CN116531710A - Method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid substances by mechanochemical reduction - Google Patents
Method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid substances by mechanochemical reduction Download PDFInfo
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- CN116531710A CN116531710A CN202310493156.7A CN202310493156A CN116531710A CN 116531710 A CN116531710 A CN 116531710A CN 202310493156 A CN202310493156 A CN 202310493156A CN 116531710 A CN116531710 A CN 116531710A
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- perfluoro
- sulfonic acid
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- polyfluoroalkyl
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- -1 perfluoro Chemical group 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 48
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 40
- 239000000126 substance Substances 0.000 title claims abstract description 30
- 230000000593 degrading effect Effects 0.000 title claims abstract description 22
- 230000009467 reduction Effects 0.000 title claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000000227 grinding Methods 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006731 degradation reaction Methods 0.000 claims abstract description 29
- 230000015556 catabolic process Effects 0.000 claims abstract description 21
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000002910 solid waste Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 claims description 4
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229960004887 ferric hydroxide Drugs 0.000 claims 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims 1
- 238000006115 defluorination reaction Methods 0.000 abstract description 47
- 239000007787 solid Substances 0.000 abstract description 23
- 238000010303 mechanochemical reaction Methods 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 6
- WFRUBUQWJYMMRQ-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WFRUBUQWJYMMRQ-UHFFFAOYSA-M 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 231100000086 high toxicity Toxicity 0.000 abstract description 2
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 150000003460 sulfonic acids Chemical class 0.000 abstract description 2
- 239000002920 hazardous waste Substances 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 59
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- 101001136034 Homo sapiens Phosphoribosylformylglycinamidine synthase Proteins 0.000 description 10
- 102100036473 Phosphoribosylformylglycinamidine synthase Human genes 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 229910002706 AlOOH Inorganic materials 0.000 description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- QDHFHIQKOVNCNC-UHFFFAOYSA-M butane-1-sulfonate Chemical compound CCCCS([O-])(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-M 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- WLGDAKIJYPIYLR-UHFFFAOYSA-M octane-1-sulfonate Chemical compound CCCCCCCCS([O-])(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-M 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002939 oilproofing Substances 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 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
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid substances by mechanochemical reduction, belonging to the technical field of high-toxicity organic solid waste treatment. The invention discloses a mechanochemical method which takes zinc powder, iron powder and metal compounds (oxide, hydroxide or oxyhydroxide) as ternary grinding agents, and realizes complete degradation and defluorination of solid hazardous waste of perfluoro/polyfluoroalkyl sulfonic acids. Compared with a single-element and binary-element grinding agent system, the defluorination efficiency of the method is higher, and the defluorination rate of the potassium perfluorooctane sulfonate can reach 100% after 3 hours of mechanochemical reaction. Compared with the existing mechanochemical treatment method, the method has the advantages of low cost, no toxicity, easy obtainment, milder mechanochemical reaction conditions, short treatment time, lower energy consumption and higher efficiency.
Description
Technical Field
The invention belongs to the technical field of high-toxicity organic solid waste treatment, and particularly relates to a method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid substances by mechanochemical reduction, in particular to a degradation method for converting perfluoro/polyfluoroalkyl sulfonic acid substances into non-toxic substances by taking aluminum oxide, zinc and iron metals as mixed grinding agents and utilizing mechanochemical action.
Background
Perfluoro/polyfluoroalkyl sulfonic acid is a widely used surfactant, but is a new pollutant which is mainly controlled by China due to strong chemical stability and high ecological toxicity. Perfluorooctanesulfonic acid (PFOS) was listed as a Persistent Organic Pollutant (POPs) in 2009, and thereafter, various perfluoro/polyfluoroalkyl sulfonic acids (pfacs) having 4 to 6 perfluorocarbons were mass-produced and used as their substitutes. The substances have the characteristics of hydrophobic and oleophobic properties, and are often used as oil-proofing agents, dust-proofing agents, pesticides, surfactants, antifogging agents and the like in the field of industrial and civil product production. Pfases are chemically stable and difficult to handle biologically and chemically. Therefore, PFASs elimination technology is receiving a great deal of attention.
