CN115814797B - Preparation method of ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment - Google Patents
Preparation method of ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 89
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 73
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- 230000033444 hydroxylation Effects 0.000 title claims abstract description 20
- 238000005805 hydroxylation reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 40
- 239000007800 oxidant agent Substances 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 230000004048 modification Effects 0.000 claims abstract description 29
- 238000012986 modification Methods 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000007605 air drying Methods 0.000 claims abstract description 6
- 238000005273 aeration Methods 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000007598 dipping method Methods 0.000 claims description 16
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 2
- 239000002351 wastewater Substances 0.000 abstract description 24
- 239000010865 sewage Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 230000004913 activation Effects 0.000 description 11
- 238000007654 immersion Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003599 detergent Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000149 chemical water pollutant Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Abstract
The invention belongs to the technical field of preparation of sewage and wastewater catalysts, and particularly relates to a preparation method of an ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment, which comprises the following steps: (1) pretreatment: selecting an iron material, and carrying out oil removal and drying pretreatment on the iron material; (2) impregnation modification: immersing the iron material obtained in the step (1) in a modifying solution containing hydroxyl radicals for modification, taking out and air-drying after the immersing is finished, so as to obtain a surface modified catalyst matrix; (3) preparing an ozone catalytic oxidant: immersing the surface modified catalyst matrix obtained in the step (2) in an organic solvent mixed solution, adding hydrogen peroxide, intermittently introducing ozone for aeration, and reacting to obtain the ozone catalytic oxidant. The catalyst prepared by the method has high-efficiency catalytic activity and stability.
Description
Technical Field
The invention belongs to the technical field of preparation of sewage and wastewater catalysts, and particularly relates to a preparation method of an ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment.
Background
In the field of organic wastewater treatment, the ozone catalytic oxidation technology is considered as a green oxidation technology, and has the characteristics of high catalytic efficiency, no secondary pollutant generation and the like. The ozone oxidation technology applied in the current market has the problems of low ozone utilization rate, large consumption and the like, so that the application cost of the ozone oxidation is high, and the ozone oxidation technology is mostly limited to terminal disinfection treatment.
In recent years, methods for improving ozone catalytic oxidation efficiency based on metal oxide supported catalysts have been developed to a certain extent in the field of ozone oxidation treatment of organic wastewater. However, the metal oxide carrier catalyst generally selects metals with stronger catalytic activity, such as Mn, co, cu and the like, and forms metal oxide to be loaded on the surface of the carrier as an active center to catalyze ozone to be oxidized and decomposed to form OH, and the problems of catalyst deactivation, low catalytic activity, high catalyst cost and the like often occur along with precipitation and ablation of metal elements in the use process of the metal oxide carrier catalyst, so that the metal oxide carrier catalyst is still difficult to popularize and apply.
Disclosure of Invention
The invention aims to solve the technical problems and provide a preparation method of an ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment, which does not need to add acid and alkali to adjust the pH value, and the prepared catalyst is efficient and stable, and has efficient catalytic activity and stability.
The technical scheme of the invention is as follows:
the preparation method of the ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment comprises the following steps:
(1) Pretreatment: selecting an iron material, and carrying out oil removal and drying pretreatment on the iron material;
(2) And (3) dipping modification: immersing the iron material obtained in the step (1) in a modifying solution containing hydroxyl radicals for immersion modification, taking out and air-drying to obtain a surface modified catalyst matrix;
(3) Preparing an ozone catalytic oxidant: immersing the surface modified catalyst matrix obtained in the step (2) in an organic solvent mixed solution, adding hydrogen peroxide, intermittently introducing ozone for aeration, and reacting to obtain the ozone catalytic oxidant.
