CN114054472B - Method for degrading halogen-containing organic pollutants - Google Patents
Method for degrading halogen-containing organic pollutants Download PDFInfo
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- CN114054472B CN114054472B CN202111237725.9A CN202111237725A CN114054472B CN 114054472 B CN114054472 B CN 114054472B CN 202111237725 A CN202111237725 A CN 202111237725A CN 114054472 B CN114054472 B CN 114054472B
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- containing organic
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- persulfate
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- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 61
- 150000002367 halogens Chemical class 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000000593 degrading effect Effects 0.000 title claims abstract description 18
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 72
- 238000000227 grinding Methods 0.000 claims abstract description 37
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 31
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000292 calcium oxide Substances 0.000 claims abstract description 25
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000619 316 stainless steel Inorganic materials 0.000 claims description 12
- 239000000356 contaminant Substances 0.000 claims description 11
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 10
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- JHBKHLUZVFWLAG-UHFFFAOYSA-N 1,2,4,5-tetrachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C=C1Cl JHBKHLUZVFWLAG-UHFFFAOYSA-N 0.000 claims description 5
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 5
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 claims description 5
- 239000006148 magnetic separator Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000005360 mashing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- LKPLKUMXSAEKID-UHFFFAOYSA-N pentachloronitrobenzene Chemical compound [O-][N+](=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl LKPLKUMXSAEKID-UHFFFAOYSA-N 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000005416 organic matter Substances 0.000 abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- 230000033558 biomineral tissue development Effects 0.000 abstract description 3
- 238000005695 dehalogenation reaction Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 239000003574 free electron Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000003082 abrasive agent Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 210000000577 adipose tissue Anatomy 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Crushing And Grinding (AREA)
Abstract
The invention discloses a method for degrading halogen-containing organic pollutants, which is characterized by comprising the following steps: the halogen-containing organic matter, persulfate and calcium oxide are mixed and then degraded by adopting a mechanical ball milling method. The invention provides a method for efficiently and thoroughly degrading halogen-containing organic pollutants by taking persulfate as an abrasive and calcium oxide as a grinding aid, wherein during the mechanical ball milling process, the calcium oxide activates the persulfate through the ways of electron transfer, alkali activation, energy transfer and the like, so that the persulfate releases hydroxyl free radicals and sulfate free radicals. The mechanical ball milling has the characteristics of mild reaction conditions, simple operation, wide application range, no secondary pollution and the like, and has obvious advantages in dehalogenation and mineralization of halogen-containing organic pollutants.
Description
Technical Field
The invention relates to the technical field of degradation of halogen-containing organic pollutants, in particular to a method for degrading halogen-containing organic pollutants.
Background
At present, methods commonly used for treating halogen-containing organic pollutants include incineration, biological, catalytic, mechanical ball milling and other technologies. The high-temperature incineration method has high energy consumption cost, and generates other toxic and harmful substances in the treatment process to cause secondary pollution; the treatment time of the biodegradation technology is long, and the degradation effect is not high enough; the catalytic method also has the problems of severe treatment conditions, difficulty in scale up, and the like. The mechanical ball milling method for treating the halogen-containing organic pollutants has the characteristics of mild reaction conditions, simple operation, wide application range, no secondary pollution and the like, and has obvious advantages in dehalogenation and mineralization of the halogen-containing organic pollutants. However, degradation of halogen-containing organics by mechanical ball milling has not been reported at present, mainly because: halogen-containing organics are lipophilic and hydrophobic, so they easily enter the food chain and accumulate in adipose tissues, pose a threat to human health, traditional abrasives include reducing abrasives, lewis base abrasives, neutral abrasives, traditional abrasives cannot degrade contaminants completely, and secondary pollution can occur.
Thus, there is a need for further improvements in the existing methods for containing halogen-containing organic contaminants.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for degrading halogen-containing organic pollutants, which has high degradation rate of halogen-containing organic pollutants and does not have secondary pollution.
The technical scheme adopted for solving the technical problems is as follows: a method for degrading halogen-containing organic contaminants, comprising: the halogen-containing organic matter, persulfate and calcium oxide are mixed and then degraded by adopting a mechanical ball milling method.
Preferably, the halogen-containing organic matter is pretreated before ball milling, the halogen-containing organic matter is dried at 45-55 ℃, smashed, added with a molecular sieve with the diameter of 1.2-2.0mm and cabot carbon black, ground, screened with a 80-mesh screen, and finally the magnetic substances in the mixture are removed by a magnetic separator. The molecular sieve and the organic halide are premixed first, which is favorable for uniform ball milling and mixing in the next step. The molecular sieve has no direct removal effect on organic halide, but in the subsequent ball milling process, a domain limiting effect can be generated under the action of the molecular sieve, and after the domain limiting, the halogen-containing organic matters and persulfate react in a tiny space in a local high concentration mode, so that the reaction efficiency is improved, the carboter carbon black has no direct removal effect, but in the subsequent ball milling process, free electrons generated by calcium oxide can be more rapidly guided to the surface of the persulfate to generate sulfate radical and hydroxyl radical under the action of the carboter carbon black, and the reaction efficiency is improved.
