CN115814797A - Preparation method of ozone catalytic oxidant based on zero-valent iron surface hydroxylation treatment - Google Patents
Preparation method of ozone catalytic oxidant 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 115
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 72
- 239000007800 oxidant agent Substances 0.000 title claims abstract description 41
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 32
- 230000033444 hydroxylation Effects 0.000 title claims abstract description 21
- 238000005805 hydroxylation reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 39
- 230000004048 modification Effects 0.000 claims abstract description 31
- 238000012986 modification Methods 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000007598 dipping method Methods 0.000 claims abstract description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000007605 air drying Methods 0.000 claims abstract description 7
- 238000005273 aeration Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 11
- 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 6
- 239000008103 glucose Substances 0.000 claims description 6
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000013589 supplement Substances 0.000 claims description 3
- 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
- 239000002351 wastewater Substances 0.000 abstract description 26
- 239000010865 sewage Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 description 17
- 238000002791 soaking Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 14
- 238000001994 activation Methods 0.000 description 12
- 230000004913 activation Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 4
- 239000003791 organic solvent mixture Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000149 chemical water pollutant Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010412 oxide-supported catalyst Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000003244 pro-oxidative effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen 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
- 230000009469 supplementation Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
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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 oxidant 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) dipping modification: dipping the ferrous material obtained in the step (1) in a modification solution containing hydroxyl free radicals for modification, taking out the ferrous material after the dipping is finished, and air-drying the ferrous material to obtain a surface-modified catalyst substrate; (3) preparing an ozone catalytic oxidant: and (3) dipping the surface modified catalyst substrate 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 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 oxidant 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 ozone oxidation is high, and most of the ozone oxidation technology is limited to terminal disinfection treatment.
In recent years, methods for improving catalytic oxidation efficiency of ozone based on metal oxide supported catalysts have been developed to some extent in the field of treating organic wastewater by ozone oxidation. However, metal oxide supported catalysts generally select metals with strong catalytic activity, such as Mn, co, cu, etc., to form metal oxides supported on the surface of the carrier as active centers to catalyze the oxidative decomposition of ozone to form-OH, and with the precipitation and ablation of metal elements during the use process, problems of catalyst deactivation, low catalytic activity, high catalyst cost, etc. often occur, so that the catalyst is still difficult to popularize and apply.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems, provides a preparation method of an ozone catalytic oxidant based on zero-valent iron surface hydroxylation treatment, according to the method, acid and alkali are not needed to be added for adjusting 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 oxidant 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) Dipping modification: immersing the ferrous material obtained in the step (1) in a modification solution containing hydroxyl radicals for impregnation modification, taking out and air-drying to obtain a surface-modified catalyst substrate;
(3) Preparing an ozone catalytic oxidant: and (3) dipping the surface modified catalyst substrate 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 substrate can generate high-efficiency catalytic performance through activation modification. If the activation process of the step (3) is lacked, the process only proceeds to the step (2), and the obtained iron oxyhydroxide attached to the surface of the catalyst substrate is not uniform and is irregularly dispersed on the surface of the substrate. If the activation in the step (3) is not carried out, iron oxide is formed on the surface of the obtained iron-based catalyst, so that the iron-based catalyst has no obvious catalytic performance.
The iron material is iron shavings or scrap iron, and the waste is used as the raw material, so that the cost is low.
In order to improve the surface modification effect of the ferrous material, preferably, in the step (2) of the present invention, the modification solution containing hydroxyl radicals is a Fenton solution.
In order to obtain a hydroxyl radical-rich modified solution, it is preferable that H in the Fenton solution is mentioned in step (2) of the present invention 2 O 2 With Fe 2+ In a molar ratio of 1:1-5, wherein H 2 O 2 Is derived from 27.5 to 30 mass percent of hydrogen peroxide.
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 24-72h.
In order to fully modify the surface of the ferrous material, in the step (2) of the present invention, preferably, the impregnation modification process is stirred by using a modification solution internal circulation mode, and the internal circulation speed is 2-5 times/h and 20-60 min/time.
In order to obtain excellent activation effect and improve catalytic activity and stability, it is preferable that the bulk density of the surface-modified catalyst substrate in the organic solvent mixture in step (3) of the present invention is 100 to 500g/L.
