CN103553204B - Method for treating water by using singlet oxygen produced from peroxymonosulfate under induction of inorganic solid peroxide - Google Patents
Method for treating water by using singlet oxygen produced from peroxymonosulfate under induction of inorganic solid peroxide Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 60
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 47
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 title claims abstract description 36
- 229910003480 inorganic solid Inorganic materials 0.000 title abstract description 48
- 230000006698 induction Effects 0.000 title description 2
- 239000007787 solid Substances 0.000 claims abstract description 23
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- 238000006243 chemical reaction Methods 0.000 claims description 10
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- 230000014759 maintenance of location Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 3
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 claims description 2
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 claims description 2
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- 229960004995 magnesium peroxide Drugs 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 15
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
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- 230000001590 oxidative effect Effects 0.000 description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 5
- 239000004343 Calcium peroxide Substances 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- 208000017983 photosensitivity disease Diseases 0.000 description 4
- 231100000434 photosensitization Toxicity 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
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- 239000007800 oxidant agent Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
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- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- UJKPHYRXOLRVJJ-MLSVHJFASA-N CC(O)C1=C(C)/C2=C/C3=N/C(=C\C4=C(CCC(O)=O)C(C)=C(N4)/C=C4\N=C(\C=C\1/N\2)C(C)=C4C(C)O)/C(CCC(O)=O)=C3C Chemical compound CC(O)C1=C(C)/C2=C/C3=N/C(=C\C4=C(CCC(O)=O)C(C)=C(N4)/C=C4\N=C(\C=C\1/N\2)C(C)=C4C(C)O)/C(CCC(O)=O)=C3C UJKPHYRXOLRVJJ-MLSVHJFASA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 229930186147 Cephalosporin Natural products 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 1
- AJTFTYHGFWNENF-UHFFFAOYSA-N azanium;hydroxy sulfate Chemical compound [NH4+].OOS([O-])(=O)=O AJTFTYHGFWNENF-UHFFFAOYSA-N 0.000 description 1
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- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 1
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- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
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- -1 fluorescent yellow Chemical compound 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229960003569 hematoporphyrin Drugs 0.000 description 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法，涉及水处理方法。本发明要解决光敏法产生单线态氧需要外加光源及产生二次污染和化学法中单线态氧利用率低的问题。本发明水处理方法为：将无机固体过氧化物和过一硫酸盐加入到待处理水中，搅拌，即可，待处理水为水源水和污水。本发明水处理方法中过氧化物溶于水后缓慢释放的过氧化氢与过一硫酸盐迅速反应，低浓度持续产生的高活性单线态氧，可被污染物高效利用，减少其自分解，提高其利用率。本发明除污染效率高，不产生有毒有害副产物，不需要额外增加设备，作为固体试剂运输、储存方便，更适用于应急处理。
The invention relates to a water treatment method which utilizes inorganic solid peroxide to induce peroxymonosulfate to generate singlet oxygen, and relates to a water treatment method. The invention aims to solve the problems that an external light source is needed to generate singlet oxygen in the photosensitive method, secondary pollution is generated, and the utilization rate of singlet oxygen in the chemical method is low. The water treatment method of the present invention is as follows: adding inorganic solid peroxide and persulfate into the water to be treated, stirring, and the water to be treated is source water and sewage. In the water treatment method of the present invention, the hydrogen peroxide released slowly after the peroxide is dissolved in water reacts rapidly with peroxymonosulfate, and the high-activity singlet oxygen continuously produced at low concentration can be efficiently utilized by pollutants to reduce its self-decomposition, increase its utilization. The invention has high pollution removal efficiency, does not produce toxic and harmful by-products, does not require additional equipment, is convenient to transport and store as a solid reagent, and is more suitable for emergency treatment.
Description
技术领域technical field
本发明涉及水处理方法，具体涉及一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法。The invention relates to a water treatment method, in particular to a water treatment method using inorganic solid peroxide to induce persulfate to generate singlet oxygen.