At present, the related PFASs elimination technology is mainly aimed at degrading and removing PFASs in water, and the technical attention of PFASs removal in solid waste is insufficient. However, pfases exist in solid media with longer half-lives and may migrate to the body of water causing secondary water pollution. High temperature incineration under aerobic conditions is a common method for treating solid waste, but perfluoro compound incineration is easy to generate greenhouse gas CF 4 And C 2 F 4 Or a corrosive gas HF. Therefore, development of a new method to replace the incineration disposal method is demanded. Mechanochemical methods are considered to be a very promising method for the treatment of POPs solid wastes. During the ball milling process, mechanical force effects such as friction, collision, extrusion and the like between the grinding balls and the grinding agent and the pollutants activate the grinding agent so as to degrade the organic pollutants. Zhang et al adopts KOH as a grinding agent, and utilizes a ball milling mechanochemical method to degrade PFOS, thus almost realizing complete defluorination; KOH is deliquescent and highly corrosive. Cagnetta et al uses La 2 O 3 Mechanochemical degradation of PFOS and perfluorooctanoic acid (PFOA) converts organic fluorine to LaOF. Hu et al and the subject group adopt Fe respectively 3 O 4 And iron powder, al 2 O 3 And aluminum powder is used as an abrasion agent to degrade PFOS or PFOA by a mechanochemical method. The combination of the metal oxide and the zero-valent metal for degrading PFOA or PFOS by a mechanochemical method shows a synergistic effect. Since the aluminum powder has a higher reducing power than the iron powder, aluminum powder and Al 2 O 3 The binary grinding agent system can efficiently degrade PFOA under milder ball milling conditions. However, the system is fallingWhen PFASs are decomposed, sulfonate is reduced into toxic and harmful gas H due to stronger reducing capability of aluminum powder 2 S, secondary pollution is caused. Furthermore, since PFOS is one CF more than PFOA 2 The units, and sulfonate groups are more stable than carboxylate groups, resulting in slower degradation of the PFOS, requiring longer reaction times or higher rotational speeds for complete defluorination. For example, la 2 O 3 The mechanochemical method for completely degrading PFOS and PFOA takes 10 hours and 4 hours respectively; al (Al) 2 O 3 And PFOA degradation of aluminum powder at 350rpm, fe 3 O 4 And iron powder degrading PFOS at 600rpm.
Disclosure of Invention
The invention solves the problems of strong corrosion of the grinding agent, high ball milling energy consumption or secondary pollution of toxic gas in the prior art. The invention provides a method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid substances (PFASs solid waste) by adopting a zinc powder, iron powder and metal compound ternary grinding agent mechanochemical reduction method at normal temperature and normal pressure, wherein perfluoro and/or polyfluoroalkyl sulfonic acid substances are adsorbed by a metal compound, the zinc powder and the iron powder provide electronic reduction C-F bonds, and perfluoro and/or polyfluoroalkyl sulfonic acid substances are degraded under the action of mechanical force effect. According to the invention, adsorbed water or coordinated unsaturated Lewis acid sites on the surface of the metal compound can adsorb perfluoro/polyfluoroalkyl sulfonic acid target pollutants through hydrogen bond/electrostatic action, terminal sulfonate of the pollutants is removed under the combined action of a mechanical force effect and the wear-resisting agent, and meanwhile, the wear-resisting agent is activated to generate electrons to attack perfluoro/polyfluoroalkyl sulfonic acid, so that the perfluoro/polyfluoroalkyl sulfonic acid target pollutants are reduced and degraded.
According to the first aspect of the invention, a method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid solid waste by mechanochemical reduction of a ternary grinding agent is provided, zinc powder, iron powder, a metal compound and alkylsulfonic acid substances are added into a ball milling tank for ball milling, the metal compound is metal oxide, metal hydroxide or metal oxyhydroxide, and the alkylsulfonic acid substances are perfluoro and/or polyfluoroalkyl sulfonic acid substances; the metal compound adsorbs perfluoro and/or polyfluoroalkyl sulfonate, zinc powder and iron powder provide electron reduction C-F bond, and degrade perfluoro and/or polyfluoroalkyl sulfonate under the action of mechanical force effect.
