CN113975702A - Method for removing dioxin POPs in copper smelting soot through synergistic retardation of microwave and sulfuric acid - Google Patents
Method for removing dioxin POPs in copper smelting soot through synergistic retardation of microwave and sulfuric acid Download PDFInfo
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- CN113975702A CN113975702A CN202111196816.2A CN202111196816A CN113975702A CN 113975702 A CN113975702 A CN 113975702A CN 202111196816 A CN202111196816 A CN 202111196816A CN 113975702 A CN113975702 A CN 113975702A
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- 239000004071 soot Substances 0.000 title claims abstract description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000003723 Smelting Methods 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000010949 copper Substances 0.000 title claims abstract description 36
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 25
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 238000010438 heat treatment Methods 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- 238000010521 absorption reaction Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000003077 lignite Substances 0.000 claims description 9
- 238000009736 wetting Methods 0.000 claims description 8
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003830 anthracite Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002802 bituminous coal Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 230000000185 dioxinlike effect Effects 0.000 claims 2
- 230000000979 retarding effect Effects 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002956 ash Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 25
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 25
- 239000002912 waste gas Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- 238000005507 spraying Methods 0.000 description 6
- 239000010881 fly ash Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 150000002013 dioxins Chemical class 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011494 foam glass Substances 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009284 supercritical water oxidation Methods 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004827 dibenzo-1,4-dioxins Chemical class 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
- A62D3/178—Microwave radiations, i.e. radiation having a wavelength of about 0.3 cm to 30cm
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/08—Toxic combustion residues, e.g. toxic substances contained in fly ash from waste incineration
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
Abstract
The invention discloses a method for removing dioxin POPs (persistent organic pollutants) in copper smelting soot by microwave and sulfuric acid synergistic retardation. The method removes dioxin POPs in copper smelting soot in a microwave tube furnace under a low-temperature condition, and the degradation rate of the dioxin in the copper smelting soot is as high as 99.95 percent. The method has the advantages of simple and easily controlled process, clean product, little pollution, low energy consumption and high degradation rate, and is suitable for wide industrial popularization and application.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for removing dioxin POPs from copper smelting soot by microwave and sulfuric acid synergistic retardation.
Background
With the rapid development of modern industry and agriculture, people pay more and more attention to a safe, efficient, clean and environment-friendly development mode on the basis of pursuing economic value, and the pollution problems of unintentionally generated Persistent Organic Pollutants (POPs), particularly dioxin and the like, are widely concerned by people. POPs are the most difficult to degrade organic pollutants existing in nature, the most common are polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and the like, and dioxins are one of the most important parts of POPs, have the characteristics of strong toxicity, high toxicity, durability, bioaccumulation and long-distance mobility, have lipophilicity, are hardly naturally discharged out of a human body after being fused into the human body, and have the hazards of carcinogenesis, distortion and mutation on the human body. Among them, 2,3,7, 8-tetrachlorodibenzodioxin (2, 3,7, 8-TCDD) is known as the most toxic compound at present.
Dioxin is various in types and is discharged in the chemical production industry, household garbage incineration, medical waste treatment and other aspects. Particularly in the secondary nonferrous resource smelting industry, the production of secondary copper is one of the industries with the most discharge of dioxin in China, and copper ash generated by a blast furnace process contains a large amount of pollutants such as dioxin. A great deal of research is carried out at home and abroad aiming at the removal of dioxin pollutants in solid wastes. The development of the method for many years forms methods such as an incineration method, a pyrolysis method, a supercritical water oxidation method, an electrochemical dechlorination technology, a biodegradation technology and the like. The methods have more or less some disadvantages, such as better treatment effect of the incineration method and the pyrolysis method, but secondary pollution is accompanied in the process and the high temperature environment has high requirement on the high temperature resistance of the incinerator; the supercritical water oxidation method has the problems of high energy consumption, easy corrosion of a device, undefined reaction mechanism and the like, the electric quantity consumption of the electrochemical dechlorination technology is extremely high, the treatment degree of the biodegradation technology is low, and the difficulty of slow process needs to be further overcome.