The step (3) is an activation modification process, and the catalyst matrix can generate more efficient catalytic performance through activation modification. If the activating process of the step (3) is absent, the process only proceeds to the step (2), and the iron oxyhydroxide attached to the surface of the obtained catalyst substrate is not uniform and is dispersed on the surface of the substrate in irregular blocks. If the activation of the step (3) is not carried out, the surface of the obtained iron-based catalyst forms ferric oxide, so that no obvious catalytic performance exists.
The iron material is iron shavings or scrap iron, waste is used as raw materials, and the cost is low.
In order to enhance the surface modification effect of the ferrous material, preferably, in the step (2) of the present invention, the modifying solution containing hydroxyl radicals is a Fenton solution.
In order to obtain the modified solution rich in hydroxyl radicals, preferably, in the step (2) of the invention, the mole ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:1-5, wherein H 2O2 is derived from hydrogen peroxide with the mass fraction of 27.5% -30%.
In order to fully modify the surface of the ferrous material, preferably, in the step (2) of the invention, the impregnation modification is carried out for 24-72 hours.
In order to fully modify the surface of the ferrous material, preferably, in the step (2), the dipping modification process is stirred by using a mode of internal circulation of the modifying liquid, wherein the internal circulation speed is 2-5 times/h and 20-60 min/time.
In order to obtain excellent activation effect and to improve catalytic activity and stability, it is preferable that the bulk density of the surface-modified catalyst substrate in the organic solvent mixture in the step (3) of the present invention is 100 to 500g/L.
In order to further enhance the activation effect, preferably, in the step (3), hydrogen peroxide is added, ozone is intermittently introduced for aeration, and the reaction is continued for 72 hours, wherein the concentration of ozone is 20-100mg/L, the molar ratio of ozone to H 2O2 is 1:1-5, H 2O2 is derived from 27.5-30% of hydrogen peroxide by mass fraction, the surface modified catalyst matrix and the ozone interact with the hydrogen peroxide, so that the surface components of the surface modified catalyst matrix are oxidized into ferric hydroxide, and the specific reaction formula is shown in the formulas (a) - (c):
Fe2++H2O2→Fe3++OH-+·OH (a)
Fe2++O3+H2O→Fe3++OH-+·OH (b)
Fe3++OH-→FeOOH+H2O (c)。
in the step (3), the solute of the organic solvent mixed solution is taken as an electron acceptor of the oxidation reaction, and is a substance which can be catalytically decomposed by ozone, preferably, the organic solvent mixed solution is an organic substance with the carbon number of less than 20 and does not contain heterocycle, preferably, an aqueous solution of potassium hydrogen phthalate or a glucose solution, the concentration of the organic solvent mixed solution is 200-1000mg/L according to COD equivalent, and the reaction formula is as follows:
RH+·OH→R·+H2O (d)。
In order to ensure that enough hydroxyl radicals are provided and promote the activation of the surface modified catalyst matrix, preferably, in the step (3) of the invention, fenton solution is supplemented into the organic solvent mixed solution every 24 hours, wherein the supplementing amount is 0.5-1.5kg/m 3, and the molar ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:1-5, wherein H 2O2 is derived from hydrogen peroxide with the mass fraction of 27.5% -30%.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the preparation and activation conditions of the ozone catalytic oxidant are simple, pH conditions of a reaction environment are not required to be maintained by acid and alkali, the addition of dangerous chemicals in the preparation process is avoided, and potential hazards are eliminated.
2. The ozone catalytic oxidant prepared by the invention can promote complex chain reaction of ozone catalytic oxidation and OH formation, can improve ozone reaction efficiency, shorten reaction time, reduce system energy consumption and effectively and efficiently remove organic pollutants in organic wastewater in wastewater treatment.
3. The ozone catalytic oxidant prepared by the invention is not easy to deactivate in the use process, and has high catalytic activity and stability.
4. The iron-based material used in the invention is prepared by using the lathe processing waste, has low cost and is easy to popularize and use in a large scale.
