WO2024077867A1 - Preparation of supported catalyst for fenton fluidized bed and method for treating industrial water - Google Patents
Preparation of supported catalyst for fenton fluidized bed and method for treating industrial water Download PDFInfo
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- WO2024077867A1 WO2024077867A1 PCT/CN2023/081845 CN2023081845W WO2024077867A1 WO 2024077867 A1 WO2024077867 A1 WO 2024077867A1 CN 2023081845 W CN2023081845 W CN 2023081845W WO 2024077867 A1 WO2024077867 A1 WO 2024077867A1
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- fenton
- fluidized bed
- supported catalyst
- oxidation tower
- wastewater
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 239000008235 industrial water Substances 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002351 wastewater Substances 0.000 claims abstract description 33
- 238000011282 treatment Methods 0.000 claims abstract description 30
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 239000004576 sand Substances 0.000 claims abstract description 18
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- 238000007605 air drying Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 230000003311 flocculating effect Effects 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
- 239000012028 Fenton's reagent Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000013043 chemical agent Substances 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 239000010412 oxide-supported catalyst Substances 0.000 abstract 2
- 238000005554 pickling Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 14
- 239000003245 coal Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 235000013980 iron oxide Nutrition 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012364 cultivation method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 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
- 238000000338 in vitro Methods 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Definitions
- the invention relates to the field of water treatment, and in particular to a method for preparing a Fenton fluidized bed carrier catalyst and a method for industrial water treatment using the carrier catalyst in a Fenton fluidized bed.
- Industrial wastewater has the characteristics of high concentration, high toxicity, large discharge volume, complex composition and difficulty in biodegradation, which poses a serious threat to my country's water resources and aquatic ecological environment. Studies have shown that industrial wastewater contains a large amount of chemical mixtures, which can have a greater impact on human health than a single compound. This type of water body is still difficult to meet the discharge standards after conventional primary treatment (pretreatment technology) and secondary treatment (biochemical treatment technology).
- the Fenton process As a classic advanced oxidation process, the Fenton process is mature, simple to operate, can produce a large number of highly efficient and non-selective hydroxyl radicals ( ⁇ OH), and has high mineralization efficiency for stubborn and toxic organic pollutants. It is widely used in the fields of pre-treatment of biological treatment and sewage discharge compliance.
- the traditional Fenton technology has problems such as high reagent cost, large amount of iron sludge produced, and narrow pH application range. Therefore, the fluidized bed Fenton technology has attracted more and more attention from researchers in the field of wastewater pretreatment and deep treatment.
- the technical mechanism of fluidized bed Fenton technology combines homogeneous chemical oxidation, fluidized bed crystallization, heterogeneous chemical oxidation and dissolution of iron oxides.
- Fe 3+ produced by homogeneous chemical oxidation is loaded on the carrier in the form of crystallization or chemical precipitation, which reduces the amount of sludge that may be produced and provides a basis for subsequent heterogeneous catalytic oxidation and The dissolution of iron oxides lays the foundation.
- Fe(OH) 3 can be converted into amorphous FeOOH and a small amount of weakly crystalline r-FeOOH, which can effectively catalyze H 2 O 2 , and can effectively support the crystallization and dissolution of iron oxides to form Fe 2+ in the huge expansion and tumbling and acidic system to continue to participate in the homogeneous Fenton reaction. Therefore, the key to fluidized bed Fenton technology lies in the formation of a loaded crystal carrier.
- the crystal cultivation cycle is relatively long, and there are also uneven, unstable and stable characteristics, which easily lead to the problem of difficult water quality standards for wastewater treatment in the early stage of project startup.
- the present invention is a method for preparing a Fenton fluidized bed carrier catalyst and treating industrial water.
- the time for original crystal cultivation is shortened and the problem of uneven and unstable crystals is overcome.
- a method for preparing a Fenton fluidized bed supported catalyst comprises the following steps:
- Step 1) the original carrier is subjected to acid washing pretreatment and natural air drying;
- Step 2) Cultivate crystals, and mix the treated carrier obtained in step 1) with iron-based raw materials, Fenton reagents and industrial wastewater of a certain concentration through stirring and tumbling procedures to prepare an iron oxide carrier catalyst for use as a filler in a Fenton oxidation tower.
- the original carrier can be any one of building sand, sea sand and gravel, and the mass load of the original carrier added to the reactor volume is 200-400 g/L.
- the low-concentration industrial wastewater is industrial wastewater with a COD value of 100-500 mg/L.
- the method may further include adjusting the pH value of the industrial wastewater to 4-6.
- the iron-based raw material is one of zero-valent iron powder, iron oxide, ferric nitrate or a mixture thereof.
- the step 2) can be carried out in a batch reactor or a fluidized bed batch reactor, with a feeding frequency of 8-12 hours each time, a continuous operation time of 24-32 hours at a bed expansion rate of 50%, and natural air drying or drying in a 60°C oven.
- the Fenton oxidation tower is a fluidized bed
- the wastewater residence time is 20-60 minutes
- the reflux expansion rate is 50%-100%.
- the above industrial water treatment method further comprises the step of adjusting the pH value of the wastewater entering the Fenton oxidation tower to 3-6 and/or adjusting the effluent of the Fenton oxidation tower to neutral with NaOH and then flocculating the effluent with PAM.
- step 2) After the filler enters the Fenton tower, the pH of the wastewater needs to be adjusted to 3-6; in the step 2), the effluent from the Fenton oxidation tower needs to be adjusted to neutral with NaOH first, and then the effluent needs to be flocculated with PAM to obtain the ideal water quality.
- the present invention has the following beneficial effects:
- the present invention adopts a method of batch intermittent culturing of carriers, the crystallization effect of the carriers is good, and the crystallization start-up time is shortened by half compared with the original fluidized bed Fenton.