背景技术Background technique
单线态氧(1O2)是一种处于激发态的分子氧，与超氧自由基(O2 -·)、羟基自由基(·OH)、硫酸根自由基(SO4 ·-)等活性氧物种类似，化学性质活泼、不稳定，在自然界中广泛存在，是化学、环境、医学等领域最长涉及的活性氧之一，具有氧化能力强、反应活性高、存活时间短、氧化后不产生有毒有害副产物等特点，属于绿色、环境友好型氧化剂。Singlet oxygen ( 1 O 2 ) is a kind of molecular oxygen in an excited state, which is reactive with superoxide radical (O 2 -· ), hydroxyl radical (·OH), sulfate radical (SO 4 ·- ), etc. Oxygen species are similar, chemically active and unstable, and widely exist in nature. It is one of the longest active oxygen species involved in the fields of chemistry, environment, and medicine. It has the characteristics of producing toxic and harmful by-products, and is a green and environment-friendly oxidant.
目前，产生单线态氧的方法主要有光敏化法和化学方法。光敏化法产生单线态氧涉及到一个光激发过程，一种光敏剂(玫瑰红、曙红、亚甲基蓝、荧光黄、叶绿素和血卟啉等)，在光照射条件下，激发态的光敏剂与体系中的基态氧(3O2)作用，进而得到单线态氧(1O2)。利用光敏化法可以快速产生单线态氧，但存在着光的限制(需要稳定的光源)及光敏剂的引入会产生二次污染的问题。化学方法产生单线态氧是由发生化学反应来实现的，最经典的方法是将过氧化氢(H2O2)与氯气(Cl2)的水溶液或次氯酸溶液混合即可产生单线态氧。这种利用化学方法产生单线态氧的生成速度快，其二级反应速率常数约为104M-1s-1，即瞬时产生量大，自分解速度快，存活时间短，有机物利用率低；化学试剂为液态的过氧化氢和次氯酸溶液或氯气，运输储存不方便，工艺操作复杂及存在安全隐患的问题。At present, the methods for generating singlet oxygen mainly include photosensitization and chemical methods. The generation of singlet oxygen by photosensitization involves a photoexcitation process, a photosensitizer (rose bengal, eosin, methylene blue, fluorescent yellow, chlorophyll and hematoporphyrin, etc.), under light irradiation conditions, the photosensitizer in the excited state and The ground state oxygen ( 3 O 2 ) in the system acts to obtain singlet oxygen ( 1 O 2 ). Singlet oxygen can be rapidly produced by photosensitization, but there are problems of light limitation (requires a stable light source) and the introduction of photosensitizer will cause secondary pollution. The chemical method to generate singlet oxygen is realized by chemical reaction, the most classic method is to mix hydrogen peroxide (H 2 O 2 ) with chlorine (Cl 2 ) aqueous solution or hypochlorous acid solution to generate singlet oxygen . This kind of singlet oxygen produced by chemical method has a fast generation rate, and its secondary reaction rate constant is about 10 4 M -1 s -1 , that is, the instantaneous production amount is large, the self-decomposition speed is fast, the survival time is short, and the utilization rate of organic matter is low. ; The chemical reagent is liquid hydrogen peroxide and hypochlorous acid solution or chlorine gas, which is inconvenient for transportation and storage, complicated process operation and potential safety hazards.
发明内容Contents of the invention
本发明的目的是提供一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法，解决如下问题：(1)光敏化法中产生单线态氧需要外加光源，很难大规模应用，且光敏剂的引入会产生二次污染；(2)化学反应法(H2O2-ClO-)中瞬时产生的单线态氧量大、易自分解、很难被污染物高效利用，且液态的过氧化氢和次氯酸溶液或氯气，运输、储存不方便，操作复杂且存在安全隐患。The purpose of this invention is to provide a kind of water treatment method that utilizes inorganic solid peroxide to induce persulfate to produce singlet oxygen, solve following problem: (1) produce singlet oxygen in photosensitization method and need to add light source, it is difficult to Large-scale application, and the introduction of photosensitizer will cause secondary pollution; (2) The singlet oxygen generated instantaneously in the chemical reaction method (H 2 O 2 -ClO - ) is large, easy to self-decompose, and difficult to be efficiently utilized by pollutants , and liquid hydrogen peroxide and hypochlorous acid solution or chlorine gas are inconvenient to transport and store, complicated to operate and have potential safety hazards.