Preferably, the metal oxide is aluminum oxide, zinc oxide, lanthanum oxide or manganese dioxide.
Preferably, the metal hydroxide is aluminum hydroxide, iron hydroxide, barium hydroxide or calcium hydroxide; the metal oxyhydroxide is aluminum oxyhydroxide, iron oxyhydroxide or cobalt oxyhydroxide.
Preferably, the alkyl sulfonic acid is octane sulfonic acid, hexane sulfonic acid, butane sulfonic acid, sulfonic acid ether, octane sulfonate, hexane sulfonate, butane sulfonate or sulfonic acid ether salt.
Preferably, the alkyl sulfonic acid substance accounts for 1-30% of the total mass of the reaction material.
Preferably, the ratio of the total mass of zero-valent metal to the amount of the substance of the metal compound is 0.1 to 5.
Preferably, the ratio of the amounts of the substances of the zinc powder and the iron powder is 0.1 to 10.
Preferably, in the ball milling process, the mass ratio of the grinding balls to the materials is 10:1-100:1.
Preferably, the rotational speed of the ball mill is 100 to 500rpm.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) The invention adopts zinc powder, iron powder and a ternary grinding agent of metal compound (oxide, hydroxide or oxyhydroxide) to reduce and degrade perfluoro/polyfluoroalkyl sulfonic acid. The adsorbed water or coordinated unsaturated Lewis acid sites on the surface of the metal compound (oxide, hydroxide or oxyhydroxide) can adsorb perfluoro/polyfluoroalkyl sulfonic acid target pollutants through hydrogen bond/static electricity/coordination, and the terminal sulfonate of the pollutants is removed under the combined action of a mechanical force effect and the wear agent, and meanwhile, the wear agent is activated to generate electrons to attack perfluoro/polyfluoroalkyl sulfonic acid, so that the reduction degradation of the perfluoro/polyfluoroalkyl sulfonic acid is realized. The zero-valent metal enhancement has a stronger reducing power than the metal oxide alone (hydroxide or oxyhydroxide), providing a greater amount of electrons to attack the perfluoro/polyfluoroalkyl sulfonic acid; zinc powder has stronger reductive defluorination capability than iron powder, but can lead sulfonate to be reduced into poisonous gas H 2 S, the added iron powder can fix S 2- Avoiding the generation of harmful gases. In addition, the interaction between the metal oxide (hydroxide or oxyhydroxide) and the perfluoro/polyfluoroalkyl sulfonic acid is stronger than that of the zero-valent metal, so that the perfluoro/polyfluoroalkyl sulfonic acid can be adsorbed on a reaction interface in a single molecule form, and the association or aggregation between the multiple molecules is avoided, thereby being beneficial to attack of the perfluoro/polyfluoroalkyl sulfonic acid by the adjacent zero-valent metal.
(2) The zinc powder, the iron powder and the ternary grinding agent of metal oxide (hydroxide or oxyhydroxide) have a synergistic effect, so that the quick defluorination and degradation of perfluoro/polyfluoroalkyl sulfonic acid can be realized, the defluorination rate and defluorination rate are superior to those of a monobasic grinding agent system and a dibasic grinding agent system, and the treatment efficiency is also higher than that of the reported grinding agent system.
(3) The grinding agents used in the invention are all commercial products which are low in cost, nontoxic and easy to obtain, and the treated products are inorganic carbon and inorganic fluorine, so that no harmful substances are generated; the whole reaction is carried out at normal temperature and normal pressure, the mechanochemical reaction condition is mild, the treatment time is short, the energy consumption is low, and the efficiency is high.
Drawings
FIG. 1 shows the use of zinc powder, iron powder and alpha-Al in the present invention 2 O 3 The PFOS defluorination rate was treated for the ternary grinding agent and the single and dual mechanochemical methods in the comparative example.