- the crystals cultured on the carrier surface of the present invention have good crystallization stability, which can overcome the unstable and uneven characteristics of traditional fluidized bed Fenton crystallization.
- the present invention adds iron-based raw materials in the preparation of the loaded catalyst, which can effectively increase the iron content on the catalyst surface, thereby effectively improving the COD removal rate of pollutants, reducing the addition of chemical agents, and widening the pH range and other characteristics.
- FIG1 is a simplified flow chart of the preparation method of the Fenton fluidized bed supported catalyst of the present invention and its application in industrial water treatment process;
- FIG2 is a result of using the catalyst prepared by the method of the present invention and the conventional method in a fluidized bed reactor for water treatment reaction;
- Fig. 4 Effect of residence time on water treatment reactions.
- coal chemical wastewater is selected as the removal object, and the preferred embodiment is The embodiments and comparative examples are described in detail below with reference to the accompanying drawings.
- a method for preparing a Fenton fluidized bed supported catalyst and an industrial water treatment method comprises the following steps:
- step (2) Treatment of wastewater: The crystal carrier produced in step (2) is placed in a fluidized bed Fenton tower to degrade coal chemical wastewater with a COD concentration of 400 mg/L.
- the water is adjusted to neutral with NaOH, and PAM flocculant is added to obtain an effluent COD removal rate of 54%. The effect is shown in Figure 2.
- the surface element (C, O, N, Fe, Si) content of the prepared supported catalyst was analyzed by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and the Fe content was 14.4% (see Table 1 for details).
- a method for preparing a Fenton fluidized bed supported catalyst and an industrial water treatment method comprises the following steps:
- step (2) Treatment of wastewater: The crystal carrier produced in step (2) was placed in a fluidized bed Fenton tower to degrade coal chemical wastewater with a COD concentration of 440 mg/L.
- the water was adjusted to neutral with NaOH, and PAM flocculant was added to obtain an effluent COD removal rate of 52%. The effect is shown in Figure 2.
- a method for preparing a Fenton fluidized bed supported catalyst and an industrial water treatment method comprises the following steps:
- step (3) Treatment of wastewater: The crystal carrier produced in step (2) was placed in a fluidized bed Fenton tower to degrade coal chemical wastewater with a COD concentration of 400 mg/L.
- the wastewater pH was adjusted to 3, 4, 5, and 6 respectively, and Fenton reagent H 2 O 2 800 mg/L and Fe 2+ 482 mg/L were added; the residence time was set to 40 min, and the reflux expansion rate was 50%.
- the water was adjusted to neutral with NaOH, and PAM flocculant was added to obtain effluent COD removal rates of 46%, 54%, 47%, and 50%, respectively.
- the effect is shown in Figure 3.
- step (3) Treatment of wastewater: The crystal carrier produced in step (2) was placed in a fluidized bed Fenton tower to degrade coal chemical wastewater with a COD concentration of 440 mg/L.
- the water was adjusted to neutral with NaOH, and PAM flocculant was added to obtain effluent COD removal rates of 46%, 47%, 47%, 54%, and 48%, respectively. The effect is shown in Figure 4.
- Comparative Example 1 adopts the original carrier direct degradation method, that is, crystals are formed on the carrier surface during water treatment in a fluidized bed Fenton tower.
- Comparative Example 2 adopts the conventional crystal cultivation method, that is, no iron source is added during the crystallization coating process on the carrier surface:
- Example 1 The same detection method as in Example 1 was used to analyze the surface element content of the supported catalysts prepared in Comparative Example 1 and Comparative Example 2. The results showed that the Fe content on the surface of the supported catalyst prepared by the method of the present invention was significantly higher than that on the surface of the supported catalysts in Comparative Example 1 and Comparative Example 2. The Fe content formed.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Provided in the present invention are a method for preparing an iron oxide supported catalyst for a Fenton fluidized bed and the use thereof in a method for treating wastewater by subjecting same to a multi-phase Fenton reaction in a Fenton fluidized bed reaction tower, which method and use are characterized by selecting and using building sand, sea sand, gravel, etc., as original carriers, subjecting same to acid pickling and natural air-drying, then mixing same with an iron-based raw material, a Fenton reagent and industrial wastewater, quickly preparing an iron oxide supported catalyst after stirring and tumbling procedures, and treating the industrial wastewater by using the supported catalyst as a filler of a Fenton oxidation tower. The process can effectively improve the removal rate of pollutants, widen the pH of a traditional Fenton fluidized bed, increase the reusability of the catalyst and reduce the use of chemical agents. In the present invention, the raw materials used are easily available, the process is simple and convenient, the period is short, the operation is easy, and the present invention has a good effect on the pre-treatment and deep treatment of industrial wastewater.
Description
本发明涉及水处理领域，具体涉及芬顿流化床载体催化剂的制备方法，以及在芬顿流化床内采用载体催化剂进行工业水处理的方法。The invention relates to the field of water treatment, and in particular to a method for preparing a Fenton fluidized bed carrier catalyst and a method for industrial water treatment using the carrier catalyst in a Fenton fluidized bed.
工业废水具有高浓度、高毒性、排放量大、成分复杂和难生物降解等特点，对我国的水资源和水生态环境造成了严重的威胁。研究表明，工业废水含有大量的化学混合物，比单一的化合物更能对人体健康产生影响。该类水体经过常规的一级处理(预处理技术)、二级处理(生化处理技术)后仍难以达到排放标准。Industrial wastewater has the characteristics of high concentration, high toxicity, large discharge volume, complex composition and difficulty in biodegradation, which poses a serious threat to my country's water resources and aquatic ecological environment. Studies have shown that industrial wastewater contains a large amount of chemical mixtures, which can have a greater impact on human health than a single compound. This type of water body is still difficult to meet the discharge standards after conventional primary treatment (pretreatment technology) and secondary treatment (biochemical treatment technology).