本发明的一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法是通过以下步骤实现的：将无机固体过氧化物和过一硫酸盐按照质量比为1:(0.5～5)的比例加入到待处理水中，搅拌，控制过一硫酸盐在待处理水中的浓度为0.3～300mg/L，水力停留反应5～60min，即完成利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理；其中，所述待处理水为水源水和污水。A kind of water treatment method that utilizes inorganic solid peroxide to induce permonosulfate to produce singlet oxygen of the present invention is realized by following steps: inorganic solid peroxide and peroxosulfate are according to mass ratio 1:(0.5 ~5) was added to the water to be treated, stirred, and the concentration of peroxosulfate in the water to be treated was controlled to be 0.3~300mg/L, and the hydraulic retention reaction was 5~60min, that is, the induction of peroxomonosulfuric acid by inorganic solid peroxide was completed. Water treatment in which salt generates singlet oxygen; wherein, the water to be treated is source water and sewage.
本发明的一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法，可以将无机固体过氧化物、过一硫酸盐按照质量比为1:(0.5～5)制成粉末试剂混合投加或分别单独投加，即为干式投加法；也可以将无机固体过氧化物、过一硫酸盐分别制成溶液，进行单独投加，即为湿式投加法。A kind of water treatment method of the present invention utilizes inorganic solid peroxide to induce persulfate to produce singlet oxygen, can make inorganic solid peroxide and peroxosulfate according to the mass ratio of 1:(0.5～5) Powder reagents are mixed or added separately, which is the dry dosing method; inorganic solid peroxide and persulfate can also be made into solutions and added separately, which is the wet dosing method.
本发明的一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法中，无机固体过氧化物(Na2O2、CaO2、MgO2、BaO2、Na2CO4、K2CO4)溶于水后会缓慢释放出过氧化氢(H2O2)，见反应式(1)和(2)，这种通过无机固体过氧化物在水中原位产生的过氧化氢，可以迅速与过一硫酸盐(HSO5 -)反应产生高活性单线态氧(1O2)，见反应式(3)，低浓度持续产生的强氧化性单线态氧可以被污染物高效利用，减少其自分解，提高其利用率，除污染效果好，且不产生有毒有害副产物。In a water treatment method of the present invention that utilizes inorganic solid peroxides to induce persulfate to generate singlet oxygen, inorganic solid peroxides (Na 2 O 2 , CaO 2 , MgO 2 , BaO 2 , Na 2 CO 4 , K 2 CO 4 ) will slowly release hydrogen peroxide (H 2 O 2 ) after dissolving in water, see reaction formulas (1) and (2), this peroxide produced in situ by inorganic solid peroxide in water Hydrogen oxide can quickly react with persulfate (HSO 5 - ) to produce highly active singlet oxygen ( 1 O 2 ), see reaction formula (3), and the strong oxidizing singlet oxygen produced continuously at low concentrations can be absorbed by pollutants Efficient utilization, reducing its self-decomposition, improving its utilization rate, good decontamination effect, and no toxic and harmful by-products.
O2 2-+2H2O→H2O2+2OH- (1)O 2 2- +2H 2 O→H 2 O 2 + 2OH- (1)
CO4 2-+H2O→H2O2+CO3 2- (2)CO 4 2- +H 2 O→H 2 O 2 +CO 3 2- (2)
H2O2+HSO5 -→1O2+SO4 2-+H2O+H+ (3)H 2 O 2 +HSO 5 - → 1 O 2 +SO 4 2- +H 2 O+H + (3)
本发明的一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法，具有如下优点：绿色新兴氧化剂过一硫酸盐与无机固体过氧化物作为粉末状固体与液态的过氧化氢和次氯酸溶液或氯气相比化学性质稳定，运输储存方便，价格适中，商业易得，操作简单易行，不需要额外增加运行设备(如O3、UV需要提供反应装置与设备)，受水体条件影响小(如Fenton试剂受pH影响比较大)，产生的环境友好型具有强氧化性的单线态氧，除污染效率高，反应过程中不产生有毒有害副产物，可以在水厂中进行大规模应用，作为固体粉末药剂投加更适用于水污染爆发时的应急处理。A water treatment method of the present invention, which utilizes inorganic solid peroxide to induce persulfate to generate singlet oxygen, has the following advantages: the green emerging oxidant persulfate and inorganic solid peroxide are used as a combination of powdery solid and liquid peroxide. Compared with hypochlorous acid solution or chlorine gas, hydrogen peroxide is chemically stable, convenient to transport and store, moderately priced, commercially available, easy to operate, and does not require additional operating equipment (such as O 3 , UV needs to provide reaction devices and equipment) , is less affected by water conditions (such as Fenton's reagent is greatly affected by pH), and produces environmentally friendly singlet oxygen with strong oxidizing properties, high pollution removal efficiency, and no toxic and harmful by-products during the reaction process, which can be used in water plants For large-scale application in China, it is more suitable for emergency treatment when water pollution breaks out when it is added as a solid powder agent.