FIG. 2 shows the use of zinc powder, iron powder and alpha-Al in the present invention 2 O 3 (AlOOH or La) 2 O 3 ) The PFOS defluorination rate is mechanically and chemically degraded for the ternary grinding agent.
FIG. 3 shows the change of the relative amounts of aluminum oxide and zero valent metal, zinc powder and iron powder, zinc powder, iron powder and alpha-Al 2 O 3 The ternary grinding agent mechanochemical disposes of the apparent defluorination rate of PFOS.
FIG. 4 shows the use of zinc powder, iron powder and alpha-Al in the present invention 2 O 3 XPS spectra of PFOS different reaction time products were mechanochemical treated with ternary grinding agents.
FIG. 5 shows the use of zinc powder, iron powder and alpha-Al in the present invention 2 O 3 Mechanochemical treatment of 1-chloroperfluoroalkyl ether sulfonic acids with ternary grinding agentsEffect graph of potassium (F-53B).
FIG. 6 is a graph of the comparative examples of the invention with KOH and La 2 O 3 Effect of mechanochemical degradation of PFOS.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention relates to a method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid solid waste by mechanochemical reduction of a ternary grinding agent, which comprises the steps of adding zinc powder, iron powder, a metal compound and alkylsulfonic acid into a ball milling tank for ball milling, wherein the metal compound is metal oxide or metal oxyhydroxide, and the alkylsulfonic acid is perfluoro and/or polyfluoroalkyl sulfonic acid; the metal compound adsorbs perfluoro and/or polyfluoroalkyl sulfonic acid, zinc powder and iron powder provide electron reduction short-chain C-F bond, and degrade perfluoro and/or polyfluoroalkyl sulfonic acid under the action of mechanical force effect to realize deep defluorination.
In some embodiments, the metal oxide is aluminum oxide, zinc oxide, lanthanum oxide, or manganese dioxide.
In some embodiments, the metal hydroxide is aluminum hydroxide, iron hydroxide, barium hydroxide, or calcium hydroxide; the metal oxyhydroxide is aluminum oxyhydroxide, iron oxyhydroxide or cobalt oxyhydroxide.
In some embodiments, the alkyl sulfonic acid is octane sulfonic acid, hexane sulfonic acid, butane sulfonic acid, sulfonic acid ether, octane sulfonate, hexane sulfonate, butane sulfonate, or sulfonic acid ether salt.
In some embodiments, the alumina comprises alpha-alumina, gamma-alumina.
In some embodiments, the alkyl sulfonic acid substance accounts for 1-30% of the total mass of the reaction, the ratio of the total mass of the zero-valent metal to the amount of the substance of the metal compound is 0.1-5, and the ratio of the amount of the substance of the zinc powder and the amount of the substance of the iron powder is 0.1-10.
In some embodiments, the mass ratio of the grinding balls to the materials is 10:1-100:1, and the rotating speed is 100-500 rpm.
The invention discloses a method for degrading perfluoro/polyfluoroalkyl acid substances by a mechanochemical reduction method, which specifically comprises the following steps:
step one: at normal temperature and pressure, PFASs solid waste, zinc powder, iron powder and metal compound (such as Al 2 O 3 ) Adding the mixture into a 250mL stainless steel ball grinding tank according to a certain proportion, and then adding a stainless steel grinding ball with the diameter of 6-15 mm. Wherein PFASs account for 1% -20% of the total material mass, and the mass ratio of the grinding balls to the material is 50:1-100:1.
Step two: the ball milling pot filled with materials and grinding balls is symmetrically fixed on the ball mill, the rotating speed of the ball mill is set to be 250-350 rpm, the ball milling time is 5-240 min, the ball mill is stopped for 2min every 20min, and the ball mill adopts a positive and negative direction alternate operation mode. When the PFASs in the material are all consumed by the reaction, the mechanochemical reaction is stopped.
In some embodiments, the Al of the invention 2 O 3 Comprising different kinds of crystal forms (alpha, gamma) or Al (OH) 3 、AlOOH、ZnO、La 2 O 3 、MnO 2 One of them.