Fenton法作为一种经典的高级氧化工艺，因其工艺成熟、操作简单，能产生大量高效且无选择性氧化的羟基自由基(·OH)，对顽固、有毒的有机污染物矿化效率高，在生物处理的前处理和污水达标排放等领域得到广泛的应用。然而，传统Fenton技术存在药剂成本高、产铁泥量大、pH适用范围窄等问题，因此，流化床Fenton技术在废水预处理和深度处理领域越来越受到研究者的重视。As a classic advanced oxidation process, the Fenton process is mature, simple to operate, can produce a large number of highly efficient and non-selective hydroxyl radicals (·OH), and has high mineralization efficiency for stubborn and toxic organic pollutants. It is widely used in the fields of pre-treatment of biological treatment and sewage discharge compliance. However, the traditional Fenton technology has problems such as high reagent cost, large amount of iron sludge produced, and narrow pH application range. Therefore, the fluidized bed Fenton technology has attracted more and more attention from researchers in the field of wastewater pretreatment and deep treatment.
流化床芬顿技术的技术机理结合了均相化学氧化、流化床结晶、非均相化学氧化和铁氧化物的溶解等反应。在流化床芬顿的流化过程中，利用均相化学氧化产生的Fe3+以结晶或化学沉淀的形式负载于载体上，减少了原本可能产生的污泥量，并为后续的非均相催化氧化和
铁氧化物的溶解奠定基础。通过对载体的表征发现，Fe(OH)3可以转化为无定型FeOOH和少量弱晶型的r-FeOOH，可以有效地催化H2O2，并且能够在巨大的膨化翻滚和酸性体系中可以有效支撑铁氧化物结晶溶解形成Fe2+继续参与均相Fenton的反应。因此流化床芬顿技术关键在于负载结晶载体的形成。然而一般工程实践培养晶体周期较长，也存在不均匀、不稳定稳定的特性，容易出现工程启动的前期废水处理水质达标难的难题。The technical mechanism of fluidized bed Fenton technology combines homogeneous chemical oxidation, fluidized bed crystallization, heterogeneous chemical oxidation and dissolution of iron oxides. In the fluidization process of fluidized bed Fenton, Fe 3+ produced by homogeneous chemical oxidation is loaded on the carrier in the form of crystallization or chemical precipitation, which reduces the amount of sludge that may be produced and provides a basis for subsequent heterogeneous catalytic oxidation and The dissolution of iron oxides lays the foundation. Through the characterization of the carrier, it was found that Fe(OH) 3 can be converted into amorphous FeOOH and a small amount of weakly crystalline r-FeOOH, which can effectively catalyze H 2 O 2 , and can effectively support the crystallization and dissolution of iron oxides to form Fe 2+ in the huge expansion and tumbling and acidic system to continue to participate in the homogeneous Fenton reaction. Therefore, the key to fluidized bed Fenton technology lies in the formation of a loaded crystal carrier. However, in general engineering practice, the crystal cultivation cycle is relatively long, and there are also uneven, unstable and stable characteristics, which easily lead to the problem of difficult water quality standards for wastewater treatment in the early stage of project startup.
因此，本发明为一种芬顿流化床载体催化剂的制备及工业水处理方法，通过对原始载体进行体外预结晶，缩短了原始培养晶体的时间，并克服晶体存在不均匀不稳定的难题。Therefore, the present invention is a method for preparing a Fenton fluidized bed carrier catalyst and treating industrial water. By pre-crystallizing the original carrier in vitro, the time for original crystal cultivation is shortened and the problem of uneven and unstable crystals is overcome.
发明内容Summary of the invention
为了解决上述技术问题，提供一种芬顿流化床载体催化剂的制备及工业水处理方法的方法。In order to solve the above technical problems, a method for preparing a Fenton fluidized bed supported catalyst and an industrial water treatment method is provided.
一种芬顿流化床载体催化剂的制备方法，包括以下步骤：A method for preparing a Fenton fluidized bed supported catalyst comprises the following steps:
步骤1)：将原始载体经酸洗前处理和自然风干；Step 1): the original carrier is subjected to acid washing pretreatment and natural air drying;
步骤2)：培养结晶晶体，将步骤1)获得的处理后的载体与铁基原料、芬顿药剂和一定浓度的工业废水经搅拌、翻滚程序后制备成铁氧化物载体催化剂用作芬顿氧化塔的填料。Step 2): Cultivate crystals, and mix the treated carrier obtained in step 1) with iron-based raw materials, Fenton reagents and industrial wastewater of a certain concentration through stirring and tumbling procedures to prepare an iron oxide carrier catalyst for use as a filler in a Fenton oxidation tower.
优选的，所述原始载体可以为建筑沙、海沙和砾石等中的任意一种，所述原始载体的投加所占反应器容积的质量负荷为200-400g/L。Preferably, the original carrier can be any one of building sand, sea sand and gravel, and the mass load of the original carrier added to the reactor volume is 200-400 g/L.
优选的，所述低浓度的工业废水为COD值在100-500mg/L的工
业废水。在所述步骤2)之前，还可以包括将所述工业废水的pH值调整至4-6的步骤。Preferably, the low-concentration industrial wastewater is industrial wastewater with a COD value of 100-500 mg/L. Before the step 2), the method may further include adjusting the pH value of the industrial wastewater to 4-6.