Chinese patent application No. CN 101293173B, a method for treating dioxin in fly ash, discloses an economical, efficient and secondary pollution-free method for degrading dioxin in fly ash of a garbage incinerator, in which a surfactant aqueous solution is used to extract dioxin in fly ash, an extraction solution containing dioxin after dehydration and filtration is acidified with an acidifying agent, then heated to 30-100 ℃ in air or enriched air, and the dioxin is degraded by the catalytic action of metal ions in the extraction solution, and the degradation rate of substances such as dioxin after treatment reaches 70-99%.
Chinese patent CN 109437573A discloses a harmless treatment method for waste incineration fly ash dioxin, the method mixes and presses waste glass powder, acid-washing sludge and dolomite powder to prepare foam glass ceramics through high-temperature melting, the dioxin in the fly ash is cracked at high temperature and reacts with alkaline earth metal oxide to be solidified in the foam glass ceramics, the generated flue gas is rapidly cooled to below 200 ℃ through a quenching device, and the dioxin is prevented from being synthesized again by residual chloride.
The invention aims to provide a method for efficiently degrading dioxin POPs compounds in copper smelting soot at low temperature, which has wide applicability.
Disclosure of Invention
The invention aims to provide a method for removing dioxin POPs in copper smelting soot by microwave and sulfuric acid synergistic retardation.
The invention aims to realize the method for removing dioxin POPs in copper smelting soot by microwave and sulfuric acid synergistic retardation, which comprises the following steps: wetting copper smelting soot with water, adding concentrated sulfuric acid and carbonaceous powder, fully stirring and mixing, standing for 6-12 hours to obtain a mixture, placing the mixture in a microwave tube type heating furnace in an air atmosphere, roasting to obtain sintering slag and tail gas, and collecting and treating the generated tail gas with an absorption liquid and then discharging.
The principle of the invention is as follows:
in the air atmosphere and in the microwave heating process, concentrated sulfuric acid in the system is decomposed to generate sulfur trioxide, and the sulfur trioxide reacts with carbonaceous powder at high temperature to generate SO2The sulfur dioxide gas can effectively prevent the dioxin precursor pentachlorophenol (PCP) from being combined with chlorine to form dioxinThe process of the dioxin realizes the purpose of efficiently removing the UPOPs of the dioxins in the soot.
The invention has the beneficial effects that:
the method removes dioxin POPs in copper smelting soot in a microwave tube furnace under a low-temperature condition, and the degradation rate of the dioxin in the copper smelting soot is as high as 99.95 percent. The quartz glass tube is sleeved in the microwave tube type furnace, so that the heating device can be effectively prevented from being corroded; the air is introduced to roast the soot and sulfuric acid mixture, so that the roasted gas product can be taken out of the microwave tube furnace, the absorption liquid is prevented from being sucked backwards, and the heating device is effectively protected. In addition, exhaust gas such as SO generated by calcination2、CO2、Cl2The waste water is collected and discharged in sequence, and then is absorbed and treated by sodium hydroxide solution and water in sequence, and then is discharged into the atmosphere, so that the environmental pollution is avoided. The method has the advantages of simple and easily controlled process, clean product, little pollution, low energy consumption and high degradation rate, and is suitable for wide industrial popularization and application.
Drawings
FIG. 1 is a flow chart of the method for removing POPs in copper smelting soot by microwave and sulfuric acid synergistic retardation.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
The invention relates to a method for removing dioxin POPs from copper smelting soot by microwave and sulfuric acid synergistic retardation, which is shown in figure 1, wherein a certain amount of water is sprayed on the copper smelting soot, concentrated sulfuric acid and carbonaceous powder are added to be fully mixed to obtain a mixture, the mixture is placed still for 6 to 12 hours, then air or oxygen is introduced into a microwave tube type heating furnace for roasting, and the generated SO2、CO2、Cl2And the tail gas is discharged after being collected and treated by the absorption liquid, and the sintering slag generated by roasting has high lead and zinc contents and can be used as a lead-zinc smelting raw material for secondary utilization.