In some embodiments, the PFASs account for 1-20% of the total reaction mass, and the mass ratio of the grinding balls to the materials is 50:1-100:1.
The following are specific examples:
example 1: zinc powder, iron powder and alpha-Al 2 O 3 Ternary grinding agent mechanochemical degradation of PFOS
0.21g of perfluorooctane sulfonate solid powder, 0.74g of zinc powder, 0.32g of iron powder and 1.94g of alpha-Al 2 O 3 Mix and then transfer to a dry stainless steel ball mill tank. Next, 10 stainless steel grinding balls of 15mm in diameter and 20 stainless steel grinding balls of 6mm in diameter were added to the tank, and the total weight of the grinding balls was 160g. The ball milling tank has a volume of 250mL, the depth inside the tank body is 70mm, and the inner diameter of the tank opening is 77mm. Ball with ball bodyThe milling tank is connected with the milling cover by a sealing ring. The ball milling tank is fixed on a ball mill, the rotating speed of the ball milling tank is set to be 350rpm, ball milling reaction is carried out at normal temperature and normal pressure, and the revolution direction of the ball milling is changed once every 20 minutes of reaction. After the ball milling mechanochemical reaction is carried out for 20, 40, 60, 80, 120, 180 and 240 minutes respectively, the ball milling tank is taken out, and solid powder in the tank is collected.
Accurately weighing 10mg of solid powder which reacts for a certain time, heating and dissolving the solid powder by 1mL of 40% sodium hydroxide solution, performing ultrasonic dispersion, centrifuging to obtain supernatant, transferring the supernatant into a volumetric flask, adding 10mL of TISAB, diluting and fixing the volume to 50mL by using distilled water, detecting the concentration of fluorine ions by adopting a fluorine ion selective electrode, and calculating the defluorination rate of PFOS and the apparent defluorination rate of quasi-zero-order reaction.
Example 2: mechanochemical degradation of PFOS (PFOS) by zinc powder, iron powder and AlOOH ternary grinding agent
0.21g of potassium perfluorooctanesulfonate solid powder, 0.74g of zinc powder, 0.32g of iron powder and 1.94g of AlOOH were mixed and then the mechanochemical degradation reaction was started as in example 1. After the ball milling mechanochemical reaction was carried out for 20, 40, 60, 80, 120, 180 and 240min, respectively, the ball milling pot was taken out, solid powder in the pot was collected, and the defluorination rate of PFOS was determined according to the analytical method in example 1.
Example 3: zinc powder, iron powder and La 2 O 3 Ternary grinding agent mechanochemical degradation of PFOS
0.21g of perfluorooctane sulfonate solid powder, 0.74g of zinc powder, 0.32g of iron powder and 1.94gLa 2 O 3 Mixing and then starting the mechanochemical degradation reaction according to the method of example 1. After the ball milling mechanochemical reaction was carried out for 20 and 40 minutes, respectively, the ball milling pot was taken out, solid powder in the pot was collected, and the defluorination rate of PFOS was measured according to the analytical method in example 1.
Example 4: zero-valent metals and alpha-Al 2 O 3 Effect of relative amounts on mechanochemical degradation of PFOS
Mixing 0.21g of potassium perfluorooctanesulfonate solid powder with a ball milling auxiliary agent, controlling the molar ratio of zinc powder to iron powder to be 2:1, and changing alpha-Al 2 O 3 Relative proportions to the metal, which is then subjected to the mechanochemical degradation reactions according to the first and second steps described above. After the ball milling mechanochemical reaction was carried out for 20 and 40min, respectively, the ball milling pot was taken out, solid powder in the pot was collected, and the defluorination rate of PFOS and the apparent defluorination rate of quasi-zero order reaction were measured according to the analytical method in example 1.
