CN115779792A - Method for treating rectifying still residues by using supercritical/subcritical water catalytic oxidation method - Google Patents
Method for treating rectifying still residues by using supercritical/subcritical water catalytic oxidation method Download PDFInfo
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- CN115779792A CN115779792A CN202211441524.5A CN202211441524A CN115779792A CN 115779792 A CN115779792 A CN 115779792A CN 202211441524 A CN202211441524 A CN 202211441524A CN 115779792 A CN115779792 A CN 115779792A
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Abstract
The invention provides a method for treating rectifying still residue by utilizing a supercritical/subcritical water catalytic oxidation method, which takes supercritical/subcritical water as a reaction medium to ensure that organic matters in the still residue and an oxidant have strong catalytic oxidation reaction in the supercritical/subcritical water, and hydrocarbon components in the organic matters are converted into carbon dioxide and water, nitrogen components are converted into nitrogen or ammonia nitrogen, and heteroatom components are converted into corresponding acid or inorganic salt in a short time. The method has the advantages of fast reaction, low energy consumption, difficult generation of secondary pollution and the like, and is more economical and efficient compared with the traditional methods such as incineration and the like.
Description
Technical Field
The invention relates to the field of solid waste disposal in the environmental protection industry, in particular to a method for treating rectifying still residue by utilizing a supercritical/subcritical water catalytic oxidation method.
Background
The DMF rectification kettle residue in the polyurethane synthetic leather industry is a black sticky semi-solid substance, and comprises organic substances such as DMF, polyurethane resin, wood powder, cloth wool and the like, inorganic substances such as light CaCO3 powdery filler and the like and water. According to the division of national records of dangerous waste (2021 edition), the hazardous waste belongs to the hazardous waste.
At present, the disposal mode of kettle residue mainly comprises landfill, incineration and combustion in coal, and the cost is high and secondary pollution is easy to cause. Before the kettle residue is buried, the kettle residue needs to be subjected to solidification and stabilization treatment, so that the volume of a treated object and the treatment cost are greatly increased, and once a containing body is broken, secondary pollution of air, soil, underground water and the like can be caused, so that the landfill is gradually unacceptable by people; incineration is a mainstream rectification kettle residue treatment technology in China, and has the advantages that kettle residues can be rapidly reduced to a greater extent, the toxic and harmful effects of the kettle residues are reduced, the treatment cost is high (about 2000-3500 yuan/ton), and the discharged incineration waste gas contains persistent organic pollutants such as polycyclic aromatic hydrocarbon, dioxin and the like; the distillation kettle residue is mixed into a coal-fired boiler for combustion, so that the heat of organic matters in the kettle residue can be utilized, and the kettle residue is treated. However, inorganic salts in the still residue are separated out in the combustion process and accumulated on the boiler wall, which is easy to cause harm to the boiler, and secondary pollution is also easy to generate when the combustion temperature is low. With the increasing attention of the country to environmental protection in recent years and the enhancement of national environmental protection concepts, the development of the synthetic leather industry cannot meet the increasingly strict environmental protection policy requirements. Although the production process of the novel PU synthetic leather using the water-based polyurethane as the raw material has made great progress, the traditional production process cannot be comprehensively replaced in a short time. Therefore, innovative development of a more economical, efficient and environment-friendly DMF distillation still residue treatment technology is urgently needed.
Disclosure of Invention
Based on the problems, the invention aims to provide a method for treating DMF (dimethyl formamide) rectifying still residues by using a supercritical/subcritical water catalytic oxidation method, which has the advantages of fast reaction, low energy consumption and difficult generation of secondary pollution, and is more economical and efficient compared with the traditional methods such as incineration.
Aiming at the problems, the following technical scheme is provided: a method for treating DMF rectification kettle residue by using a supercritical/subcritical water catalytic oxidation method is characterized by carrying out harmless treatment on the rectification kettle residue according to the following steps:
(1) Filling distillation kettle residues generated by a DMF (dimethyl formamide) distillation tower of a polyurethane synthetic leather enterprise into a high-pressure reaction kettle, and adding water with the mass 5-20 times of that of the kettle residues, oxidant with the chemical oxygen demand 1-10 times of that of the kettle residues and metal oxide catalyst with the mass 0.01-10% of that of the kettle residues;
(2) Heating a high-pressure reaction kettle to 300-500 ℃, wherein the reaction time is 2-30 minutes, so that the kettle residue and an oxidant generate strong catalytic oxidation reaction in supercritical/subcritical water, hydrocarbon components in the kettle residue are converted into carbon dioxide and water, nitrogen components are converted into nitrogen or ammonia nitrogen, and heteroatom components are converted into corresponding acid or inorganic salt;
(3) And after the reaction is finished, recovering the waste heat by using a heat exchanger until the temperature in the reaction kettle is close to room temperature, adsorbing and treating gases such as carbon dioxide, nitrogen and the like in the reaction kettle by using activated carbon, then discharging, mixing the wastewater in the reaction kettle with other production wastewater of an enterprise and domestic sewage of staff, and then discharging into a sewage treatment system for treatment, wherein solid residues in the reaction kettle are mainly metal oxides and are used as catalysts after recovery.