The spraying water amount is 5-10% of the mass of the soot, the adding amount of concentrated sulfuric acid is 0.5-1.0 time of the mass of the soot, and the adding amount of carbonaceous powder is 3% -5% of the mass of the soot.
The concentrated sulfuric acid concentration is 98%.
The microwave power of the microwave tube type heating furnace is 200-1000W, and the microwave heating frequency is 2450 MHz.
And the gas inlet of the microwave tube type heating furnace is connected with a gas source, and the gas outlet of the microwave tube type heating furnace is connected with a gas collecting device.
The roasting mode is as follows: introducing air with the flow rate of 20-50L/h into a microwave tube type heating furnace, heating to 200-400 ℃, and then preserving heat for 1-3 h.
The temperature of the mixture is raised to 200-400 ℃ within 50-120 s.
Tail gas generated by roasting the soot is collected and then sequentially absorbed and treated by alkaline solution and water.
The alkaline solution is 15% -30% of sodium hydroxide solution.
The carbonaceous powder is one or more of lignite, bituminous coal or anthracite.
Example 1
Spraying water with the mass of 10% of the ash in the copper smelting ash, wetting, mixing the ash, 98% concentrated sulfuric acid and lignite according to the mass ratio of 100:50:3, fully stirring to form a mixture, and standing for 12 hours.
Putting 1kg of the mixture into a tubular microwave heating device with microwave heating frequency of 2450MHz, controlling the air flow to be 25L/h and the microwave power to be 500W, heating to 300 ℃ and preserving the heat for 1 hour to obtain sinter and waste gas, absorbing acid gases such as sulfur dioxide, carbon monoxide, chlorine and the like in the waste gas by using a 20% sodium hydroxide solution, and performing secondary absorption by using water after the acid gases are not completely absorbed in the sodium hydroxide solution.
And detecting the sinter, wherein the degradation rate of the dioxin in the soot reaches 98.4%.
Example 2
Spraying water with the mass of 6% of the ash in the copper smelting ash, wetting, mixing the ash, 98% concentrated sulfuric acid and lignite according to the mass ratio of 100:60:3, fully stirring to form a mixture, and standing for 11 hours.
Putting 1kg of the mixture into a tubular microwave heating device with microwave heating frequency of 2450MHz, controlling the air flow to be 30L/h and the microwave power to be 400W, heating to 200 ℃ and preserving the heat for 1 hour to obtain sinter and waste gas, absorbing acid gases such as sulfur dioxide, carbon monoxide, chlorine and the like in the waste gas by using a 20% sodium hydroxide solution, and performing secondary absorption by using water after the acid gases are not completely absorbed in the sodium hydroxide solution.
And detecting the sinter, wherein the degradation rate of the dioxin in the soot reaches 98.8%.
Example 3
Spraying water with the mass of 7% of the ash in the copper smelting ash, wetting, mixing the ash, 98% concentrated sulfuric acid and lignite according to the mass ratio of 30:20:1, fully stirring to form a mixture, and standing for 6 hours.
Putting 1kg of the mixture into a tubular microwave heating device with microwave heating frequency of 2450MHz, controlling the air flow to be 35L/h and the microwave power to be 700W, heating to 250 ℃, and preserving the heat for 2 hours to obtain sinter and waste gas, wherein acid gases such as sulfur dioxide, carbon monoxide, chlorine and the like in the waste gas are absorbed by 15 percent sodium hydroxide solution, and water is used for secondary absorption after the acid gases are not completely absorbed by the sodium hydroxide solution.
And detecting the sinter, wherein the degradation rate of the dioxin in the soot reaches 99.2%.
Example 4
Spraying water with the mass of 8% of the ash in the copper smelting ash, wetting, mixing the ash, 98% concentrated sulfuric acid and lignite according to the mass ratio of 30:25:1, fully stirring to form a mixture, and standing for 7 hours.