Preferably, the mass ratio of the halogen-containing organic matters to the molecular sieve to the cabot carbon black is 15:1:1-25:1:1.
Preferably, the mass ratio of the total mass of the halogen-containing organic matter, persulfate and calcium oxide to the grinding balls is 1: 20-50; the mass ratio of the halogen-containing organic matters, the persulfates and the calcium oxide is 1:1:1-1:10:10. The ball-milling tank is filled with the grinding balls due to the fact that the mass ratio of the balls is too low, the grinding balls do not have enough space to perform full movement, impact of the grinding balls is reduced, and degradation effect on organic pollutants is weakened; if the mass ratio of the balls is too high, the effective impact of the grinding balls on the materials is less, the accumulation of energy in the system is also lower, and the degradation effect is also reduced. In the mass ratio of the halogen-containing organic matters, the persulfates and the calcium oxide, if the content of the halogen-containing organic matters is too high and the mass sum of the persulfates and the calcium oxide is too low, the persulfates cannot be fully contacted with the calcium oxide and cannot be well activated, so that the removal efficiency is reduced; if the content of halogen-containing organic matters is too low and the mass sum of persulfate and calcium oxide is too high, the persulfate may be in direct contact with the halogen-containing organic matters and not be activated well, thereby reducing the removal efficiency. Under a proper mass ratio, the calcium oxide grinding aid releases free electrons in the ball milling process, so that the persulfate grinding aid is effectively activated, sulfate free radicals and hydroxyl free radicals with strong oxidability can be generated under the ball milling condition after the persulfate grinding aid is activated by the free electrons, the free radicals attack halogen-containing organic matters to destroy carbon halogen bonds of the persulfate grinding aid and generate ring-opening reaction, and meanwhile, the persulfate can oxidize the halogen-containing organic matters, so that the purpose of degrading the halogen-containing organic matters is always achieved.
Preferably, the rotation speed of the ball mill is 800-1500 rpm, and the grinding time is 3-5 h. The energy generated by too low ball mill rotation speed and too short grinding time can not fully activate the persulfate by the calcium oxide, so that the degradation effect is not achieved, and the too high ball mill rotation speed and too long grinding time can cause secondary pollutants to be generated, so that the degradation purpose is not achieved.
Preferably, the ball milling mode of the ball mill is vibration ball milling, the materials of the grinding balls and the ball milling tank are 316 stainless steel, the ball size is 8-10mm, the volume of the ball milling tank is 200mL, and the total mass of each time halogen-containing organic matters, sodium persulfate and calcium oxide is 10-20 g. The vibration ball milling is performed in a vibration mode, and compared with a traditional ball milling machine, the vibration ball milling machine is easy to perform amplification experiments, has low energy consumption and can accommodate more pollutants, so that the halogen-containing organic matters can be degraded in one step. The stainless steel grinding ball has higher collision energy and is economical and durable. Undersize can result in lower collision energy due to its light weight, and failure to input energy can not effectively activate the abrasive, and thus can not completely degrade contaminants. The large-size grinding balls can generate larger collision energy, but because the large-size grinding balls are limited by the volume of the ball milling tank, the number of the grinding balls which can be put is small, the impact frequency is low, and the capability of degrading pollutants is reduced due to insufficient energy generated, in addition, dead angles are easy to generate when the large-size grinding balls move in the ball milling tank, the ball milling reaction is insufficient due to the fact that the ball milling reaction is unfavorable for fully milling materials, and therefore the pollutants cannot be completely degraded.
Preferably, the persulfate is sodium persulfate.
Preferably, the halogen-containing organic matter is at least one of 2, 4-dichlorophenol, hexachloroethane, 1,2,4, 5-tetrachlorobenzene, pentachloronitrobenzene and tetrabromobisphenol A.
Preferably, the degradation rate of the halogen-containing organic matter is 90% or more.
Compared with the prior art, the invention has the advantages that: the invention provides a method for efficiently and thoroughly degrading halogen-containing organic pollutants by taking persulfate as an abrasive and calcium oxide as a grinding aid, wherein during the mechanical ball milling process, the calcium oxide activates the persulfate through the ways of electron transfer, alkali activation, energy transfer and the like, so that the persulfate releases hydroxyl free radicals and sulfate free radicals. The mechanical ball milling has the characteristics of mild reaction conditions, simple operation, wide application range, no secondary pollution and the like, and has obvious advantages in dehalogenation and mineralization of halogen-containing organic pollutants.