Example 5: influence of relative amounts of zinc powder and iron powder on PFOS degradation of ternary grinding agent by mechanochemical method
Mixing 0.21g of perfluor octane sulfonate potassium solid powder with a ball milling auxiliary agent, and keeping alpha-Al 2 O 3 1.93g, zinc powder, iron powder, and total mass of 1.06g, the relative proportions of zinc powder and iron powder were varied, and then mechanochemical degradation reaction was initiated as in example 1. After the ball milling mechanochemical reaction was carried out for 20 and 40min, respectively, the ball milling pot was taken out, solid powder in the pot was collected, and the defluorination rate of PFOS and the apparent defluorination rate of quasi-zero order reaction were measured according to the analytical method in example 1.
Example 6: zinc powder, iron powder and alpha-Al 2 O 3 Influence of ternary grinding agent on mechanochemical degradation of F-53B
Mixing 0.21g of 1-chloro-perfluoroalkyl ether sulfonate solid powder with a ball milling auxiliary agent to keep alpha-Al 2 O 3 1.93g, zinc powder, iron powder, 1.06g, and starting the mechanochemical degradation reaction according to the method of example 1. After the ball milling mechanochemical reaction was carried out for 20, 40, 60, and 80 minutes, respectively, the ball milling pot was taken out, solid powder in the pot was collected, and the defluorination rate of PFOS was measured according to the analytical method in example 1.
Example 7: zinc powder, iron powder and alpha-Al 2 O 3 XPS characterization of ternary grinding agent mechanochemical degradation PFOS product
The procedure of example 1 was repeated in the same manner as described, and 50mg of the ball-milling reaction 0, 60 and 240min samples were weighed in the second step and subjected to an X-ray photoelectron spectroscopy characterization test.
Comparative example 1: mechanochemical degradation of PFOS with a single grinding agent
Mixing 0.21g of potassium perfluorooctanesulfonate solid powder with 3g of alpha-Al respectively 2 O 3 Mixing 3g of zinc powder and 3g of iron powder, and then starting the mechanochemical degradation reaction according to the first step and the second step. After the ball milling mechanochemical reaction was carried out for 20, 40, 60, 80, 120, 240min, respectively, the ball milling pot was taken out, solid powder in the pot was collected, and the defluorination rate of PFOS was measured according to the analytical method in example 1.
Comparative example 2: binary grinding agent mechanochemical degradation PFOS
0.21g of potassium perfluorooctanesulfonate solid powder was mixed with 1.93g of alpha-Al, respectively 2 O 3 And 1.06g of iron powder, 1.93g of alpha-Al 2 O 3 And 1.06g zinc powder, 2.1g iron powder and 0.90g zinc powder, which were then subjected to mechanochemical degradation reactions according to the above steps one and two. After the ball milling mechanochemical reaction was carried out for 20, 40, 60, 80, 120, 240min, respectively, the ball milling pot was taken out, solid powder in the pot was collected, and the defluorination rate of PFOS was measured according to the analytical method in example 1.
Comparative example 3: KOH or La 2 O 3 Mechanochemical degradation of PFOS
0.21g of potassium perfluorooctanesulfonate solid powder was mixed with 3g of KOH solid and 1.93g of Fe 3 O 4 And 1.06g of iron powder, and then starting the mechanochemical degradation reaction according to the first and second steps. After the ball milling mechanochemical reaction was carried out for 20, 40, 60, 80, 120, 240min, respectively, the ball milling pot was taken out, solid powder in the pot was collected, and the defluorination rate of PFOS was measured according to the analytical method in example 1.