Drawings
FIG. 1 is a flow chart of the preparation process of the ozone catalytic oxidizer of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment comprises the following steps:
(1) Pretreatment: 2kg of iron shavings are selected as raw materials, repeatedly soaked and washed for 2 times by using a commercially available detergent to remove oil, and the obtained product is placed in a cool and ventilated place for natural drying after the oil removal;
(2) And (3) dipping modification: immersing the iron shavings pretreated in the step (1) in Fenton solution completely for immersion modification, wherein the mole ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:3, H 2O2 is from 30% hydrogen peroxide, the immersion modification is carried out for 24 hours at room temperature, an internal circulation (a modification solution is in a reactor and continuously flows in a mode of being externally provided with a water pump) is used for stirring during the immersion, the internal circulation mode of the modification solution is lower in and upper out, the internal circulation speed is 2 times/H, 30 min/time, and the catalyst is naturally air-dried in a cool and ventilated place after the immersion is completed, so that a surface modified catalyst matrix is prepared;
(3) Preparing an ozone catalytic oxidant: immersing the prepared surface modified catalyst matrix in a potassium hydrogen phthalate aqueous solution with COD equivalent of 200mg/L, wherein the volume density of the surface modified catalyst matrix in the potassium hydrogen phthalate aqueous solution is 100g/L, intermittently (after 8 hours of ozone is introduced, 2 hours of air is introduced, and circulation) introducing the ozone with the concentration of 20mg/L, wherein the molar ratio of ozone to H 2O2 is 1:5, H 2O2 is derived from 30% hydrogen peroxide by mass, fenton solution is supplemented every 24 hours, the supplementing amount is 0.5kg/m 3 each time, the molar ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:3, and the H 2O2 is derived from 30% hydrogen peroxide by mass, and continuously reacting for 72 hours to obtain the activated ozone catalyst.
Example 2
The preparation method of the ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment comprises the following steps:
(1) Pretreatment: 2kg of iron shavings are selected as raw materials, repeatedly soaked and washed for 2 times by using a commercially available detergent to remove oil, and the obtained product is placed in a cool and ventilated place for natural drying after the oil removal;
(2) And (3) dipping modification: immersing the iron shavings pretreated in the step (1) in Fenton solution completely for immersion modification, wherein the mole ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:1, H 2O2 is from hydrogen peroxide with the mass fraction of 27.5%, the immersion modification is carried out for 48 hours at room temperature, an internal circulation (the modification solution is in the reactor and continuously flows by a peripheral water pump) mode is used for stirring during the immersion, the internal circulation speed is 3 times/H, 50 min/time, and the catalyst substrate with the surface modified is prepared by naturally air-drying at a cool ventilation position after the immersion is completed;
(3) Preparing an ozone catalytic oxidant: immersing the prepared surface modified catalyst matrix in a potassium hydrogen phthalate aqueous solution with COD equivalent of 800mg/L, intermittently (after 8 hours of ozone is introduced, 2 hours of air is introduced, circulation) introducing the ozone concentration of 40mg/L, wherein H 2O2 is derived from 27.5% of hydrogen peroxide by mass, fenton reagent is supplemented every 24 hours, the supplementing amount is 1.5kg/m 3, the mole ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:1, and the activated ozone catalytic oxidant is prepared after the reaction is continuously carried out for 72 hours, wherein H 2O2 is derived from 27.5% of hydrogen peroxide by mass.