Detailed Description
The present invention is described in further detail below with reference to examples.
The invention provides 4 examples and 2 comparative examples, wherein the examples and the comparative examples are prepared by pretreating halogen-containing organic matters before ball milling, drying the halogen-containing organic matters in a vacuum drying oven at 50 ℃, then mashing, adding 0.05g SBA-15 molecular sieve with the diameter of 1.2-2.0mm and 0.05g REGAL 400R cabobot carbon black, grinding, sieving with a 80-mesh screen, and finally removing magnetic matters in the mixture by using a magnetic separator.
Example 1
1g of 2, 4-dichlorophenol, 6.5g of calcium oxide and 6.5g of sodium persulfate are weighed, 420g of 316 stainless steel balls with different diameters of 8-10mm are placed in a 200mL 316 stainless steel ball grinding tank, the ball grinding tank is placed in a ball mill, the ball milling mode is vibration ball milling, the rotating speed is 1200rpm, the time is 3h, the ball milling process is working for 30min, the interval is 5min, and the process is sequentially and circularly carried out. The samples before and after the reaction were subjected to the processes of dissolution, ultrasound, centrifugation, filtration, dilution, and the like, and were measured using a weather chromatograph.
Example 2
1g of hexachloroethane, 6.5g of calcium oxide and 6.5g of sodium persulfate are weighed, 420g of 316 stainless steel balls with different diameters of 8-10mm are placed in a 200mL 316 stainless steel ball grinding tank, the ball grinding tank is placed in a ball mill, the ball milling mode is vibration ball milling, the rotating speed is set to be 1000rpm, the time is 5h, the ball milling process is operated for 30min, and the interval is 5min, and the process is sequentially and circularly carried out. The samples before and after the reaction were subjected to the processes of dissolution, ultrasound, centrifugation, filtration, dilution, and the like, and were measured using a weather chromatograph.
Example 3
1g of 1,2,4, 5-tetrachlorobenzene, 6.5g of calcium oxide and 6.5g of sodium persulfate are weighed, 420g of 316 stainless steel balls with different diameters of 8-10mm are placed in a 200mL 316 stainless steel ball grinding tank, the ball grinding tank is placed in a ball mill, the ball milling mode is vibration ball milling, the rotating speed is 800rpm, the time is 5h, the ball milling process is working for 30min, and the interval is 5min, and the process is sequentially and circularly carried out. The samples before and after the reaction were subjected to the processes of dissolution, ultrasound, centrifugation, filtration, dilution, and the like, and were measured using a weather chromatograph.
Example 4
1g of tetrabromobisphenol A, 6.5g of calcium oxide and 6.5g of sodium persulfate are weighed, 420g of 316 stainless steel balls with the diameters of 8-10mm are placed in a 200mL 316 stainless steel ball grinding tank, the ball grinding tank is placed in a ball mill, the ball milling mode is vibration ball milling, the rotating speed is 1200rpm, the time is 3h, the ball milling process works for 30min, and the interval is 5min, and the process is sequentially and circularly carried out. The samples before and after the reaction were subjected to the processes of dissolution, sonication, centrifugation, filtration, dilution, and the like, and were measured using liquid chromatography.
Comparative example 1
1g of tetrabromobisphenol A, 420g of 316 stainless steel balls with the diameters of 8-10mm and a 200mL ball milling tank are weighed, the ball milling tank is placed in a ball mill, the ball milling mode is vibration ball milling, the rotating speed is 1200rpm, the time is 5h, the ball milling process is 30min, and the intervals are 5min, and the process is sequentially and circularly carried out. The samples before and after the reaction were subjected to the processes of dissolution, sonication, centrifugation, filtration, dilution, and the like, and were measured using liquid chromatography.
Comparative example 2
Weighing tetrabromobisphenol A1 g, fe-SO 2 6.5g of reagent, 420g of 316 stainless steel balls with different diameters of 8-10mm and a 200mL ball milling tank, wherein the ball milling tank is arranged in a ball mill, the ball milling mode is vibration ball milling, the rotating speed is 1200rpm, the time is 5h, and the ball milling process is 3 workAnd (5) carrying out circulation in sequence at intervals of 5min for 0 min. The samples before and after the reaction were subjected to the processes of dissolution, sonication, centrifugation, filtration, dilution, and the like, and were measured using liquid chromatography.