Results and analysis
Zinc powder, iron powder and alpha-Al were tested as in example 1 2 O 3 Effect of ternary grinding agent mechanochemical degradation of PFOS. As shown in a of fig. 1, the defluorination rate of the ternary grinding agent system to the PFOS is 85.94% when ball milling mechanochemical reaction is carried out for 60 min; after the reaction was continued for 180min, the PFOS was completely defluorinated. However, as shown in b of FIG. 1, in comparative example 1, zinc powder, iron powder or α -Al is used alone 2 O 3 When the PFOS is used as a grinding agent, the defluorination speed is slow, and the defluorination rate is only 9.07%, 11.80% and 46.76% after 60 minutes of reaction (shown as b in figure 1); in comparative example 2 (as in FIG. 1Indicated by a) in the formula, alpha-Al is used respectively 2 O 3 And zinc powder, alpha-Al 2 O 3 And iron powder, zinc powder and iron powder as the grinding agent, the defluorination rate of PFOS is improved in 60min to be 70.15%, 82.64% and 17.40%, respectively, in contrast to zinc powder, iron powder and alpha-Al 2 O 3 The defluorination rate of the ternary grinding agent in the early stage of mechanochemical reaction is obviously higher than that of other binary systems and monobasic systems. The defluorination rate of PFOS and time within 40min at the initial stage of the reaction accord with the quasi-zero order reaction kinetics, namely the ratio of the defluorination rate of PFOS to the time can be used as the apparent rate constant of the reaction. In contrast, zinc powder, iron powder and alpha-Al 2 O 3 Apparent defluorination rate of PFOS (PFOS) degraded by mechanochemical method of ternary grinding agent is 2.04min –1 alpha-Al alone 2 O 3 13.28, 9.92 and 2.63 times of the zinc powder and the iron powder are alpha-Al 2 O 3 And zinc powder and alpha-Al 2 O 3 And about 1.4 times of the binary system of the iron powder.
In accordance with the methods of examples 2 and 3, either AlOOH or La 2 O 3 Respectively forms a ternary system with zinc powder and iron powder to mechanically and chemically degrade PFOS. As shown in FIG. 2, zinc powder, iron powder and La were reacted mechanically for 4 hours 2 O 3 The defluorination rate of the ternary grinding agent system to the existing PFOS is 82.4%; the defluorination rate of the zinc powder, the iron powder and the AlOOH ternary grinding agent system to PFOS is 57.9%.
The zero valent metal and alpha-Al were tested as in examples 4 and 5 2 O 3 Influence of relative amounts of zinc powder and iron powder on the defluorination rate of PFOS. First, the ratio of the amounts of substances to fix the zinc powder and the iron powder (n Zn /n Fe ) 2, change alpha-Al 2 O 3 Quality and ball milling auxiliary agent (containing alpha-Al) 2 O 3 Ratio to zero-valent metal) total mass (m Al2O3 /m T ). The results are shown in FIG. 3 a when the zero valent metal (Zn/Fe) alone is used as the control (m Al2O3 /m T =0), the defluorination rate of PFOS is only 0.34min –1 The method comprises the steps of carrying out a first treatment on the surface of the Then gradually increase alpha-Al 2 O 3 The defluorination rate of PFOS increases sharply, when m Al2O3 /m T At=0.64, the defluorination rate of PFOS reachesMaximum 2.04min –1 The method comprises the steps of carrying out a first treatment on the surface of the While continuing to increase alpha-Al 2 O 3 At a lower defluorination rate of PFOS, alpha-Al alone 2 O 3 At the time, the defluorination rate of PFOS was 0.86min –1 . Then, fix m Al2O3 /m T =0.64, change n Zn /n Fe . The result is shown in FIG. 3b when the ratio of the amounts of the substances of zinc powder and iron powder (n Zn /n Fe ) Increasing the defluorination rate from 0 to 2 for 40min to 1.50min –1 Increasing the temperature to 2.04min –1 The method comprises the steps of carrying out a first treatment on the surface of the Continue to increase n Zn /n Fe The defluorination rate of PFOS gradually decreases.
The collected samples were subjected to X-ray photoelectron spectroscopy (XPS) analysis according to example 7. The results are shown in FIG. 4. A in FIG. 4 is a high resolution spectrum of C1s, and components with binding energy of 284.8 and 292.5eV are respectively assigned to exogenous pollution carbon and C-F bond in PFOS before ball milling mechanochemical reaction; when mechanochemical treatment was carried out for 3 hours, the peak of organic C-F disappeared, and inorganic carbon was generated at 284.8 eV. B in FIG. 4 is XPS high resolution spectrum of F1s, and the component with binding energy at 689.05eV in the sample is C-F bond in PFOS before mechanochemical reaction; as the reaction proceeds, the peak intensity of the organic C-F bond gradually decreases, inorganic fluoride ions are generated at 685.16eV, and the peak gradually increases; the reaction was carried out for 3h, and the F1s peak corresponding to the C-F bond was completely disappeared, indicating that PFOS achieved complete defluorination.