In order to further improve the activation effect, preferably, in the step (3) of the invention, 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, and the ozone and H 2 O 2 The molar ratio is 1:1-5, wherein H 2 O 2 The surface-modified catalyst is prepared from 27.5-30% of hydrogen peroxide by mass, the surface-modified catalyst substrate, ozone and the hydrogen peroxide interact with each other to oxidize surface components of the surface-modified catalyst substrate into iron oxyhydroxide, and the specific reaction formula is as shown in formulas (a) - (c):
Fe 2+ +H 2 O 2 →Fe 3+ +OH - +·OH (a)
Fe 2+ +O 3 +H 2 O→Fe 3+ +OH - +·OH (b)
Fe 3+ +OH - →FeOOH+H 2 O (c)。
in step (3) of the present invention, the solute of the organic solvent mixture is an electron acceptor for oxidation reaction, and is a substance that can be catalytically decomposed by ozone, preferably, the organic solvent mixture is an organic substance having a carbon number of less than 20 and containing no heterocyclic ring, preferably, an aqueous solution of potassium hydrogen phthalate or a glucose solution, and has a concentration of 200-1000mg/L in terms of COD equivalent, and the reaction formula (d) is as follows:
RH+·OH→R·+H 2 O (d)。
in order to ensure that enough hydroxyl radicals are provided to promote the activation of the surface modified catalyst substrate, it is preferable that the Fenton solution is supplemented into the organic solvent mixture every 24 hours in step (3) of the present invention, and the supplementation amount is 0.5-1.5kg/m 3 H in the Fenton solution 2 O 2 With Fe 2+ In a molar ratio of 1:1-5, wherein H 2 O 2 Is derived from 27.5 to 30 mass percent of hydrogen peroxide.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the ozone catalytic oxidant has simple preparation and activation conditions, does not need to maintain the pH condition of the reaction environment by acid or alkali, avoids the addition of dangerous chemicals in the preparation process, and eliminates potential hazards.
2. The ozone catalytic oxidant prepared by the invention can promote the complex chain reaction formed by catalytic oxidation of ozone and OH, can improve the ozone reaction efficiency, shorten the reaction time, reduce the energy consumption of a system and effectively and efficiently remove the organic pollutants in the organic wastewater in the treatment of the wastewater containing the organic pollutants.
3. The ozone catalytic oxidant prepared by the invention is not easy to inactivate in the using process, and has high-efficiency catalytic activity and stability.
4. The iron base used in the invention is prepared by using lathe processing waste materials, has low cost and is easy to popularize and use in a large range.
Drawings
FIG. 1 is a flow chart of the process for preparing the ozone catalytic oxidizer of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the ozone catalytic oxidant based on zero-valent iron surface hydroxylation treatment comprises the following steps:
(1) Pretreatment: selecting 2kg of iron shavings as a raw material, repeatedly soaking and cleaning the iron shavings by using a commercially available detergent for 2 times to remove oil, and naturally drying the iron shavings in a cool and ventilated place after removing the oil;
(2) Dipping modification: completely immersing the iron shavings pretreated in the step (1) in a Fenton solution for impregnation modification, wherein H in the Fenton solution 2 O 2 With Fe 2+ In a molar ratio of 1:3, wherein H 2 O 2 Soaking and modifying for 24 hours at room temperature by using 30% hydrogen peroxide, stirring in an internal circulation mode (the modified liquid flows continuously in a reactor by an external water pump) during soaking, wherein the internal circulation mode of the modified liquid is that the modified liquid enters from the bottom and goes out from the top, the internal circulation speed is 2 times/h and 30 min/time, and after soaking, placing the modified liquid in a cool and ventilated place for natural air drying to prepare a surface modified catalyst substrate;
(3) Preparing an ozone catalytic oxidant: immersing the prepared surface modified catalyst substrate in a potassium hydrogen phthalate water solution with COD equivalent of 200mg/L, wherein the bulk density of the surface modified catalyst substrate in the potassium hydrogen phthalate water solution is 100g/L, intermittently (introducing ozone for 8 hours, introducing air for 2 hours, and circulating) introducing ozone with the concentration of 20mg/L, and mixing ozone and H 2 O 2 The molar ratio is 1:5, where H 2 O 2 Is derived from 30 percent hydrogen peroxide, and the Fenton solution is supplemented every 24 hours, and the supplementing amount is 0.5kg/m 3 H in Fenton solution mentioned 2 O 2 With Fe 2+ In a molar ratio of 1:3, wherein H 2 O 2 Is prepared from 30 percent of hydrogen peroxide by mass percent, and continuously reacts for 72 hours to prepare the activated ozone catalytic oxidant.