Example 3
The preparation method of the ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment comprises the following steps:
(1) Pretreatment: selecting 2kg of scrap iron as a raw material, repeatedly soaking and cleaning the raw material by using a commercially available detergent for 2 times to remove oil, and naturally drying the raw material in a cool and ventilated place after removing the oil;
(2) And (3) dipping modification: immersing the iron shavings pretreated in the step (1) in Fenton solution completely for dipping modification, wherein the mole ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:5, H 2O2 is from hydrogen peroxide with the mass fraction of 27.5%, dipping modification is carried out for 72 hours at room temperature, stirring is carried out in an internal circulation (the modified solution is in a reactor and continuously flows in a mode of being externally provided with a water pump) mode, the internal circulation speed is 5 times/H, 60 min/time, and the catalyst substrate with the surface modified is prepared by naturally air-drying at a cool and ventilated place after the dipping is completed;
(3) Preparing an ozone catalytic oxidant: immersing the prepared surface modified catalyst matrix in a glucose solution with the COD equivalent of 1000mg/L, intermittently (after 8 hours of ozone is introduced, 2 hours of air is introduced, circulation) introducing the ozone with the concentration of 100mg/L, wherein H 2O2 is derived from hydrogen peroxide with the mass fraction of 27.5%, fenton reagent is supplemented once every 24 hours, the supplementing amount is 1.0kg/m 3, the mole ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:5, wherein H 2O2 is derived from hydrogen peroxide with the mass fraction of 27.5%, and continuously reacting for 72 hours, so as to obtain the activated ozone catalytic oxidant.
Comparative example 1
The preparation method of the ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment comprises the following steps:
(1) Pretreatment: selecting 2kg of scrap iron as a raw material, repeatedly soaking and cleaning the raw material by using a commercially available detergent for 2 times to remove oil, and naturally drying the raw material in a cool and ventilated place after removing the oil;
(2) And (3) dipping modification: immersing the iron shavings pretreated in the step (1) in tap water equal to Fenton solution in the step (2) in the embodiment 3 for 72 hours, stirring in an internal circulation (the modified solution continuously flows in the reactor through a peripheral water pump) mode during the immersion, wherein the internal circulation speed is 5 times/h, 60 minutes/time, and naturally drying in a cool and ventilated place to prepare an iron-based catalyst matrix;
(3) Preparing an ozone catalytic oxidant: immersing the iron-based catalyst matrix prepared in the step (2) in a glucose solution with COD equivalent of 1000mg/L, intermittently (after 8 hours of ozone is introduced, 2 hours of air is introduced, circulation) introducing the ozone with the concentration of 100mg/L, wherein H 2O2 is derived from hydrogen peroxide with the mass fraction of 27.5%, fenton solution is supplemented once every 24 hours, the supplementing amount is 1.0kg/m 3, the mole ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:5, wherein H 2O2 is derived from hydrogen peroxide with the mass fraction of 27.5%, and continuously reacting for 72 hours, so as to obtain the activated iron-based catalyst for the control group.
Comparative example 2
The preparation method of the ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment comprises the following steps (compared with the example 1 without the step (3)):
(1) Pretreatment: 2kg of iron shavings are selected as raw materials, repeatedly soaked and washed for 2 times by using a commercially available detergent to remove oil, and the obtained product is placed in a cool and ventilated place for natural drying after the oil removal;
(2) And (3) dipping modification: immersing the iron shavings pretreated in the step (1) in Fenton solution completely for dipping modification, wherein the mole ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:3, H 2O2 is from 30% hydrogen peroxide, dipping modification is carried out for 24 hours at room temperature, an internal circulation (a modifying solution is in a reactor and continuously flows in a mode of a peripheral water pump) mode is used for stirring during dipping, the internal circulation mode of the modifying solution is lower in and upper out, the internal circulation speed is 2 times/H, 30 min/time, and the surface modified catalyst matrix is prepared by naturally air-drying at a cool and ventilated place after dipping.