Zinc powder, iron powder and alpha-Al were tested according to example 6 2 O 3 The effect of the ternary grinding agent on degrading F-53B by a mechanochemical method. As shown in FIG. 5, the defluorination rate of F-53B can reach 82.5% in 80min ball milling reaction, which shows that the ternary grinding agent system is also suitable for degradation defluorination of perfluoro/polyfluoroalkyl sulfonate ether.
Zinc powder, iron powder and alpha-Al were tested according to comparative example 3 2 O 3 Ternary wear agent system with reported KOH and Fe 3 O 4 And a method for degrading PFOS by an iron powder binary system. As shown in FIG. 6, zinc powder, iron powder and alpha-Al were ball-milled for 3 hours under the same experimental conditions 2 O 3 The defluorination rate of the ternary grinding agent system to PFOS is 100 percent, which is obviously higher than that of KOH (32.2 percent) and Fe 3 O 4 System of grinding aid/Fe (72.0%). Compared with the system reported in the literature, the ball milling mechanochemical reaction condition of the ternary grinding agent system for treating PFOS is milder, and the energy consumption is lower.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid solid waste by mechanochemical reduction of a ternary grinding agent is characterized in that zinc powder, iron powder, a metal compound and alkylsulfonic acid substances are added into a ball milling tank for ball milling, wherein the metal compound is metal oxide, metal hydroxide or metal oxyhydroxide, and the alkylsulfonic acid substances are perfluoro and/or polyfluoroalkyl sulfonic acid substances; the metal compound adsorbs perfluoro and/or polyfluoroalkyl sulfonate, zinc powder and iron powder provide electron reduction C-F bond, and degrade perfluoro and/or polyfluoroalkyl sulfonate under the action of mechanical force effect.
2. The method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid solid waste by mechanochemical reduction of a ternary grinding agent according to claim 1, wherein the metal oxide is aluminum oxide, zinc oxide, lanthanum oxide or manganese dioxide.
3. The method for mechanochemical reduction degradation of perfluoro and/or polyfluoroalkyl sulfonic acid solid wastes by using a ternary grinding agent according to claim 1 or 2, wherein the metal hydroxide is aluminum hydroxide, ferric hydroxide, barium hydroxide or calcium hydroxide; the metal oxyhydroxide is aluminum oxyhydroxide, iron oxyhydroxide or cobalt oxyhydroxide.
4. The method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid solid waste by mechanochemical reduction of a ternary grinding agent according to claim 1, wherein the alkylsulfonic acid is octanesulfonic acid, hexanesulfonic acid, butanesulfonic acid, sulfonic acid ether, octanesulfonic acid salt, hexanesulfonic acid salt, butanesulfonic acid salt or sulfonic acid ether salt.
5. The method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid solid waste by mechanochemical reduction of a ternary grinding agent according to claim 1, wherein the mass fraction of the alkylsulfonic acid substance in the total reaction material is 1-30%.
6. The method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid solid waste by mechanochemical reduction of a ternary grinding agent according to claim 1, wherein the ratio of the total mass of zero-valent metal to the amount of the substance of the metal compound is 0.1 to 5.
7. The method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid solid waste by mechanochemical reduction of the ternary grinding agent as claimed in claim 1 or 6, wherein the ratio of the amounts of the substances of zinc powder and iron powder is 0.1-10.
8. The method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid solid waste by mechanochemical reduction of a ternary grinding agent as claimed in claim 1, wherein the mass ratio of grinding balls to materials in the ball milling process is 10:1-100:1.
9. The method for degrading perfluoro and/or polyfluoroalkyl sulfonic acid solid waste by mechanochemical reduction of a ternary grinding agent as claimed in claim 1, wherein the rotation speed of the ball mill is 100-500 rpm.
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