优选的，所述原始载体的酸洗使用的是pH＝1-2的盐酸，静置时间为18-24h后，水洗至pH＝7并自然烘干。Preferably, the original carrier is acid-washed with hydrochloric acid at pH=1-2, and after standing for 18-24 hours, it is washed with water to pH=7 and dried naturally.
所述铁基原料为零价铁粉、氧化铁、硝酸铁中的一种或其混合。优选的，铁基原料为质量比零价铁:氧化铁:硝酸铁＝(0.5-1.5):2:3的混合，铁基原料的质量负荷为2-4g/L。The iron-based raw material is one of zero-valent iron powder, iron oxide, ferric nitrate or a mixture thereof. Preferably, the iron-based raw material is a mixture of zero-valent iron: iron oxide: ferric nitrate = (0.5-1.5): 2: 3 by mass ratio, and the mass load of the iron-based raw material is 2-4 g/L.
优选的，所述芬顿药剂和工业废水的质量浓度比按Fe2+:H2O2:COD＝(2-3):(2-3):1的比例投加。Preferably, the mass concentration ratio of the Fenton reagent and the industrial wastewater is Fe 2+ :H 2 O 2 :COD=(2-3):(2-3):1.
优选的，所述步骤2)可以在釜式间歇反应器或者流化床间歇反应器中进行，投料频率在8-12h每次，在床层膨胀率为50％下连续运行的时间在24-32h,并自然风干或置于60℃烘箱烘干。Preferably, the step 2) can be carried out in a batch reactor or a fluidized bed batch reactor, with a feeding frequency of 8-12 hours each time, a continuous operation time of 24-32 hours at a bed expansion rate of 50%, and natural air drying or drying in a 60°C oven.
本发明还提供了一种采用上述方法制备的催化剂作为填料，在芬顿氧化塔中进行工业水处理的方法，包括：向所述芬顿氧化塔中按照水质特征加入芬顿药剂，所述芬顿氧化塔出水经过中和混凝沉淀后得到净水；优选的，所述芬顿氧化塔内芬顿药剂的投药比例为质量浓度比Fe2+:H2O2:COD＝(0.5-1.5):(2-3):1。The present invention also provides a method for treating industrial water in a Fenton oxidation tower using the catalyst prepared by the above method as filler, comprising: adding a Fenton agent into the Fenton oxidation tower according to water quality characteristics, and obtaining purified water after neutralization, coagulation and precipitation of the effluent from the Fenton oxidation tower; preferably, the dosage ratio of the Fenton agent in the Fenton oxidation tower is a mass concentration ratio of Fe2 + : H2O2 :COD=(0.5-1.5):(2-3):1.
优选的，所述芬顿氧化塔为流化床，废水停留时间在20-60min，回流膨化率50％-100％。Preferably, the Fenton oxidation tower is a fluidized bed, the wastewater residence time is 20-60 minutes, and the reflux expansion rate is 50%-100%.
优选的，上述工业水处理的方法方法还包括将进入芬顿氧化塔的废水的pH值调节至3-6和/或将芬顿氧化塔出水需要先用NaOH调节至中性再用PAM絮凝出水的步骤。进一步优选的，所述步骤2)中
填料进入芬顿塔后，需将废水中的pH调节至3-6；所述步骤2)中从芬顿氧化塔出水需要先用NaOH调节至中性，再用PAM絮凝出水得到理想水质。Preferably, the above industrial water treatment method further comprises the step of adjusting the pH value of the wastewater entering the Fenton oxidation tower to 3-6 and/or adjusting the effluent of the Fenton oxidation tower to neutral with NaOH and then flocculating the effluent with PAM. Further preferably, in step 2) After the filler enters the Fenton tower, the pH of the wastewater needs to be adjusted to 3-6; in the step 2), the effluent from the Fenton oxidation tower needs to be adjusted to neutral with NaOH first, and then the effluent needs to be flocculated with PAM to obtain the ideal water quality.
与现有技术相比，本发明的有益效果在于：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明采用序批间歇培养载体的方法，载体的结晶效果好，结晶启动时间比原来的流化床芬顿缩短一半。(1) The present invention adopts a method of batch intermittent culturing of carriers, the crystallization effect of the carriers is good, and the crystallization start-up time is shortened by half compared with the original fluidized bed Fenton.
(2)本发明在载体表面培养的晶体具有较好的结晶稳定性，可克服传统流化床芬顿结晶不稳定、不均的的特点。(2) The crystals cultured on the carrier surface of the present invention have good crystallization stability, which can overcome the unstable and uneven characteristics of traditional fluidized bed Fenton crystallization.
(3)本发明在负载催化剂的制备中投加铁基原料，可有效增加催化剂表面铁元素含量，从而可有效的提高污染物COD去除率，减少化学药剂的投加，拓宽pH范围等特性。(3) The present invention adds iron-based raw materials in the preparation of the loaded catalyst, which can effectively increase the iron content on the catalyst surface, thereby effectively improving the COD removal rate of pollutants, reducing the addition of chemical agents, and widening the pH range and other characteristics.
图1本发明的芬顿流化床载体催化剂制备方法及其用于工业水处理工艺的流程简图；FIG1 is a simplified flow chart of the preparation method of the Fenton fluidized bed supported catalyst of the present invention and its application in industrial water treatment process;
图2在流化床反应器中采用本发明方法和常规方法制备的催化剂用于水处理反应的结果；FIG2 is a result of using the catalyst prepared by the method of the present invention and the conventional method in a fluidized bed reactor for water treatment reaction;
图3废水pH值对水处理反应的影响；Fig. 3 Effect of wastewater pH on water treatment reactions;
图4停留时间对水处理反应的影响。Fig. 4 Effect of residence time on water treatment reactions.