Putting 1kg of the mixture into a tubular microwave heating device with microwave heating frequency of 2450MHz, controlling the air flow rate to be 40L/h and the microwave power to be 600W, heating to 300 ℃ and preserving heat for 3 hours to obtain sinter and waste gas, absorbing acid gases such as sulfur dioxide, carbon monoxide, chlorine and the like in the waste gas by using a 15% sodium hydroxide solution, and performing secondary absorption by using water after the acid gases are not completely absorbed in the sodium hydroxide solution.
And detecting the sinter, wherein the degradation rate of the dioxin in the soot reaches 99.4%.
Example 5
Spraying water with the mass of 9% of the ash in the copper smelting ash, wetting, mixing the ash, 98% concentrated sulfuric acid and lignite according to the mass ratio of 100:60:4, fully stirring to form a mixture, and standing for 10 hours.
Putting 1kg of the mixture into a tubular microwave heating device with microwave heating frequency of 2450MHz, controlling the air flow rate to be 20L/h and the microwave power to be 300W, heating to 350 ℃ and preserving the heat for 2.5 hours to obtain sinter and waste gas, absorbing acid gases such as sulfur dioxide, carbon monoxide, chlorine and the like in the waste gas by using 15% sodium hydroxide solution, and performing secondary absorption by using water after the sodium hydroxide solution is used for preventing incomplete absorption.
And detecting the sinter, wherein the degradation rate of the dioxin in the soot reaches 99.8%.
Example 6
After the copper smelting soot is wetted by water with the mass of 10% of the soot, 98% concentrated sulfuric acid and lignite are mixed according to the mass ratio of 100:80:5, fully stirred into a mixture, and kept stand for 9 hours.
Putting 1kg of the mixture into a tubular microwave heating device with microwave heating frequency of 2450MHz, controlling the air flow rate to be 50L/h and the microwave power to be 800W, heating to 400 ℃, preserving the heat for 2.5 hours to obtain sinter and waste gas, absorbing acid gases such as sulfur dioxide, carbon monoxide, chlorine and the like in the waste gas by using 25% sodium hydroxide solution, and performing secondary absorption by using water after the sodium hydroxide solution is used for preventing incomplete absorption.
And detecting the sinter, wherein the degradation rate of the dioxin in the soot reaches 99.95 percent.
Example 7
Adding water with the mass of 8% of the soot into the copper smelting soot, mixing the soot, 98% concentrated sulfuric acid and bituminous coal according to the mass ratio of 100:70:4, fully stirring the mixture into a mixture, and standing the mixture for 8 hours.
Putting 1kg of the mixture into a tubular microwave heating device with microwave heating frequency of 2450MHz, controlling the air flow to be 35L/h and the microwave power to be 1000W, heating to 400 ℃, and preserving the heat for 1 hour to obtain sinter and waste gas, wherein acid gases such as sulfur dioxide, carbon monoxide, chlorine and the like in the waste gas are absorbed by 30 percent sodium hydroxide solution, and water is used for secondary absorption after the sodium hydroxide solution is used for preventing incomplete absorption.
And detecting the sinter, wherein the degradation rate of the dioxin in the soot reaches 99.71 percent.
Example 8
Adding water with the mass of 6% of the ash into the copper smelting ash, mixing the ash, 98% concentrated sulfuric acid and anthracite according to the mass ratio of 100:50:3, fully stirring to form a mixture, and standing for 12 hours.
Putting 1kg of the mixture into a tubular microwave heating device with microwave heating frequency of 2450MHz, controlling the air flow rate to be 20L/h and the microwave power to be 900W, heating to 200 ℃ and preserving the heat for 2.5 hours to obtain sinter and waste gas, absorbing acid gases such as sulfur dioxide, carbon monoxide, chlorine and the like in the waste gas by using 15% sodium hydroxide solution, and performing secondary absorption by using water after the sodium hydroxide solution is used for preventing incomplete absorption.
And detecting the sinter, wherein the degradation rate of the dioxin in the soot reaches 99.58%.
