge of the high-salt and high-concentration organic wastewater treatment is realized, the problems of high operating cost and incomplete treatment in the prior art are solved, and the high-salt and high-COD wastewater with the salt content of more than 25 wt% can be treated;
2) the integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation designed by the invention realizes self-sufficiency of heat energy in the system, utilizes the heat generated in the wet reaction process, can maintain the self-use heat of the wet reaction, and can realize heating of an evaporator in a steam-rich mode, thereby saving energy;
3) LaMn adopted by the inventionxCo1-xO3The perovskite catalyst has better catalytic activity on high-salinity wastewater of about 10-20 wt% and better stability, the COD removal rate is up to more than 90%, and the catalyst can continuously work for more than 300 hours.
Drawings
FIG. 1 is an integrated process flow for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
[ example 1 ]
As shown in figure 1, the COD in the wastewater is 100000-200000 mg/L, the salt content is 25-35 wt%,
the process comprises the following steps:
s1, introducing the high-salt and high-COD wastewater into a wastewater buffer tank for settling and desanding, and separating large-particle sand and other substances to avoid the abrasion of the pump and the blockage of a pipe network caused by the sand in the wastewater, and even the interference and the damage of the biochemical treatment process;
and S2, introducing the wastewater in the wastewater buffer into an evaporator by using a sewage pump, heating the wastewater by using hot steam generated by a wet oxidation reactor, and concentrating the high-salinity wastewater by evaporation, wherein the evaporation amount of the wastewater is preferably 15-35% of the total amount of the wastewater. Simultaneously obtaining condensed water and concentrated solution, cooling the concentrated solution, crystallizing and separating soluble salt substances in the high-salinity wastewater, and filtering to obtain a crystallized salt compound and a crystallized mother solution;
and S3, adding the crystallization mother liquor into a water distribution tank, wherein a wastewater salinity detection device is arranged in the water distribution tank, the wastewater salinity detection device is connected with a microcomputer controller, and the microcomputer controller is used for controlling the addition amount of condensed water. The salinity in the water distribution tank is adjusted to be between 10 and 15 weight percent by utilizing the condensed water in the evaporator.
S4, introducing the sewage in the water distribution tank into a wet oxidation reactor, carrying out wet oxidation at a certain temperature, carrying out oxidative decomposition on macromolecular organic matters in the wastewater by a strong oxidant, breaking double bonds in the organic matter structure, oxidizing the macromolecules into micromolecules, further oxidizing the micromolecules into carbon dioxide and water, and greatly reducing the COD (chemical oxygen demand) and greatly improving the BOD/COD value; the wet oxidation reactor is a free radical generator, and the free radical generator is loaded with a composite catalyst; further preferably, the free radical generator comprises a high-pressure air feeding device, and the high-pressure air feeding device comprises an air compressor, a high-pressure buffer tank and an air flow meter. The composite catalyst is a LaMnxCo1-xO3 perovskite catalyst, wherein the value of x is 0.01-0.2;
s4, directly introducing the wastewater discharged from the wet oxidation reactor into a microbial degradation pool for microbial degradation;
and S5, filtering the degradation liquid by a biochar filter bed, introducing the degradation liquid into a reverse osmosis membrane treatment device for output rate, using the degradation liquid after reverse osmosis, and carrying out low-temperature evaporation and crystallization on the reverse osmosis high-salt concentrated water to generate industrial salt which can be reused. The reverse osmosis membrane is made of cellulose acetate, polyamide, polyimide, etc., and the operation pressure is preferably 1.5-2.5 MPa.
By utilizing the integrated process, the zero discharge of the high-salt and high-concentration organic wastewater treatment is realized, the problems of high operating cost and incomplete treatment in the prior art are solved, and the high-salt and high-COD wastewater with the salt content of more than 25 wt% can be treated; the integrated process for treating the high-salinity high-COD industrial wastewater through the tubular free radical oxidation realizes the self-sufficiency of heat energy in the system, utilizes the heat generated in the wet reaction process, maintains the self-use heat of the wet reaction, can realize the heating of the evaporator in a steam-rich mode, and saves energy.
[ example 2 ]
Screening and cultivating microorganisms: screening and culturing halotolerant bacteria with high tolerance to salt concentration; the traditional microorganism screening method is changed, culture medium with 10 wt% -20 wt% of salt concentration gradient is configured to culture microorganisms, salt-tolerant bacteria with high tolerance to salt concentration are obtained through purification and separation, the salt-tolerant bacteria cultured in the high-salinity culture medium have high tolerance to salinity, and the salt-tolerant bacteria grow in high salinity to obtain the microorganism, namely the salt-tolerant bacteria, which can normally grow in high salinity.
[ example 3 ]
Preparing a composite catalyst:
1) weighing 1mol of lanthanum nitrate, 0.2mol of manganese nitrate and 0.8mol of cobalt nitrate according to a stoichiometric ratio, dissolving the lanthanum nitrate, the manganese nitrate and the cobalt nitrate in 5L of deionized water to prepare a mixed metal salt solution, adding 2.5mol of citric acid, and stirring until the citric acid is completely dissolved to form sol;
2) drying the sol at 100 ℃, cooling to room temperature, fully grinding and sieving with a 80-mesh sieve;
3) and adding the sieved powder into a calcining device, and carrying out microwave heating calcination under an air atmosphere, wherein the microwave power is 1500ww, the heating temperature is 900 ℃, and the heating time is 5 minutes, so as to obtain the LaMn0.2Co0.8O3 perovskite catalyst.