为使本发明更明显易懂，兹选以煤化工废水为去除对象，优选实
施例和对比例并配合附图作详细说明如下。In order to make the present invention more obvious and easy to understand, coal chemical wastewater is selected as the removal object, and the preferred embodiment is The embodiments and comparative examples are described in detail below with reference to the accompanying drawings.
实施例1Example 1
一种芬顿流化床载体催化剂的制备及工业水处理方法的方法，包括以下步骤：A method for preparing a Fenton fluidized bed supported catalyst and an industrial water treatment method comprises the following steps:
(1)原始载体的处理：将原始海沙载体使用pH＝1的盐酸浸泡24小时后，水洗至中性并自然烘干。(1) Treatment of the original carrier: The original sea sand carrier was soaked in hydrochloric acid with pH = 1 for 24 hours, washed with water until neutral and dried naturally.
(2)晶体的制备培养：将海沙载体置于流化床反应器，海沙的质量负荷为300g/L，加入COD浓度为400mg/L的煤化工废水，加入铁源物质(质量比为零价铁：氧化铁：硝酸铁＝1:2:3)，总的质量负荷为2g/L，废水的pH调节为4，芬顿药剂投加为H2O2＝800mg/L，Fe2+＝1040mg/L。铁源物质和芬顿试剂的投药频率为8小时每次，床层膨胀率为50％，连续运行24小时后取样自然风干。(2) Preparation and cultivation of crystals: The sea sand carrier was placed in a fluidized bed reactor, the mass load of the sea sand was 300 g/L, coal chemical wastewater with a COD concentration of 400 mg/L was added, and iron source material (mass ratio of zero-valent iron: iron oxide: iron nitrate = 1:2:3) was added, the total mass load was 2 g/L, the pH of the wastewater was adjusted to 4, and the Fenton reagent was added with H 2 O 2 = 800 mg/L and Fe 2+ = 1040 mg/L. The frequency of dosing of the iron source material and Fenton reagent was 8 hours each time, the bed expansion rate was 50%, and the samples were taken and naturally air-dried after continuous operation for 24 hours.
(3)废水的处理：将步骤(2)产生的结晶载体置于流化床芬顿塔中，降解COD浓度为400mg/L的煤化工废水。调整废水pH＝4,投加芬顿试剂H2O2＝800mg/L，Fe2+＝482mg/L，设置停留时间为40min，回流膨化率为50％。取出水用NaOH调节至中性，投加PAM絮凝剂得到出水COD去除率为54％。效果参见图2。(3) Treatment of wastewater: The crystal carrier produced in step (2) is placed in a fluidized bed Fenton tower to degrade coal chemical wastewater with a COD concentration of 400 mg/L. The wastewater pH is adjusted to 4, Fenton reagent H 2 O 2 = 800 mg/L, Fe 2+ = 482 mg/L is added, the residence time is set to 40 min, and the reflux expansion rate is 50%. The water is adjusted to neutral with NaOH, and PAM flocculant is added to obtain an effluent COD removal rate of 54%. The effect is shown in Figure 2.
采用扫描电镜-能谱(SEM-EDS)对制备载体催化剂进行表面元素(C、O、N、Fe、Si)含量分析，Fe含量为14.4％(详见表1)。The surface element (C, O, N, Fe, Si) content of the prepared supported catalyst was analyzed by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and the Fe content was 14.4% (see Table 1 for details).
实施例2Example 2
一种芬顿流化床载体催化剂的制备及工业水处理方法的方法，包括以下步骤：
A method for preparing a Fenton fluidized bed supported catalyst and an industrial water treatment method comprises the following steps:
(1)原始载体的处理：将原始建筑沙载体使用pH＝2的盐酸浸泡24小时后，水洗至中性并自然烘干。(1) Treatment of the original carrier: The original construction sand carrier was soaked in hydrochloric acid with a pH of 2 for 24 hours, then washed with water until neutral and dried naturally.
(2)晶体的制备培养：将海沙载体置于流化床反应器，海沙的质量负荷为200g/L，加入COD浓度为400mg/L的石油化工废水，加入铁源物质(质量比为零价铁：氧化铁：硝酸铁＝0.5:2:2)，总的质量负荷为2g/L，废水的pH调节为5，芬顿药剂投加为H2O2＝800mg/L，Fe2+＝960mg/L。铁源物质和芬顿试剂的投药频率为8小时每次，床层膨胀率为70％，连续运行24小时后取样自然风干。(2) Preparation and cultivation of crystals: The sea sand carrier was placed in a fluidized bed reactor, the mass load of the sea sand was 200 g/L, petrochemical wastewater with a COD concentration of 400 mg/L was added, and an iron source (mass ratio of zero-valent iron: iron oxide: iron nitrate = 0.5:2:2) was added, the total mass load was 2 g/L, the pH of the wastewater was adjusted to 5, and the Fenton reagent was added with H 2 O 2 = 800 mg/L and Fe 2+ = 960 mg/L. The frequency of dosing the iron source and Fenton reagent was 8 hours each time, the bed expansion rate was 70%, and the samples were taken and naturally air-dried after continuous operation for 24 hours.
(3)废水的处理：将步骤(2)产生的结晶载体置于流化床芬顿塔中，降解COD浓度为440mg/L的煤化工废水。调整废水pH＝6，投加芬顿试剂H2O2＝800mg/L，Fe2+＝482mg/L，设置停留时间为40min，回流膨化率为50％。取出水用NaOH调节至中性，投加PAM絮凝剂得到出水COD去除率为52％。效果参见图2。(3) Treatment of wastewater: The crystal carrier produced in step (2) was placed in a fluidized bed Fenton tower to degrade coal chemical wastewater with a COD concentration of 440 mg/L. The wastewater pH was adjusted to 6, Fenton reagent H 2 O 2 = 800 mg/L, Fe 2+ = 482 mg/L was added, the residence time was set to 40 min, and the reflux expansion rate was 50%. The water was adjusted to neutral with NaOH, and PAM flocculant was added to obtain an effluent COD removal rate of 52%. The effect is shown in Figure 2.