附图说明Description of drawings
图1是具体实施方式二十一中水源水中内分泌干扰物-双酚A的去除率曲线图。Fig. 1 is a graph showing the removal rate of endocrine disruptor-bisphenol A in water source water in the twenty-first embodiment.
具体实施方式Detailed ways
本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
具体实施方式一：本实施方式为一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法，其是通过以下步骤实现的：将无机固体过氧化物和过一硫酸盐按照质量比为1:(0.5～5)的比例加入到待处理水中，搅拌，控制过一硫酸盐在待处理水中的浓度为0.3～300mg/L，水力停留反应5～60min，即完成利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理；其中，所述待处理水为水源水和污水。Embodiment 1: This embodiment is a water treatment method that utilizes inorganic solid peroxide to induce persulfate to produce singlet oxygen, which is achieved through the following steps: combine inorganic solid peroxide and persulfate According to the mass ratio of 1: (0.5 ~ 5), it is added to the water to be treated, stirred, and the concentration of persulfate in the water to be treated is controlled to be 0.3 ~ 300mg/L, and the hydraulic retention reaction is 5 ~ 60min, that is, the utilization of inorganic Water treatment for generating singlet oxygen from peroxymonosulfate induced by solid peroxide; wherein, the water to be treated is source water and sewage.
本实施方式中的无机固体过氧化物和过一硫酸盐在使用前分开存放。The inorganic solid peroxide and persulfate in this embodiment are stored separately before use.
本实施方式中所述无机固体过氧化物和过一硫酸盐可以按照质量比为1:(0.5～5)制成粉末试剂混合投加或分别单独投加，即为干式投加法；也可以将无机固体过氧化物和过一硫酸盐分别制成溶液，进行单独投加，即为湿式投加法。The inorganic solid peroxide and peroxymonosulfate described in this embodiment can be made into powder reagents according to the mass ratio of 1:(0.5-5) and added together or added separately, which is the dry-type addition method; The inorganic solid peroxide and persulfate are made into solutions and added separately, which is the wet dosing method.
本实施方式的一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法中，无机固体过氧化物溶于水后会缓慢释放出过氧化氢(H2O2)，这种通过无机固体过氧化物在水中原位产生的过氧化氢，可以迅速与过一硫酸盐(HSO5 -)反应产生高活性单线态氧(1O2)，低浓度持续产生的强氧化性单线态氧可以被污染物高效利用，减少其自分解，除污染效果好，且不产生有毒有害副产物。In a water treatment method of this embodiment that utilizes inorganic solid peroxide to induce persulfate to generate singlet oxygen, the inorganic solid peroxide will slowly release hydrogen peroxide (H 2 O 2 ) after being dissolved in water, This kind of hydrogen peroxide produced in situ by inorganic solid peroxide in water can quickly react with peroxymonosulfate (HSO 5 - ) to produce highly active singlet oxygen ( 1 O 2 ), and the strong oxidation produced continuously at low concentration Sexual singlet oxygen can be efficiently utilized by pollutants, reducing its self-decomposition, good decontamination effect, and does not produce toxic and harmful by-products.
本实施方式的一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法的优点为：绿色新兴氧化剂过一硫酸盐与无机固体过氧化物作为粉末状固体与液态的过氧化氢和次氯酸溶液或氯气相比化学性质稳定，运输储存方便，价格适中，商业易得，操作简单易行，不需要额外增加运行设备，受水体条件影响小，产生的强氧化性单线态氧，除污染效率高，反应过程中不产生有毒有害副产物，可以在水厂中进行大规模应用，更适用于应急处理。The advantage of the water treatment method of this embodiment, which utilizes inorganic solid peroxide to induce persulfate to generate singlet oxygen, is that the green emerging oxidant persulfate and inorganic solid peroxide are used as a combination of powdery solid and liquid peroxide. Compared with hypochlorous acid solution or chlorine gas, hydrogen oxide has stable chemical properties, convenient transportation and storage, moderate price, easy commercial availability, simple and easy operation, no need for additional operating equipment, little influence by water body conditions, and strong oxidizing single line State oxygen, high efficiency of decontamination, no toxic and harmful by-products in the reaction process, can be used in large-scale water plants, and is more suitable for emergency treatment.