The obtained 4 examples and 2 comparative examples are subjected to tests before and after ball milling of pollutants, and the specific test method is as follows:
before and after ball milling, 0.05g of the materials in each pot is taken into a 10mL centrifuge tube, 10mL of normal hexane is added, ultrasonic dissolution is carried out for 20min, centrifugation is carried out at 8000rpm for 1min, filtration is carried out through a 0.25 mu m organic filter membrane, the model of high-efficiency gas chromatography used in the experiment is Agilent 6890, and a chromatographic column is an HP-INNOWAX capillary column (30 m multiplied by 0.32mm multiplied by 0.5 mu m) and a flame ionization detector is adopted. After 4 hours of treatment, the pollution concentration of 2, 4-dichlorophenol before ball milling in example 1 was 71.4mg/kg, and the pollution concentration of 2, 4-dichlorophenol after ball milling was 0mg/kg. Example 2 the concentration of hexachloroethane before ball milling was 71.4mg/kg and the concentration of hexachloroethane after ball milling was 0.65mg/kg. Example 3 the concentration of 1,2,4, 5-tetrachlorobenzene contamination before ball milling was 71.4mg/kg and the concentration of 1,2,4, 5-tetrachlorobenzene contamination after ball milling was 0.65mg/kg. Example 4 tetrabromobisphenol A contamination concentration before ball milling was 71.4mg/kg, and tetrabromobisphenol A contamination concentration after ball milling was 0mg/kg. Comparative example 1 tetrabromobisphenol A contamination concentration before ball milling was 71.4mg/kg, and tetrabromobisphenol A contamination concentration after ball milling was 71.4mg/kg. Comparative example 2 tetrabromobisphenol A contamination concentration before ball milling was 71.4mg/kg, and tetrabromobisphenol A contamination concentration after ball milling was 44.3mg/kg.
Under the conditions of proper mass ratio, rotating speed, grinding ball size and materials, the calcium oxide grinding aid releases free electrons in the ball milling process, the free electrons are rapidly transferred to the surface of the persulfate grinding aid under the action of the cabot carbon black, the persulfate grinding aid is activated after capturing the free electrons, the activated persulfate grinding aid can generate sulfate radical and hydroxyl radical with strong oxidizing property under the ball milling condition, the free radicals attack halogen-containing organic matters, a limited field effect is generated under the influence of a molecular sieve, the halogen-containing organic matters and the persulfate react in a local high concentration in a tiny space after the limited field, carbon halogen bonds of the halogen-containing organic matters are broken, ring-opening reaction is generated, meanwhile, inorganic matters such as sodium sulfate, sodium chloride and the like are generated, so that the purpose of harmless pollutants is achieved.
Claims (7)
1. A method for degrading halogen-containing organic contaminants, comprising: mixing halogen-containing organic matters, persulfate and calcium oxide, and then degrading the halogen-containing organic pollutants by adopting a ball milling method of a ball mill; the mass ratio of the halogen-containing organic matters to the persulfates to the calcium oxide is 1:1:1-1:10:10; pretreating the halogen-containing organic matters before ball milling, drying the halogen-containing organic matters at 45-55 ℃, mashing, adding a molecular sieve with the diameter of 1.2-2.0mm and cabot carbon black, grinding, sieving with a 80-mesh sieve, and finally removing magnetic matters in the mixture by using a magnetic separator; the mass ratio of the halogen-containing organic matters to the molecular sieve to the cabot carbon black is 15:1:1-25:1:1.
2. A method of degrading halogen-containing organic contaminants according to claim 1 wherein: the mass ratio of the total mass of the halogen-containing organic matters, the persulfates and the calcium oxide to the grinding balls is 1: 20-50.
3. A method of degrading halogen-containing organic contaminants according to claim 1 wherein: the rotating speed of the ball mill is 800-1500 rpm, and the grinding time is 3-5 h.
4. A method of degrading halogen-containing organic contaminants according to claim 1 wherein: the ball milling mode of the ball mill adopts the materials of a vibration ball milling ball and a ball milling tank of 316 stainless steel, the ball size is 8-10mm, the volume of the ball milling tank is 200mL, and the total mass of each time halogen-containing organic matters, sodium persulfate and calcium oxide are added is 10-20 g.
5. A method of degrading halogen-containing organic contaminants according to claim 1 wherein: the persulfate is sodium persulfate.
6. A method of degrading halogen-containing organic contaminants according to claim 1 wherein: the halogen-containing organic pollutant is at least one of 2, 4-dichlorophenol, hexachloroethane, 1,2,4, 5-tetrachlorobenzene, pentachloronitrobenzene and tetrabromobisphenol A.
7. A method of degrading halogen-containing organic contaminants according to any one of claims 1 to 6, characterized in that: the degradation rate of the halogen-containing organic matters is more than 90 percent.
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