Test example 1: the ozone catalytic oxidant has the catalytic treatment effect on the organic wastewater
The performance test of the catalyst is carried out by taking the effect of ozone catalytic oxidation on high, medium and low concentration organic wastewater treatment as the performance test of the catalyst: and (5) inspecting the COD of the water quality and judging the catalytic effect. The testing process comprises the following steps: the modified iron shavings are placed into a fixed bed ozone catalytic oxidation reaction device for ozone test. Wherein the high-concentration organic wastewater sample is landfill leachate of a landfill, and the COD is 1500-2000mg/L; the water sample of the medium-concentration organic wastewater is the inlet water of a sewage treatment plant in a chemical industry park, and the COD is 200-400mg/L; the water sample of the low-concentration organic wastewater is produced water in a secondary sedimentation tank of a white spirit wastewater centralized treatment plant, and the COD is 100-200mg/L. The bulk density of the iron-based catalyst matrix is 0.3kg/m 3; before the reaction, pH value is not required to be regulated, and 2.5ml/L, 1.5ml/L and 1.0ml/L auxiliary oxidants (specifically, 30% hydrogen peroxide by mass fraction) are respectively added into the high-concentration wastewater, the medium-concentration wastewater and the low-concentration wastewater; 1.0L of wastewater; ozone concentration is 45mg/L. The treatment time of the high, medium and low concentration organic wastewater is respectively 80min, 50min and 20min.
The wastewater at the water inlet of the ozone reaction device and the quality of the treated produced water are detected, and the obtained test results are shown in tables 1-3 below.
TABLE 1 comparison of catalytic treatment effects of high concentration organic wastewater
| Examples | COD before reaction (mg/L) | COD after reaction (mg/L) | Removal efficiency (%) |
| Example 1 | 1788 | 833 | 53.4％ |
| Example 2 | 1750 | 766 | 56.2％ |
| Example 3 | 1558 | 749 | 55.8％ |
| Comparative example 1 | 1680 | 1463 | 12.9％ |
| Comparative example 2 | 1700 | 1611 | 5.2％ |
Comparison of catalytic treatment effects of concentrated organic wastewater in Table 2
TABLE 3 comparison of catalytic treatment effects of Low concentration organic wastewater
| Examples | COD before reaction (mg/L) | COD after reaction (mg/L) | Removal efficiency (%) |
| Example 1 | 147 | 51 | 65.3％ |
| Example 2 | 145 | 55 | 61.2％ |
| Example 3 | 137 | 47 | 65.7％ |
| Comparative example 1 | 133 | 112 | 18％ |
| Comparative example 2 | 151 | 125 | 16.6％ |
As can be seen from tables 1-3, the ozone catalytic oxidation agent prepared by the method can improve the ozone catalytic oxidation speed and improve the pollutant removal efficiency, particularly in the step (2) of the invention, the modified solution containing hydroxyl radicals is adopted for soaking, so that the surface of the ferrous material is oxidized to form ferric hydroxide, the subsequent activation is carried out, the activity of the ozone catalytic oxidation agent is improved, the catalytic oxidation efficiency is improved, and if the step is absent, the activation of the subsequent step is influenced, and the obtained catalyst has poor catalytic effect; when the step (2) is only carried out and the step (3) activation treatment is not carried out, the iron oxyhydroxide attached to the surface of the obtained catalyst matrix is not uniform and is irregularly dispersed in a block shape, and if the step (3) activation is absent, the iron-based catalyst surface can form iron oxide in the subsequent use, so that the catalyst has no obvious catalytic performance.
Test example 2: the ozone catalytic oxidant of the invention has continuous catalytic treatment effect on organic wastewater
The effect of ozone continuous catalytic oxidation high-concentration organic wastewater treatment is used as a catalyst performance test: and (5) inspecting the COD of the effluent water quality in different reaction time, and judging the catalytic performance and stability of the catalyst. The testing process comprises the following steps: ozone test was performed using the ozone catalytic oxidation catalyst prepared in example 1 placed in a fixed bed ozone catalytic oxidation reaction apparatus. Wherein the high-concentration organic wastewater sample is landfill leachate of a landfill, the COD is 1500-2000mg/L, and the wastewater amount is 1.65L; HRT is 60min; the bulk density of the iron-based catalyst matrix is 0.3kg/m 3; before the reaction, the pH value is not required to be regulated, and the addition amount of the auxiliary oxidant (specifically, 30% hydrogen peroxide by mass fraction) is 2.5ml/L; ozone concentration is 45mg/L.