The invention is further set up to use high pressure air, high pressure oxygen or hydrogen peroxide as oxidant.
The present invention is further configured such that a metal oxide such as copper oxide, manganese dioxide, or cerium oxide is used as a catalyst.
The invention is further configured that the catalyst is applied in the form of skeleton metal, wire mesh, metal particles, metal chips, and the like.
The invention further comprises the following steps: the wastewater in the reaction kettle is mixed with other production wastewater of enterprises and domestic sewage of staff, and the reaction tail water with poor biochemical property can be treated by biological treatment processes such as a moving bed biofilm reactor, an anaerobic-anoxic-aerobic method and the like, so that the sewage treatment cost is reduced.
The invention has the beneficial effects that: adopts supercritical fluid green chemical technology, takes supercritical/subcritical water as reaction medium, and carries out catalytic oxidation reaction in a high-pressure reaction kettle. The supercritical/subcritical water is used as a reaction medium, so that organic matters in the kettle residue and an oxidant generate a strong catalytic oxidation reaction in the supercritical/subcritical water, hydrocarbon components in the organic matters are converted into carbon dioxide and water, nitrogen components are converted into nitrogen or ammonia nitrogen, and heteroatom components are converted into corresponding acid or inorganic salt. The method has the advantages of fast reaction, low energy consumption, difficult generation of secondary pollution and the like, realizes the reduction and the harmlessness of the solid waste, and is more economic and efficient compared with the traditional methods such as incineration and the like.
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FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
As shown in figure 1, the method for treating DMF rectification kettle residue by using the supercritical/subcritical water catalytic oxidation method is characterized by comprising the following steps of:
(1) Filling distillation kettle residues generated by a DMF (dimethyl formamide) distillation tower of a polyurethane synthetic leather enterprise into a high-pressure reaction kettle, and adding water with the mass of 5-20 times of that of the kettle residues, oxidant with the chemical oxygen demand of 1-10 times of that of the kettle residues and metal oxide catalyst with the mass of 0.01-10% of that of the kettle residues;
(2) Heating a high-pressure reaction kettle to 300-500 ℃, wherein the reaction time is 2-30 minutes, so that the kettle residue and an oxidant generate strong catalytic oxidation reaction in supercritical/subcritical water, hydrocarbon components in the kettle residue are converted into carbon dioxide and water, nitrogen components are converted into nitrogen or ammonia nitrogen, and heteroatom components are converted into corresponding acid or inorganic salt;
(3) And after the reaction is finished, recovering the waste heat by using a heat exchanger until the temperature in the reaction kettle is close to room temperature, adsorbing and treating gases such as carbon dioxide, nitrogen and the like in the reaction kettle by using activated carbon, then discharging, mixing the wastewater in the reaction kettle with other production wastewater of an enterprise and domestic sewage of staff, and then discharging into a sewage treatment system for treatment, wherein solid residues in the reaction kettle are mainly metal oxides and are used as catalysts after recovery.
In the above steps, high pressure air, high pressure oxygen or hydrogen peroxide is used as an oxidant.
In the above step, a metal oxide such as copper oxide, manganese dioxide, or cerium oxide is used as a catalyst.
In the above steps, the catalyst is applied in the form of framework metal, wire mesh, metal particles, metal chips and the like.
The kettle residue at the bottom of the DMF rectifying tower of the polyurethane synthetic leather enterprise is treated by the steps. The Total Organic Carbon (TOC) content of the still residue sample was determined to be about 0.338g/g. The results of the industrial analysis of the still residue are shown in Table 1, and the results of the elemental analysis are shown in Table 2.
TABLE 1 Industrial analysis results of DMF distillation residue samples
TABLE 2 elemental analysis results of DMF distillation still residue samples
By employing the above procedure, example 1: the mass ratio of kettle residue to water =1, the multiple of oxidant =1.75, the catalyst addition =0.0%, the reaction temperature =400 ℃, and the reaction time =10 minutes. After the reaction is finished, the kettle residue contains Total Organic Carbon (TOC), chemical Oxygen Demand (COD), total Nitrogen (TN) and ammonia Nitrogen (NH) 4 + N) of the wastewater are respectively 98.7 percent, 99.5 percent, 36.5 percent and 50.5 percent, and the wastewater concentration is respectively 325mg/L, 440mg/L, 505mg/L and 432mg/L.