实施例3Example 3
一种芬顿流化床载体催化剂的制备及工业水处理方法的方法，包括以下步骤：A method for preparing a Fenton fluidized bed supported catalyst and an industrial water treatment method comprises the following steps:
(1)原始载体的处理：将原始海沙载体使用pH＝1的盐酸浸泡24小时后，水洗至中性并自然烘干。(1) Treatment of the original carrier: The original sea sand carrier was soaked in hydrochloric acid with pH = 1 for 24 hours, washed with water until neutral and dried naturally.
(2)晶体的制备培养：将海沙载体置于流化床反应器，海沙的质量负荷为400g/L，加入COD浓度为400mg/L的煤化工废水，加入铁源物质(质量比为零价铁：氧化铁：硝酸铁＝1:2:3)，总的质量负荷为2g/L，废水的pH调节为4，芬顿药剂投加为H2O2＝800mg/L，
Fe2+＝1040mg/L。铁源物质和芬顿试剂的投药频率为8小时每次，床层膨胀率为50％，连续运行24小时后取样自然风干。(2) Preparation and cultivation of crystals: A sea sand carrier was placed in a fluidized bed reactor, the mass load of the sea sand was 400 g/L, coal chemical wastewater with a COD concentration of 400 mg/L was added, and an iron source material (mass ratio of zero-valent iron: iron oxide: iron nitrate = 1:2:3) was added, the total mass load was 2 g/L, the pH of the wastewater was adjusted to 4, and the Fenton agent was added at 800 mg/L of H 2 O 2 . Fe 2+ = 1040 mg/L. The dosing frequency of the iron source and Fenton's reagent was 8 hours each time, the bed expansion rate was 50%, and the samples were taken and naturally air-dried after continuous operation for 24 hours.
(3)废水的处理：将步骤(2)产生的结晶载体置于流化床芬顿塔中，降解COD浓度为400mg/L的煤化工废水。分别调整废水pH＝3、4、5、6,投加芬顿试剂H2O2 800mg/L，Fe2+482mg/L；设置停留时间为40min，回流膨化率为50％。取出水用NaOH调节至中性，投加PAM絮凝剂得到出水COD去除率分别为46％、54％、47％、50％。效果参见图3。(3) Treatment of wastewater: The crystal carrier produced in step (2) was placed in a fluidized bed Fenton tower to degrade coal chemical wastewater with a COD concentration of 400 mg/L. The wastewater pH was adjusted to 3, 4, 5, and 6 respectively, and Fenton reagent H 2 O 2 800 mg/L and Fe 2+ 482 mg/L were added; the residence time was set to 40 min, and the reflux expansion rate was 50%. The water was adjusted to neutral with NaOH, and PAM flocculant was added to obtain effluent COD removal rates of 46%, 54%, 47%, and 50%, respectively. The effect is shown in Figure 3.
实施例4Example 4
步骤(1)-(2)催化剂制备同实施例1。Steps (1)-(2) The catalyst preparation is the same as in Example 1.
(3)废水的处理：将步骤(2)产生的结晶载体置于流化床芬顿塔中，降解COD浓度为440mg/L的煤化工废水。分别调整废水pH＝4,投加芬顿试剂H2O2＝800mg/L，Fe2+＝482mg/L，设置停留时间为10min、20min、30min、40min、50min，回流膨化率为50％。取出水用NaOH调节至中性，投加PAM絮凝剂得到出水COD去除率分别为46％、47％、47％、54％、48％。效果参见图4。(3) Treatment of wastewater: The crystal carrier produced in step (2) was placed in a fluidized bed Fenton tower to degrade coal chemical wastewater with a COD concentration of 440 mg/L. The wastewater pH was adjusted to 4, Fenton reagent H 2 O 2 = 800 mg/L, Fe 2+ = 482 mg/L were added, the residence time was set to 10 min, 20 min, 30 min, 40 min, 50 min, and the reflux expansion rate was 50%. The water was adjusted to neutral with NaOH, and PAM flocculant was added to obtain effluent COD removal rates of 46%, 47%, 47%, 54%, and 48%, respectively. The effect is shown in Figure 4.
对比例1Comparative Example 1
对比例1采用原始载体直接降解法，即流化床芬顿塔内进行水处理的过程中在载体表面形成结晶。Comparative Example 1 adopts the original carrier direct degradation method, that is, crystals are formed on the carrier surface during water treatment in a fluidized bed Fenton tower.
(1)原始载体的处理：将原始海沙载体使用pH＝1的盐酸浸泡24小时后，水洗至中性并自然烘干。(1) Treatment of the original carrier: The original sea sand carrier was soaked in hydrochloric acid with pH = 1 for 24 hours, washed with water until neutral and dried naturally.
(2)废水的处理：将海沙载体置于流化床反应器，海沙的质量负荷
为400g/L，加入COD浓度为400mg/L的煤化工废水，废水的pH调节为4，投加芬顿试剂H2O2 800mg/L，Fe2+482mg/L，设置停留时间为40min，回流膨化率为50％。取出水用NaOH调节至中性，投加PAM絮凝剂得到出水COD去除率20％。效果参见图2。(2) Wastewater treatment: The sea sand carrier is placed in a fluidized bed reactor, and the mass load of the sea sand The concentration of COD in coal chemical industry is 400g/L, and the COD concentration of 400mg/L is added. The pH of the wastewater is adjusted to 4. Fenton reagent H2O2 800mg /L and Fe2 + 482mg/L are added. The residence time is set to 40min, and the reflux expansion rate is 50%. The water is adjusted to neutral with NaOH, and PAM flocculant is added to obtain a COD removal rate of 20% in the effluent. The effect is shown in Figure 2.