Example 9
Adding water with the mass of 6% of the ash into the copper smelting ash, mixing the ash, 98% concentrated sulfuric acid, anthracite and lignite according to the mass ratio of 100:63:1:2, fully stirring to form a mixture, and standing for 8 hours.
Putting 1kg of the mixture into a tubular microwave heating device with microwave heating frequency of 2450MHz, controlling the air flow to be 35L/h and the microwave power to be 850W, heating to 120 ℃, and preserving the heat for 1.5 hours to obtain sinter and waste gas, wherein acid gases such as sulfur dioxide, carbon monoxide, chlorine and the like in the waste gas are absorbed by 15 percent sodium hydroxide solution, and water is used for secondary absorption after the sodium hydroxide solution is used for preventing incomplete absorption.
And detecting the sinter, wherein the degradation rate of the dioxin in the soot reaches 99.77%.
Example 10
Adding water with the mass of 6% of the ash into the copper smelting ash, mixing the ash, 98% concentrated sulfuric acid and anthracite according to the mass ratio of 100:68:3, fully stirring to form a mixture, and standing for 10 hours.
Putting 1kg of the mixture into a tubular microwave heating device with microwave heating frequency of 2450MHz, controlling the air flow rate to be 40L/h and the microwave power to be 850W, heating to 130 ℃, keeping the temperature for 1.2 hours to obtain sinter and waste gas, absorbing acid gases such as sulfur dioxide, carbon monoxide, chlorine and the like in the waste gas by using 25% sodium hydroxide solution, and performing secondary absorption by using water after the sodium hydroxide solution is used for preventing incomplete absorption.
And detecting the sinter, wherein the degradation rate of the dioxin in the soot reaches 99.49 percent.
Claims (8)
1. A method for removing dioxin POPs in copper smelting soot by microwave and sulfuric acid synergistic retardation is characterized by comprising the steps of wetting the copper smelting soot with water, adding concentrated sulfuric acid and carbonaceous powder, fully stirring and mixing, standing for 6-12 hours to obtain a mixture, roasting the mixture in a microwave tube type heating furnace in an air atmosphere to obtain sintering slag and tail gas, and collecting and treating the generated tail gas by an absorption liquid and then discharging the tail gas.
2. The method for removing dioxin POPs from copper smelting soot through synergistic retardation of microwave and sulfuric acid according to claim 1, wherein the amount of water added for wetting the soot is 5-10% of the mass of the soot, the amount of concentrated sulfuric acid added is 0.5-1.0 times of the mass of the soot, and the amount of carbonaceous powder added is 3% -5% of the mass of the soot.
3. The method for removing dioxin-like POPs from copper smelting soot by microwave-sulfuric acid synergistic retardation according to claim 1 or 2, wherein the concentrated sulfuric acid concentration is 98%.
4. The method for removing dioxin POPs from copper smelting soot by microwave and sulfuric acid synergistic retardation is characterized in that the roasting mode is as follows: introducing air with the flow rate of 20-50L/h into a microwave tube type heating furnace, heating to 200-400 ℃, and then preserving heat for 1-3 h.
5. The method for removing dioxin POPs from copper smelting soot through microwave and sulfuric acid synergistic retardation according to claim 1, wherein the microwave power of the microwave tube type heating furnace is 200-1000W, and the microwave heating frequency is 2450 MHz.
6. The method for removing dioxin POPs from copper smelting soot by microwave-sulfuric acid synergistic retardation according to claim 1, wherein tail gas generated by soot roasting is collected and sequentially subjected to alkaline solution and water absorption treatment.
7. The method for removing dioxin POPs from copper smelting soot through synergistic retarding of microwave and sulfuric acid according to claim 6, wherein the alkaline solution is 15% -30% of sodium hydroxide solution.
8. The method for removing dioxin-like POPs from copper smelting soot by microwave-sulfuric acid synergistic retardation according to claim 1, wherein the carbonaceous powder is one or more of lignite, bituminous coal or anthracite.
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Application publication date: 20220128 |