[ example 3 ]
And (3) treating sample sewage:
the sample sewage is high-salt high-COD wastewater of a chemical plant, the COD in the wastewater is 100000-200000 mg/L, and the salt content is 25-35 wt%.
The method is processed according to the flow shown in figure 1, the composite catalyst prepared in the example 3 is loaded in a free radical generator, and the halophilic bacteria screened in the example 2 are inoculated in a degradation pool. The wastewater with the salt content of 25 wt%, 30 wt% and 35 wt% is treated by the integrated procedure of the embodiment 1, the pressure of the free radical generator is controlled at 8Mpa, the temperature of the reactor is raised to 250 ℃ by utilizing heat conducting oil in the initial stage of the reaction, the heating is stopped after the reaction is normal, the subsequent treatment process does not carry out any heating operation and continuously operates for 300 hours, the COD of the effluent is tested, and the results are shown in the table 1,
TABLE 1
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.
Claims (7)
1. An integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation is characterized by comprising the following steps: s1, introducing the high-salt and high-COD wastewater into a wastewater buffer tank for sedimentation and desanding, and separating out large-particle sand substances so as to avoid abrasion of the pump and blockage of a pipe network caused by sand in the wastewater, and even avoid the interference of the sand in the wastewater and the destruction of the biochemical treatment process; s2, introducing the wastewater in the wastewater buffer into an evaporator by using a sewage pump, evaporating, cooling and crystallizing, concentrating the high-salt wastewater by evaporation to obtain condensed water and a concentrated solution, cooling the concentrated solution to separate out soluble salt substances in the high-salt wastewater by crystallization, and filtering to obtain a crystallized salt compound and a crystallized mother solution; s3, adding the crystallization mother liquor into a water distribution tank, and adjusting the salinity in the water distribution tank to 10-15 wt% by using the condensed water in the evaporator; s4, introducing the sewage in the water distribution tank into a wet oxidation reactor, carrying out wet oxidation at a certain temperature, carrying out oxidative decomposition on macromolecular organic matters in the wastewater by a strong oxidant, breaking double bonds in the organic matter structure, oxidizing the macromolecules into micromolecules, further oxidizing the micromolecules into carbon dioxide and water, and greatly reducing the COD (chemical oxygen demand) and greatly improving the BOD/COD value; s4, directly introducing the wastewater discharged from the wet oxidation reactor into a microbial degradation pool for microbial degradation; s5, filtering the degradation liquid through a biochar filter bed, introducing the degradation liquid into a reverse osmosis membrane treatment device for carrying out the yield, carrying out the reuse after the reverse osmosis is carried out, and carrying out low-temperature evaporation and crystallization on the reverse osmosis high-salinity concentrated water to generate industrial salt which can be reused; in the step S4, the wet oxidation reactor is a free radical generator, and the free radical generator is loaded with a composite catalyst; the composite catalyst is a LaMnxCo1-xO3 perovskite catalyst, wherein the value of x is 0.01-0.2;
the preparation method of the composite catalyst comprises the following steps: 1) weighing lanthanum soluble salt, manganese soluble salt and cobalt soluble salt according to a stoichiometric ratio, dissolving the lanthanum soluble salt, the manganese soluble salt and the cobalt soluble salt in a certain amount of deionized water to prepare a mixed metal salt solution, adding a certain amount of citric acid, and stirring until the mixed metal salt solution is completely dissolved to form sol; 2) drying the sol, cooling to room temperature, fully grinding and sieving; 3) and adding the sieved powder into a calcining device, and carrying out microwave heating calcination under an air atmosphere to obtain the LaMnxCo1-xO3 type perovskite catalyst.
2. The integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation according to claim 1, characterized in that: the heating source in the evaporator in step S2 is derived from the wet oxidation reactor in step S4.
3. The integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation according to claim 1, characterized in that: the evaporation amount of the wastewater in the step S2 is preferably 15-35% of the total amount of the wastewater.
4. The integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation according to claim 1, characterized in that: and step S3, arranging a wastewater salinity detection device in the distribution tank, connecting the wastewater salinity detection device with the microcomputer controller, and controlling the amount of added condensed water by using the microcomputer controller.
5. The integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation according to claim 1, characterized in that: the free radical generator comprises a high-pressure air feeding device, and the high-pressure air feeding device comprises an air compressor, a high-pressure buffer tank and an air flow meter.
6. The integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation according to claim 1, characterized in that: the halophilic bacteria in the step S5 are halophilic bacteria with high tolerance, which are screened and cultured by utilizing high-salinity wastewater with the concentration of 10-15 wt%.
7. The integrated process for treating high-salinity high-COD industrial wastewater by tubular free radical oxidation according to claim 1, characterized in that: the reverse osmosis membrane in the step S5 is made of cellulose acetate, polyamide or polyimide, and the operation pressure is preferably 1.5-2.5 MPa.
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| CN103357396A (en) * | 2012-04-09 | 2013-10-23 | 中国科学院大连化学物理研究所 | Perovskite hollow ball catalyst having high activity, and preparation and application |
| CN107828773A (en) * | 2017-11-08 | 2018-03-23 | 常州文诺纺织品有限公司 | A kind of preparation method of the domestication agent of the activated sludge of brine waste processing |
| CN109293160A (en) * | 2018-11-07 | 2019-02-01 | 苏州工业园区承叶环境科技有限公司 | A kind for the treatment of process of used water difficult to degradate with high salt |
| CN109759077A (en) * | 2019-01-08 | 2019-05-17 | 南京航空航天大学 | A kind of perovskite oxide catalyst and its preparation method and application |
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