The wastewater at the water inlet of the ozone reaction device and the quality of the treated produced water are detected at regular time every day, and the obtained test results are shown in the following table 4.
TABLE 4 continuous catalytic treatment effect of high concentration organic wastewater
As is clear from Table 4, the high concentration organic wastewater treated by the ozone catalytic oxidizer prepared in example 1 of the present invention has a high removal effect after long-term use, i.e. the effect is different from that just after the ozone catalytic oxidizer is put into use, which shows that the ozone catalytic oxidizer prepared in example 1 of the present invention is stable and has high catalytic activity.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (9)
1. The preparation method of the ozone catalytic oxidation agent based on zero-valent iron surface hydroxylation treatment is characterized by comprising the following steps:
(1) Pretreatment: selecting an iron material, and carrying out oil removal and drying pretreatment on the iron material;
(2) And (3) dipping modification: immersing the iron material obtained in the step (1) in a modifying solution containing hydroxyl radicals for impregnation modification, and taking out and air-drying after the impregnation is finished to obtain a surface modified catalyst matrix;
(3) Preparing an ozone catalytic oxidant: immersing the surface modified catalyst matrix obtained in the step (2) in an organic solvent mixed solution, adding hydrogen peroxide, intermittently introducing ozone for aeration, and reacting to obtain an ozone catalytic oxidant;
in the step (3), the organic solvent mixed solution is an organic matter which has the carbon number lower than 20 and does not contain heterocycle, and the concentration of the organic matter is 200-1000mg/L according to COD equivalent.
2. The method for preparing the ozone catalytic oxidizer based on zero-valent iron surface hydroxylation treatment as claimed in claim 1, which is characterized in that: in the step (2), the modified solution containing hydroxyl radicals is Fenton solution.
3. The method for preparing the ozone catalytic oxidizer based on zero-valent iron surface hydroxylation treatment as claimed in claim 1, which is characterized in that: in the step (2), the dipping modification is carried out for 24-72h.
4. The method for preparing the ozone catalytic oxidizer based on zero-valent iron surface hydroxylation treatment as claimed in claim 1, which is characterized in that: in the step (3), the organic solvent mixed solution is potassium hydrogen phthalate aqueous solution or glucose solution.
5. The method for preparing the ozone catalytic oxidizer based on zero-valent iron surface hydroxylation treatment as claimed in claim 1, which is characterized in that: in the step (3), the volume density of the surface modified catalyst matrix in the organic solvent mixed solution is 100-500g/L.
6. The method for preparing the ozone catalytic oxidizer based on zero-valent iron surface hydroxylation treatment as claimed in claim 1, which is characterized in that: in the step (3), hydrogen peroxide is added, ozone is intermittently introduced for aeration, and the reaction is continued for 72 hours, wherein the concentration of the ozone is 20-100mg/L.
7. The method for preparing the ozone catalytic oxidizer based on zero-valent iron surface hydroxylation treatment as claimed in claim 1, which is characterized in that: in the step (3), the molar ratio of ozone to H 2O2 is 1:1-5, wherein H 2O2 is derived from hydrogen peroxide with the mass fraction of 27.5% -30%.
8. The method for preparing the ozone catalytic oxidizer based on zero-valent iron surface hydroxylation treatment as claimed in claim 2, which is characterized in that: in the step (3), fenton solution is supplemented into the organic solvent mixed solution every 24 hours, and the supplementing amount is 0.5-1.5kg/m 3 each time.
9. The method for preparing the ozone catalytic oxidizer based on zero-valent iron surface hydroxylation treatment as claimed in claim 2 or 8, wherein: the mole ratio of H 2O2 to Fe 2+ in the Fenton solution is 1:1-5, wherein H 2O2 is derived from hydrogen peroxide with the mass fraction of 27.5% -30%.
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