Example 2
The preparation method of the ozone catalytic oxidant based on zero-valent iron surface hydroxylation treatment comprises the following steps:
(1) Pretreatment: selecting 2kg of iron shavings as a raw material, repeatedly soaking and cleaning the iron shavings by using a commercially available detergent for 2 times to remove oil, and naturally drying the iron shavings in a cool and ventilated place after removing the oil;
(2) Dipping modification: completely immersing the iron shavings pretreated in the step (1) in a Fenton solution for impregnation modification, wherein H in the Fenton solution 2 O 2 With Fe 2+ In a molar ratio of 1:1, wherein H 2 O 2 Derived from mass fraction27.5 percent of hydrogen peroxide is soaked and modified for 48 hours at room temperature, stirring is carried out in an internal circulation mode (the modified solution flows continuously in the reactor through an external water pump) during the soaking period, the internal circulation speed is 3 times/h and 50 min/time, and after the soaking is finished, the mixture is placed in a cool and ventilated place for natural air drying to prepare a surface modified catalyst substrate;
(3) Preparing an ozone catalytic oxidant: immersing the prepared surface modified catalyst substrate in a potassium hydrogen phthalate water solution with COD equivalent of 800mg/L, wherein the bulk density of the surface modified catalyst substrate in the potassium hydrogen phthalate water solution is 200g/L, intermittently (after 8 hours of ozone introduction, 2 hours of air introduction and circulation) introducing ozone with concentration of 40mg/L, and ozone and H are introduced 2 O 2 The molar ratio is 1:3, where H 2 O 2 Is derived from 27.5 percent of hydrogen peroxide, and the Fenton reagent is supplemented every 24 hours, wherein the supplement amount is 1.5kg/m 3 Reference to H in Fenton's solution 2 O 2 With Fe 2+ In a molar ratio of 1:1, wherein H 2 O 2 The ozone catalytic oxidant is prepared by continuously reacting 27.5 mass percent hydrogen peroxide for 72 hours.
Example 3
The preparation method of the ozone catalytic oxidant 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 scrap iron for 2 times by using a commercially available detergent to remove oil, and naturally drying the scrap iron in a cool and ventilated place after removing the oil;
(2) Dipping modification: completely immersing the iron shavings pretreated in the step (1) in a Fenton solution for impregnation modification, wherein H in the Fenton solution 2 O 2 With Fe 2+ In a molar ratio of 1:5, wherein H 2 O 2 Soaking and modifying with 27.5% hydrogen peroxide at room temperature for 72 hr, stirring with internal circulation (modification solution flowing in reactor via external water pump) at speed of 5 times/h for 60 min/time, and air drying in shade to obtain the final productA surface-modified catalyst substrate;
(3) Preparing an ozone catalytic oxidant: immersing the prepared surface modified catalyst substrate in a glucose solution with the COD equivalent of 1000mg/L, wherein the bulk density of the surface modified catalyst substrate in the glucose solution is 500g/L, intermittently (after 8 hours of ozone introduction, 2 hours of air introduction and circulation) introducing the ozone concentration of 100mg/L, and the ozone and H are mixed 2 O 2 The molar ratio is 1:3, where H 2 O 2 Is derived from 27.5 percent of hydrogen peroxide, and the Fenton reagent is supplemented every 24 hours, wherein the supplement amount is 1.0kg/m 3 Reference to H in Fenton's solution 2 O 2 With Fe 2+ In a molar ratio of 1:5, wherein H 2 O 2 Is prepared from 27.5 percent of hydrogen peroxide by mass percent, and continuously reacts for 72 hours to prepare the activated ozone catalytic oxidant.