具体实施方式二：本实施方式与具体实施方式一不同的是：所述无机固体过氧化物是过氧化钠(Na2O2)、过氧化钙(CaO2)、过氧化镁(MgO2)、过氧化钡(BaO2)、过碳酸钠(Na2CO4)、过碳酸钾(K2CO4)中的一种或几种按任意比混合的混合物。其它参数与具体实施方式一相同。Specific embodiment two: the difference between this embodiment and specific embodiment one is: the inorganic solid peroxide is sodium peroxide (Na 2 O 2 ), calcium peroxide (CaO 2 ), magnesium peroxide (MgO 2 ) , barium peroxide (BaO 2 ), sodium percarbonate (Na 2 CO 4 ), potassium percarbonate (K 2 CO 4 ) or a mixture of several mixed in any ratio. Other parameters are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二不同的是：过一硫酸盐是过一硫酸钠(NaHSO5)、过一硫酸钾(KHSO5)、过一硫酸铵(NH4HSO5)、过一硫酸钙(Ca(HSO5)2)、过一硫酸镁(Mg(HSO5)2)中的一种或几种按任意比混合的混合物。其它参数与具体实施方式一或二相同。Specific embodiment three: the difference between this embodiment and specific embodiment one or two is: permonosulfate is sodium persulfate (NaHSO 5 ), potassium persulfate (KHSO 5 ), ammonium peroxosulfate (NH 4 HSO 5 ), calcium persulfate (Ca(HSO 5 ) 2 ), magnesium persulfate (Mg(HSO 5 ) 2 ), or a mixture of several in any ratio. Other parameters are the same as those in Embodiment 1 or Embodiment 2.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是：过一硫酸盐浓度为0.5～250mg/L。其它步骤及参数与具体实施方式一至三之一相同。Embodiment 4: This embodiment differs from Embodiment 1 to Embodiment 3 in that the concentration of peroxymonosulfate is 0.5-250 mg/L. Other steps and parameters are the same as those in Embodiments 1 to 3.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是：过一硫酸盐浓度为1～200mg/L。其它步骤及参数与具体实施方式一至四之一相同。Embodiment 5: This embodiment is different from Embodiment 1 to Embodiment 4 in that the concentration of peroxymonosulfate is 1-200 mg/L. Other steps and parameters are the same as in one of the specific embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是：过一硫酸盐浓度为1.5～150mg/L。其它步骤及参数与具体实施方式一至五之一相同。Embodiment 6: This embodiment differs from Embodiment 1 to Embodiment 5 in that the concentration of peroxymonosulfate is 1.5-150 mg/L. Other steps and parameters are the same as one of the specific embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是：过一硫酸盐浓度为2～100mg/L。其它步骤及参数与具体实施方式一至六之一相同。Embodiment 7: This embodiment differs from Embodiment 1 to Embodiment 6 in that the concentration of peroxymonosulfate is 2-100 mg/L. Other steps and parameters are the same as one of the specific embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同的是：过一硫酸盐浓度为5～75mg/L。其它步骤及参数与具体实施方式一至七之一相同。Embodiment 8: This embodiment differs from Embodiments 1 to 7 in that the concentration of peroxymonosulfate is 5-75 mg/L. Other steps and parameters are the same as one of the specific embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是：过一硫酸盐浓度为10～50mg/L。其它步骤及参数与具体实施方式一至八之一相同。Embodiment 9: This embodiment differs from Embodiments 1 to 8 in that the concentration of peroxymonosulfate is 10-50 mg/L. Other steps and parameters are the same as those in Embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是：过一硫酸盐浓度为15～30mg/L。其它步骤及参数与具体实施方式一至九之一相同。Embodiment 10: This embodiment is different from Embodiment 1 to Embodiment 9 in that: the concentration of peroxymonosulfate is 15-30 mg/L. Other steps and parameters are the same as one of the specific embodiments 1 to 9.
具体实施方式十一：本实施方式与具体实施方式一至十之一不同的是：过一硫酸盐浓度为20mg/L。其它步骤及参数与具体实施方式一至十之一相同。Embodiment 11: This embodiment is different from Embodiments 1 to 11 in that the concentration of peroxymonosulfate is 20 mg/L. Other steps and parameters are the same as those in Embodiments 1 to 11.