By adopting the above procedure, example 2: the mass ratio of kettle residue to water =1, the multiple of oxidant =1.50, the catalyst addition =0.0%, the reaction temperature =360 ℃, and the reaction time =20 minutes. After the reaction is finished, the kettle residue contains Total Organic Carbon (TOC), chemical Oxygen Demand (COD), total Nitrogen (TN) and ammonia Nitrogen (NH) 4 + -N) of the wastewater are respectively 96.9%, 98.0%, 7.2%, -119.0%, and the wastewater concentrations are respectively 883mg/L, 2095mg/L, 861mg/L and 733mg/L.
By employing the above procedure, example 3: the mass ratio of kettle residue to water =1, the multiple of oxidant =1.50, the addition of CuO catalyst =10%, the reaction temperature =340 ℃, and the reaction time =10 minutes. After the reaction is finished, the kettle residue contains Total Organic Carbon (TOC), chemical Oxygen Demand (COD), total Nitrogen (TN) and ammonia Nitrogen (NH) 4 + The degradation rates of-N) are respectively 98.2%, 98.3%, 4.3%, -149.3%, and the concentrations are respectively 514mg/L, 1856mg/L, 888mg/L and 834mg/L.
In this example, a Moving Bed Biofilm Reactor (MBBR) was used to treat mixed wastewater of reaction wastewater and worker domestic sewage, and the filler addition rate =20% and Chemical Oxygen Demand (COD), total Nitrogen (TN), and ammonia Nitrogen (NH) were added for a Hydraulic Retention Time (HRT) =48 hours 4 + N) and Total Phosphorus (TP) are respectively 71.3%, 92.9%, 99.5% and 55.6%, the concentration is 458mg/L, 14.9mg/L, 0.92mg/L and 12.3mg/L, the three-level standard (GB 8978-1996) meeting the comprehensive discharge standard of sewage can be discharged into a town sewage treatment plant for subsequent treatmentAnd (6) processing.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and those modifications and variations assumed in the above are also considered to be within the protective scope of the present invention.
Claims (5)
1. A method for treating rectifying still residue by utilizing a supercritical/subcritical water catalytic oxidation method is characterized by comprising the following steps of:
(1) Filling distillation kettle residues generated by a DMF (dimethyl formamide) distillation tower of a polyurethane synthetic leather enterprise into a high-pressure reaction kettle, and adding water with the mass of 5-20 times of that of the kettle residues, oxidant with the chemical oxygen demand of 1-10 times of that of the kettle residues and metal oxide catalyst with the mass of 0.01-10% of that of the kettle residues;
(2) Heating a high-pressure reaction kettle to 300-500 ℃, wherein the reaction time is 2-30 minutes, so that the kettle residue and an oxidant generate strong catalytic oxidation reaction in supercritical/subcritical water, hydrocarbon components in the kettle residue are converted into carbon dioxide and water, nitrogen components are converted into nitrogen or ammonia nitrogen, and heteroatom components are converted into corresponding acid or inorganic salt;
(3) And after the reaction is finished, recovering the waste heat by using a heat exchanger until the temperature in the reaction kettle is close to room temperature, adsorbing and treating gases such as carbon dioxide, nitrogen and the like in the reaction kettle by using activated carbon, then discharging, mixing the wastewater in the reaction kettle with other production wastewater of an enterprise and domestic sewage of staff, and then discharging into a sewage treatment system for treatment, wherein solid residues in the reaction kettle are mainly metal oxides and are used as catalysts after recovery.
2. The method for treating the rectifying still residue by using the supercritical/subcritical water catalytic oxidation method according to claim 1, wherein high-pressure air, high-pressure oxygen or hydrogen peroxide is used as an oxidant.
3. The method for treating DMF rectification residue by using supercritical/subcritical water catalytic oxidation method according to claim 1, characterized in that metal oxides such as copper oxide, manganese dioxide, cerium oxide and the like are used as catalysts.
4. The method for treating the rectifying still residue by using the supercritical/subcritical water catalytic oxidation method according to claim 3, wherein the catalyst is applied in the form of skeleton metal, metal wire mesh, metal particles, metal chips and the like.
5. The method for treating the rectifying still residue by the supercritical/subcritical water catalytic oxidation method according to claim 1, wherein the water obtained by mixing the wastewater in the reaction still with the rest of the industrial wastewater of an enterprise and the domestic wastewater of staff is treated by biological treatment processes such as a moving bed biofilm reactor, an anaerobic-anoxic-aerobic method and the like.
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