Comparative example 1
The preparation method of the ozone catalytic oxidant 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 scrap iron for 2 times by using a commercially available detergent to remove oil, and naturally drying the scrap iron in a cool and ventilated place after removing the oil;
(2) Dipping modification: completely immersing the iron shavings pretreated in the step (1) in tap water with the same amount as the Fenton solution in the step (2) in the embodiment 3, soaking for 72 hours, stirring in an internal circulation (the modified solution continuously flows in the reactor in an external water pump) mode during the soaking period, and placing the reactor in a cool and ventilated place for natural drying at the internal circulation speed of 5 times/h and 60 min/time to prepare an iron-based catalyst matrix;
(3) Preparing an ozone catalytic oxidant: immersing the iron-based catalyst substrate prepared in the step (2) in a glucose solution with the COD equivalent of 1000mg/L, wherein the volume density of the iron-based catalyst substrate in the glucose solution is 500g/L, intermittently (introducing ozone for 8 hours, introducing air for 2 hours, and circulating) introducing ozone with the concentration of 100mg/L, and mixing ozone and H 2 O 2 The molar ratio is 1:5, wherein H 2 O 2 Is prepared from 27.5 percent of hydrogen peroxide by mass percent and is supplemented every 24 hourssub-Fenton solution with a make-up of 1.0kg/m 3 Reference to H in Fenton's solution 2 O 2 With Fe 2+ In a molar ratio of 1:5, wherein H 2 O 2 The catalyst is prepared from 27.5% hydrogen peroxide by mass percent, and the reaction is continued for 72 hours to prepare the control group iron-based catalyst after activation.
Comparative example 2
A method for preparing an ozone catalytic oxidizer based on zero-valent iron surface hydroxylation treatment, comprising the following steps (compared with example 1 without step (3)):
(1) Pretreatment: selecting 2kg of iron shavings as a raw material, repeatedly soaking and cleaning the iron shavings by using a commercially available detergent for 2 times to remove oil, and naturally drying the iron shavings in a cool and ventilated place after removing the oil;
(2) Dipping modification: completely immersing the iron shavings pretreated in the step (1) in a Fenton solution for impregnation modification, wherein H in the Fenton solution 2 O 2 With Fe 2+ In a molar ratio of 1:3, wherein H 2 O 2 The surface-modified catalyst base body is prepared by soaking and modifying 30% hydrogen peroxide at room temperature for 24 hours, stirring in an internal circulation mode (modification liquid flows continuously in a reactor through an external water pump) during soaking, allowing the modification liquid to enter and exit from the bottom at an internal circulation speed of 2 times/h for 30 min/time, and naturally air-drying in a cool and ventilated place after soaking.
Test example 1: the catalytic treatment effect of the ozone catalytic oxidant 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: the COD of the water quality is inspected and the catalytic effect is judged. The testing process comprises the following steps: and placing the modified iron shavings into a fixed bed ozone catalytic oxidation reaction device for an ozone test. Wherein the high-concentration organic wastewater sample is landfill leachate of a certain refuse landfill, and the COD is 1500-2000mg/L; the medium-concentration organic wastewater sample is the inlet water of a sewage treatment plant in a certain chemical industrial park, and the COD is 200-400mg/L; the low-concentration organic wastewater water sample is water produced by a secondary sedimentation tank of a certain white spirit wastewater centralized treatment plant, and the COD is 100-200mg/L. The bulk density of the iron-based catalyst substrate is0.3kg/m 3 (ii) a Before the reaction, the pH value does not need to be adjusted, and 2.5ml/L, 1.5ml/L and 1.0ml/L of pro-oxidants (specifically, 30% hydrogen peroxide by mass) are respectively added into the high-concentration wastewater, the medium-concentration wastewater and the low-concentration wastewater; the amount of wastewater was 1.0L; the ozone concentration was 45mg/L. The treatment time of the high, medium and low concentration organic wastewater is respectively 80min, 50min and 20min.
The quality of 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.
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％ |
TABLE 2 comparison of catalytic treatment effect of concentrated organic wastewater
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 to 3, the ozone catalytic oxidation agent prepared by the method of the present invention can increase the ozone catalytic oxidation speed and improve the pollutant removal efficiency, and particularly in step (2) of the present invention, the modified solution containing hydroxyl radicals is used for impregnation, so that the surface of the ferrous material is oxidized to form iron oxyhydroxide, and then the subsequent activation is performed to improve the activity of the ozone catalytic oxidation agent, thereby improving the catalytic oxidation efficiency, if this step is lacked, the activation of the subsequent step is affected, and the catalytic effect of the obtained catalyst is poor; and when the step (2) is carried out only and the step (3) is not carried out, the iron oxyhydroxide attached to the surface of the obtained catalyst substrate is not uniform and is dispersed in an irregular block shape, if the activation of the step (3) is lacked, iron oxide can be formed on the surface of the iron-based catalyst 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 performance test of the catalyst takes the effect of ozone continuous catalytic oxidation treatment of high-concentration organic wastewater as the test: and (4) observing the COD (chemical oxygen demand) of the effluent water at different reaction times, and judging the catalytic performance and stability of the catalyst. The testing process comprises the following steps: the ozone catalytic oxidizing agent prepared in example 1 was placed in a fixed bed ozone catalytic oxidation reaction apparatus to perform an ozone test. Wherein the high-concentration organic wastewater sample is landfill leachate of a certain refuse landfill, COD is 1500-2000mg/L, and the wastewater amount is 1.65L; HRT 60min; the bulk density of the iron-based catalyst substrate is 0.3kg/m 3 (ii) a Before the reaction, the pH value does not need to be adjusted, and the adding amount of the pro-oxidant (specifically, 30 mass percent of hydrogen peroxide) is 2.5ml/L; the ozone concentration was 45mg/L.