具体实施方式十二：本实施方式与具体实施方式一至十一之一不同的是：无机固体过氧化物和过一硫酸盐的质量比为1:(0.6～4)。其它参数与具体实施方式一一至十一之一相同。Embodiment 12: This embodiment differs from Embodiments 1 to 11 in that the mass ratio of inorganic solid peroxide to persulfate is 1:(0.6-4). Other parameters are the same as those in Embodiments 11 to 11.
具体实施方式十三：本实施方式与具体实施方式一至十二之一不同的是：无机固体过氧化物和过一硫酸盐的质量比为1:(0.7～3)。其它参数与具体实施方式一至十二之一相同。Embodiment 13: This embodiment is different from Embodiment 1 to Embodiment 12 in that the mass ratio of inorganic solid peroxide to persulfate is 1:(0.7-3). Other parameters are the same as those in Embodiments 1 to 12.
具体实施方式十四：本实施方式与具体实施方式一至十三之一不同的是：无机固体过氧化物和过一硫酸盐的质量比为1:(0.8～2)。其它参数与具体实施方式一至十三之一相同。Embodiment 14: The difference between this embodiment and Embodiment 1 to 13 is that the mass ratio of inorganic solid peroxide to persulfate is 1:(0.8-2). Other parameters are the same as those in the first to thirteenth specific embodiments.
具体实施方式十五：本实施方式与具体实施方式一至十四之一不同的是：无机固体过氧化物和过一硫酸盐的质量比为1:(0.9～1.5)。其它参数与具体实施方式一至十四之一相同。Embodiment 15: This embodiment is different from Embodiment 1 to Embodiment 14 in that the mass ratio of inorganic solid peroxide to persulfate is 1:(0.9-1.5). Other parameters are the same as in one of the specific embodiments 1 to 14.
具体实施方式十六：本实施方式与具体实施方式一至十五之一不同的是：无机固体过氧化物和过一硫酸盐的质量比为1:1。其它参数与具体实施方式一至十五之一相同。Embodiment 16: This embodiment is different from Embodiment 1 to Embodiment 15 in that the mass ratio of inorganic solid peroxide to persulfate is 1:1. Other parameters are the same as those in Embodiments 1 to 15.
具体实施方式十七：本实施方式与具体实施方式一至十六之一不同的是：控制反应时间为10～50min。其它步骤及参数与具体实施方式一至十六之一相同。Embodiment 17: This embodiment is different from Embodiment 1 to Embodiment 16 in that: the reaction time is controlled to be 10-50 minutes. Other steps and parameters are the same as those in Embodiments 1 to 16.
具体实施方式十八：本实施方式与具体实施方式一至十七之一不同的是：控制反应时间为20～40min。其它步骤及参数与具体实施方式一至十七之一相同。Embodiment 18: This embodiment differs from Embodiments 1 to 17 in that the reaction time is controlled to be 20-40 minutes. Other steps and parameters are the same as those in Embodiments 1 to 17.
具体实施方式十九：本实施方式与具体实施方式一至十八之一不同的是：控制反应时间为30min。其它步骤及参数与具体实施方式一至十八之一相同。Embodiment Nineteen: This embodiment is different from Embodiment One to Embodiment One Eighteen in that: the control reaction time is 30 minutes. Other steps and parameters are the same as those in Embodiments 1 to 18.
具体实施方式二十：本实施方式为一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法，其是通过以下步骤实现的：将无机固体过氧化物和过一硫酸盐按照质量比为1:1加入到待处理污水中，搅拌，控制过一硫酸盐在待处理污水中的浓度为100mg/L，水力停留反应时间为30min，即完成利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理。Specific Embodiment Twenty: This embodiment is a water treatment method that utilizes inorganic solid peroxide to induce persulfate to generate singlet oxygen, which is achieved through the following steps: combine inorganic solid peroxide and peroxymonosulfuric acid Salt is added to the sewage to be treated according to the mass ratio of 1:1, stirred, and the concentration of persulfate in the sewage to be treated is controlled to 100 mg/L, and the hydraulic retention reaction time is 30 minutes, that is, the use of inorganic solid peroxides to induce Permonosulfate produces singlet oxygen in water treatment.