对比例2Comparative Example 2
对比例2采用常规晶体培养法，即载体表面结晶覆膜的过程中不投加铁源：Comparative Example 2 adopts the conventional crystal cultivation method, that is, no iron source is added during the crystallization coating process on the carrier surface:
(1)原始载体的处理：将原始海沙载体使用pH＝1的盐酸浸泡24小时后，水洗至中性并自然烘干。(1) Treatment of the original carrier: The original sea sand carrier was soaked in hydrochloric acid with pH = 1 for 24 hours, washed with water until neutral and dried naturally.
(2)晶体的制备培养：将海沙载体置于流化床反应器，海沙的质量负荷为300g/L，加入COD浓度为400mg/L的煤化工废水，调节废水的pH调节为4，芬顿药剂投加为H2O2 800mg/L，Fe2+1040mg/L，芬顿试剂的投药频率为8小时每次，床层膨胀率为50％，连续运行72小时后取样自然风干。(2) Preparation and cultivation of crystals: A sea sand carrier was placed in a fluidized bed reactor with a mass load of 300 g/L of sea sand. Coal chemical wastewater with a COD concentration of 400 mg/L was added, and the pH of the wastewater was adjusted to 4. The Fenton reagent was added with 800 mg/L H2O2 and 1040 mg/L Fe2+. The dosing frequency of Fenton reagent was every 8 hours, the bed expansion rate was 50%, and samples were taken after continuous operation for 72 hours and naturally air-dried.
(3)废水的处理：将步骤(1)-(2)产生的载体催化剂置于流化床芬顿塔中，降解COD浓度为440mg/L的煤化工废水。调整废水pH＝4,投加芬顿试剂H2O2 800mg/L，Fe2+482mg/L；设置停留时间为40min，回流膨化率为50％。取出水用NaOH调节至中性，投加PAM絮凝剂得到出水COD去除率为22％。效果参见图2。(3) Treatment of wastewater: The supported catalyst produced in steps (1)-(2) was placed in a fluidized bed Fenton tower to degrade coal chemical wastewater with a COD concentration of 440 mg/L. The pH of the wastewater was adjusted to 4, and Fenton reagent H 2 O 2 800 mg/L and Fe 2+ 482 mg/L were added; the residence time was set to 40 min, and the reflux expansion rate was 50%. The water was adjusted to neutral with NaOH, and PAM flocculant was added to obtain an effluent COD removal rate of 22%. The effect is shown in Figure 2.
采用与实施例1相同的检测方法分析对比例1、对比例2制备得到的载体催化剂的表面元素含量，结果表明，本发明的方法制备的载体催化剂表面Fe含量明显高于对比例1和对比例2的载体表面结晶
形成的Fe含量。The same detection method as in Example 1 was used to analyze the surface element content of the supported catalysts prepared in Comparative Example 1 and Comparative Example 2. The results showed that the Fe content on the surface of the supported catalyst prepared by the method of the present invention was significantly higher than that on the surface of the supported catalysts in Comparative Example 1 and Comparative Example 2. The Fe content formed.
表1样品SEM-EDS表征分析
Table 1 SEM-EDS characterization analysis of samples
Table 1 SEM-EDS characterization analysis of samples
Claims (11)
- 一种芬顿流化床载体催化剂的制备方法，包括以下步骤：A method for preparing a Fenton fluidized bed supported catalyst comprises the following steps:步骤1)：将原始载体经酸洗前处理和自然风干；Step 1): the original carrier is subjected to acid washing pretreatment and natural air drying;步骤2)：培养结晶晶体，将步骤1)获得的处理后的载体与铁基原料、芬顿药剂和一定浓度的工业废水经搅拌、翻滚程序后制备成铁氧化物载体催化剂用作芬顿氧化塔的填料。Step 2): Cultivate crystals, and mix the treated carrier obtained in step 1) with iron-based raw materials, Fenton reagents and industrial wastewater of a certain concentration through stirring and tumbling procedures to prepare an iron oxide carrier catalyst for use as a filler in a Fenton oxidation tower.
- 如权利要求1所述的一种芬顿流化床载体催化剂的制备方法，所述的原始载体可以为建筑沙、海沙和砾石等中的任意一种，所述原始载体的投加所占反应器容积的质量负荷为200-400g/L。A method for preparing a Fenton fluidized bed supported catalyst as described in claim 1, wherein the original support can be any one of building sand, sea sand and gravel, and the mass load of the original support added to the reactor volume is 200-400g/L.
- 如权利要求1所述的一种芬顿流化床载体催化剂的制备方法，所述低浓度的工业废水为COD值在100-500mg/L的工业废水。A method for preparing a Fenton fluidized bed supported catalyst as described in claim 1, wherein the low-concentration industrial wastewater is industrial wastewater with a COD value of 100-500 mg/L.
- 如权利要求1-3所述的一种芬顿流化床载体催化剂的制备及工业水处理方法，其特征在于：在所述步骤2)之前将所述工业废水的pH值调整至4-6。A method for preparing a Fenton fluidized bed supported catalyst and treating industrial water as described in claims 1-3, characterized in that the pH value of the industrial wastewater is adjusted to 4-6 before step 2).
- 如权利要求1所述的一种芬顿流化床载体催化剂的制备方法，所述原始载体的酸洗使用的是pH＝1-2的盐酸，静置时间为18-24h。A method for preparing a Fenton fluidized bed supported catalyst as described in claim 1, wherein the acid washing of the original support uses hydrochloric acid with a pH of 1-2 and the standing time is 18-24 hours.