The quality of the wastewater at the water inlet of the ozone reaction device and the treated produced water is regularly detected 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 can be seen from Table 4, the ozone oxidizing catalyst prepared in example 1 of the present invention still has a high removal effect after a long period of time, i.e., no difference from the effect immediately after the ozone oxidizing catalyst is put into use, when it is used for treating high concentration organic wastewater, which indicates that the ozone oxidizing catalyst prepared in example 1 of the present invention is stable and has a high catalytic activity.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. The preparation method of the ozone catalytic oxidant based on zero-valent iron surface hydroxylation treatment is characterized by comprising the following steps of:
(1) Pretreatment: selecting an iron material, and carrying out oil removal and drying pretreatment on the iron material;
(2) Dipping modification: immersing the ferrous material obtained in the step (1) in a modification solution containing hydroxyl radicals for impregnation modification, taking out the ferrous material after the impregnation is finished, and air-drying the ferrous material to obtain a surface-modified catalyst substrate;
(3) Preparing an ozone catalytic oxidant: and (3) dipping the surface modified catalyst substrate 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.
2. The method for preparing the ozone catalytic oxidizer based on the zero-valent iron surface hydroxylation treatment, as claimed in claim 1, wherein: in the step (2), the modification solution containing hydroxyl radicals is a Fenton solution.
3. The method for preparing the ozone catalytic oxidizer based on the zero-valent iron surface hydroxylation treatment, as claimed in claim 1, wherein: in the step (2), the impregnation modification is carried out for 24-72h.
4. The method for preparing the ozone catalytic oxidizer based on the zero-valent iron surface hydroxylation treatment, as claimed in claim 1, wherein: in the step (3), the organic solvent mixed solution is an organic substance with carbon number less than 20 and no heterocyclic ring, and the concentration of the organic solvent mixed solution is 200-1000mg/L based on COD equivalent.
5. The method for preparing the ozone catalytic oxidizer based on the zero-valent iron surface hydroxylation treatment, according to claim 4, wherein the method comprises the following steps: in the step (3), the organic solvent mixed solution is potassium hydrogen phthalate water solution or glucose solution.
6. The method for preparing the ozone catalytic oxidizer based on the zero-valent iron surface hydroxylation treatment, as claimed in claim 1, wherein: in the step (3), the bulk density of the surface modified catalyst substrate in the organic solvent mixed solution is 100-500g/L.
7. The method for preparing the ozone catalytic oxidizer based on zero-valent iron surface hydroxylation according to claim 1, wherein: and (3) adding hydrogen peroxide, intermittently introducing ozone for aeration, and continuously reacting for 72 hours, wherein the concentration of the ozone is 20-100mg/L.
8. The method for preparing the ozone catalytic oxidizer based on the zero-valent iron surface hydroxylation treatment, as claimed in claim 1, wherein: in the step (3), ozone and H 2 O 2 The molar ratio is 1:1-5, wherein H 2 O 2 Is derived from 27.5 to 30 mass percent of hydrogen peroxide.
9. The method for preparing the ozone catalytic oxidizer based on the zero-valent iron surface hydroxylation treatment as set forth in claim 2, wherein: in the step (3), the Fenton solution is supplemented into the organic solvent mixed solution every 24 hours, and the supplement amount is 0.5-1.5kg/m 3 。
10. The method for preparing an ozone catalytic oxidizer based on zero-valent iron surface hydroxylation according to claim 2 or 9, wherein: reference to H in Fenton solution 2 O 2 With Fe 2+ In a molar ratio of 1:1-5, wherein H 2 O 2 Is derived from 27.5 to 30 mass percent of hydrogen peroxide.
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