本实施方式中所述无机固体过氧化物和过一硫酸盐的投加方式为按照质量比1:1制成混合粉末试剂形式投加。本实施方式中的无机固体过氧化物为任意比的过碳酸钠和过碳酸钾的混合物；过一硫酸盐为任意比的过一硫酸钾和过一硫酸钠的混合物。In this embodiment, the inorganic solid peroxide and persulfate are added in the form of a mixed powder reagent with a mass ratio of 1:1. The inorganic solid peroxide in this embodiment is a mixture of sodium percarbonate and potassium percarbonate in any ratio; the persulfate is a mixture of potassium persulfate and sodium persulfate in any ratio.
本实施方式一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法中，经氧化处理后，污水中的污染物(氯酚、溴酚、碘酚、硝基酚、苯胺、莠去津、2,4-D)的去除率达90%以上。In this embodiment, in a water treatment method that utilizes inorganic solid peroxide to induce persulfate to generate singlet oxygen, after the oxidation treatment, the pollutants in the sewage (chlorophenol, bromophenol, iodophenol, nitrophenol, The removal rate of aniline, atrazine, 2,4-D) is more than 90%.
具体实施方式二十一：本实施方式为一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法，其是通过以下步骤实现的：将无机固体过氧化钙和过一硫酸钾按照质量比为1:2加入到待处理水源水中，搅拌，控制过一硫酸盐在待处理污水中的浓度为20mg/L，水力停留反应时间为30min，即完成利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法。Specific Embodiment 21: This embodiment is a water treatment method that utilizes inorganic solid peroxide to induce persulfate to generate singlet oxygen, which is achieved through the following steps: combine inorganic solid calcium peroxide and peroxymonosulfate Potassium sulfate is added to the source water to be treated according to the mass ratio of 1:2, stirred, and the concentration of persulfate in the sewage to be treated is controlled to be 20mg/L, and the hydraulic retention reaction time is 30min, that is, the use of inorganic solid peroxide is completed. Water treatment method for inducing singlet oxygen generation from permonosulfate.
本实施方式中所述无机固体过氧化钙和过一硫酸钾的投加方式为按照质量比1:2分别以粉末试剂形式投加。In this embodiment, the inorganic solid calcium peroxide and potassium persulfate are added in the form of powder reagents at a mass ratio of 1:2.
本实施方式一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法中，水源水中含有0.1mg/L的内分泌干扰物-双酚A，经氧化处理后，双酚A的去除率达99%以上，如图1所示。In this embodiment, in a water treatment method that uses inorganic solid peroxide to induce persulfate to generate singlet oxygen, the source water contains 0.1 mg/L of endocrine disruptor-bisphenol A. After oxidation treatment, bisphenol A The removal rate is over 99%, as shown in Figure 1.
具体实施方式二十二：本实施方式为一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法，其是通过以下步骤实现的：将无机固体过氧化钙和过一硫酸钠按照质量比为1:2.5加入到待处理水源水中，搅拌，水力停留反应时间为150mg/L，水力停留反应时间为20min，即完成利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法。Specific Embodiment 22: This embodiment is a water treatment method that utilizes inorganic solid peroxide to induce peroxymonosulfate to generate singlet oxygen, which is achieved through the following steps: inorganic solid calcium peroxide and peroxy Add sodium sulfate into the source water to be treated according to the mass ratio of 1:2.5, stir, the hydraulic retention reaction time is 150mg/L, and the hydraulic retention reaction time is 20min, that is, the use of inorganic solid peroxide to induce persulfate to produce singlet Oxygen water treatment method.
本实施方式中所述固体漂白粉和无机固体过氧化物的投加方式为按照质量比1:2.5分别配制成溶液形式投加。In this embodiment, the solid bleaching powder and the inorganic solid peroxide are added in the form of solutions according to a mass ratio of 1:2.5.
本实施方式一种利用无机固体过氧化物诱导过一硫酸盐产生单线态氧的水处理方法中，经氧化处理后，污水中的污染物(四环素、青霉素、头孢、卡马西平、三氯生、雌酮、壬基酚)的去除率达90%以上。In this embodiment, in a water treatment method that utilizes inorganic solid peroxide to induce persulfate to generate singlet oxygen, after the oxidation treatment, the pollutants in the sewage (tetracycline, penicillin, cephalosporin, carbamazepine, triclosan , estrone, nonylphenol) removal rate of more than 90%.
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