- 如权利要求1所述的一种芬顿流化床载体催化剂的制备及工业水处理方法，所述铁基原料为零价铁粉、氧化铁、硝酸铁中的一种或其混合；优选的，所述铁基原料为质量比零价铁:氧化铁:硝酸铁＝(0.5-1.5):2:3的混合，铁基原料的质量负荷为2-4g/L。According to the method for preparing a Fenton fluidized bed supported catalyst and treating industrial water as described in claim 1, the iron-based raw material is one of zero-valent iron powder, iron oxide, and ferric nitrate, or a mixture thereof; preferably, the iron-based raw material is a mixture of zero-valent iron: iron oxide: ferric nitrate = (0.5-1.5): 2:3 by mass ratio, and the mass load of the iron-based raw material is 2-4 g/L.
- 如权利要求1所述的一种芬顿流化床载体催化剂的制备方法，所述芬顿药剂和工业废水的质量浓度比按Fe2+:H2O2:COD＝(2-3): (2-3):1的比例投加。The method for preparing a Fenton fluidized bed supported catalyst according to claim 1, wherein the mass concentration ratio of the Fenton agent to the industrial wastewater is Fe 2+ :H 2 O 2 :COD=(2-3): (2-3):1 ratio of addition.
- 如权利要求1所述的一种芬顿流化床载体催化剂的制备方法，其特征在于：所述步骤2)在釜式间歇反应器或者流化床间歇反应器中进行，投料频率在8-12h每次，且连续运行的时间在24-32h。The method for preparing a Fenton fluidized bed supported catalyst as described in claim 1 is characterized in that: the step 2) is carried out in a kettle batch reactor or a fluidized bed batch reactor, the feeding frequency is 8-12 hours each time, and the continuous operation time is 24-32 hours.
- 一种芬顿氧化塔工业水处理的方法，其特征在于，所述芬顿氧化塔中的填料为权利要求1-8任一项方法制备的载体催化剂，包括：向所述芬顿氧化塔中按照水质特征加入芬顿药剂，所述芬顿氧化塔出水经过中和混凝沉淀后得到净水；优选的，所述芬顿氧化塔内芬顿药剂的投药比例为质量浓度比Fe2+:H2O2:COD＝(0.5-1.5):(2-3):1。A method for industrial water treatment using a Fenton oxidation tower, characterized in that the filler in the Fenton oxidation tower is a supported catalyst prepared by the method of any one of claims 1 to 8, comprising: adding a Fenton agent to the Fenton oxidation tower according to water quality characteristics, and obtaining purified water after neutralization, coagulation and precipitation of effluent from the Fenton oxidation tower; preferably, the dosage ratio of the Fenton agent in the Fenton oxidation tower is a mass concentration ratio of Fe2 + : H2O2 : COD =(0.5-1.5):(2-3):1.
- 如权利要求9所述的一种芬顿氧化塔工业水处理方法，其特征在于：所述芬顿氧化塔为流化床，废水停留时间在20-60min，回流膨化率50％-100％。A Fenton oxidation tower industrial water treatment method as described in claim 9, characterized in that: the Fenton oxidation tower is a fluidized bed, the wastewater residence time is 20-60 minutes, and the reflux expansion rate is 50%-100%.
- 如权利要求9或10所述的一种芬顿氧化塔工业水处理方法，其特征在于：还包括将进入芬顿氧化塔的废水的pH值调节至3-6和/或将芬顿氧化塔出水需要先用NaOH调节至中性再用PAM絮凝出水的步骤。 A Fenton oxidation tower industrial water treatment method as described in claim 9 or 10, characterized in that it also includes the step of adjusting the pH value of the wastewater entering the Fenton oxidation tower to 3-6 and/or adjusting the effluent of the Fenton oxidation tower to neutral with NaOH and then flocculating the effluent with PAM.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104192979A (en) * | 2014-09-23 | 2014-12-10 | 南京大学 | Fenton fluidized bed biochemical tail water advanced treatment method |
| CN105884005A (en) * | 2016-06-29 | 2016-08-24 | 盐城工学院 | Novel Fenton fluidized bed and wastewater treatment method thereof |
| CN109201085A (en) * | 2018-10-29 | 2019-01-15 | 江苏哈宜环保研究院有限公司 | A kind of preparation method and applications of fluidized bed fenton catalyst |
| CN115624974A (en) * | 2022-10-11 | 2023-01-20 | 麦王环境技术股份有限公司 | Preparation of Fenton fluidized bed carrier catalyst and industrial water treatment method |
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| CN212151913U (en) * | 2020-05-07 | 2020-12-15 | 山东双融环保工程有限公司 | Fenton oxidation tower sewage treatment plant |
| CN112551677A (en) * | 2020-11-20 | 2021-03-26 | 联合环境技术(天津)有限公司 | Novel Fenton oxidation method industrial wastewater treatment process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104192979A (en) * | 2014-09-23 | 2014-12-10 | 南京大学 | Fenton fluidized bed biochemical tail water advanced treatment method |
| CN105884005A (en) * | 2016-06-29 | 2016-08-24 | 盐城工学院 | Novel Fenton fluidized bed and wastewater treatment method thereof |
| CN109201085A (en) * | 2018-10-29 | 2019-01-15 | 江苏哈宜环保研究院有限公司 | A kind of preparation method and applications of fluidized bed fenton catalyst |
| CN115624974A (en) * | 2022-10-11 | 2023-01-20 | 麦王环境技术股份有限公司 | Preparation of Fenton fluidized bed carrier catalyst and industrial water treatment method |
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