CN114644388A - Catalytic oxidation treatment method for sulfur-containing wastewater - Google Patents
Catalytic oxidation treatment method for sulfur-containing wastewater Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 49
- 239000011593 sulfur Substances 0.000 title claims abstract description 49
- 239000002351 wastewater Substances 0.000 title claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 27
- -1 sulfur ion Chemical class 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 11
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 11
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 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 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 150000003567 thiocyanates Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 1
- 101150019148 Slc7a3 gene Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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- 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
-
- 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
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
- B01J2523/17—Copper
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
- B01J2523/31—Aluminium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/842—Iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- 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
- C02F2209/02—Temperature
-
- 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
- C02F2209/03—Pressure
-
- 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
- C02F2209/40—Liquid flow rate
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- Chemical & Material Sciences (AREA)
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- 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)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a catalytic oxidation treatment method of sulfur-containing wastewater, which comprises the following steps: firstly, mixing sulfur-containing wastewater and hydrogen peroxide through a mixer; then, the mixture enters a catalytic reactor to carry out catalytic reaction. The invention has simple process, convenient operation, good catalytic effect and no secondary pollution, the catalyst can be repeatedly used, and the treated water can be reused for production.
Description
Technical Field
The invention relates to a method for treating sulfur-containing wastewater, belonging to the technical field of treatment of industrial refractory wastewater in the environmental protection industry.
Background
The sulfur-containing wastewater has the characteristics of high foul smell, high toxicity and the like, can not only corrode equipment, but also cause serious pollution to the environment. The method for treating the sulfur-containing wastewater comprises a biological treatment method and a chemical method. Chemical methods are commonly used, and mainly include alkali liquor absorption, chemical precipitation and chemical oxidation. Wherein, the alkali liquor absorption method can generate hydrogen sulfide and has complex working procedures, and is not used independently in general; the chemical precipitation method has the problems of subsequent treatment and precipitation, and the working procedures are also complex; the chemical oxidation method comprises advanced oxidation and chemical agent oxidation (hydrogen peroxide, ozone, potassium permanganate, chlorine and the like), and the chemical agent oxidation method has low oxidation rate (hydrogen peroxide) or higher price (ozone, potassium permanganate, chlorine and the like); in the advanced oxidation method, the wet oxidation treatment is effective, but the cost is high.
Disclosure of Invention
In order to overcome the defects of the prior deep treatment of the sulfur-containing wastewater, the invention provides a catalytic oxidation treatment process of the sulfur-containing wastewater, which has simple process and no secondary pollution. The catalyst used in the process has no secondary pollution, and the treated sulfur ions in the effluent reach the national first-grade emission standard.
The invention uses hydrogen peroxide as an oxidant and selects a heterogeneous catalyst to treat the sulfur-containing wastewater, thereby solving the problems of complex treatment process, low oxidation rate and high treatment cost of the sulfur-containing wastewater. Moreover, the treated wastewater can be reused for production, thereby further improving the economy.
The invention provides a catalytic oxidation treatment method of sulfur-containing wastewater, which comprises the following steps: mixing the sulfur-containing wastewater with a solution containing an oxidant, and carrying out contact reaction with a catalyst; the catalyst is a supported catalyst and is made of Al2O3The carrier is loaded with M element; wherein, the M element is selected from any one of Mn, Fe, Co, Ni, Cu and Zn; the content of M element is Al2O30.2 to 5wt.% of the support.
The mixing method of the present invention can be realized by selecting conventional mixing means and equipment according to actual needs by those skilled in the art, for example, a mixer, preferably a cyclone mixer, can be used for mixing.
The reaction of contacting with the catalyst according to the present invention preferably employs a catalytic reactor, and one skilled in the art can select a conventional catalytic reactor, such as a fixed bed catalytic reactor or a fluidized bed catalytic reactor, according to actual needs; namely, the evenly mixed sulfur-containing wastewater and the oxidant enter a catalytic reactor, and sulfur ions contact with a catalyst in the catalytic reactor to generate an oxidation reaction.
The catalyst used in the invention is a supported catalyst M/Al2O3The heterogeneous catalyst is prepared by adopting an impregnation method, a coprecipitation method or a blending method, and a carrier or a precursor is mixed with a solution of a compound containing an M element, formed and fired. The compound containing M element can be selected by those skilled in the art according to actual needsGenerally, the M salt or the organic M compound can be dissolved in the corresponding solvent, and the common choices are: nitrate, sulfate or chloride of transition metal such as Mn, Fe, Co, Ni, Cu, Zn, etc.
Preferably, the concentration of the sulfur ions in the sulfur-containing wastewater is less than 500 mg/L.
Preferably, the oxidant is hydrogen peroxide.
Preferably, the mass fraction of the hydrogen peroxide is 20-30 wt.%, and the addition amount of the hydrogen peroxide is H2O2/S2-The molar ratio is 4-20.
Preferably, the reaction temperature is 20-40 ℃; the reaction pressure is normal pressure; the hourly space velocity of the sulfur-containing wastewater liquid is 0.5-2 h-1。
Preferably, the reaction temperature is 20-40 ℃, the reaction pressure is normal pressure, and the hourly space velocity of the waste water liquid is 0.5-2 h-1Under the condition, the removal rate of the sulfur ions reaches over 90 percent.
The invention optimizes the process conditions of the existing sulfur-containing wastewater treatment, adopts the supported transition metal catalyst, can directly treat the sulfur-containing wastewater, obviously improves the removal rate of sulfur ions, greatly simplifies the treatment process and effectively reduces the treatment cost of the sulfur-containing wastewater.
Drawings
FIG. 1 shows the results of continuous reaction evaluation of Cat1 catalyst for treating low-concentration sulfur-containing wastewater.
Detailed Description
The method comprises the step of reacting at the temperature of 20-40 ℃ under the condition of normal pressure and under the condition of reaction pressure containing M/Al2O3In reactors with heterogeneous catalysts, with H2O2The deep treatment process is used as an oxidant for oxidizing sulfide in the sulfur-containing wastewater into sulfate.
The catalytic oxidation treatment method of the sulfur-containing wastewater mainly comprises a two-stage process:
the first stage is as follows: sulfur-containing wastewater and H2O2Mixing and then entering a catalytic reactor.
And a second stage: the sulfide ions or thiocyanates are oxidized on the catalyst.
The second stage is the key of the process, and the oxidation process is as follows: first, H2O2In M/Al2O3Hydroxyl radicals with strong oxidizing property are generated on the catalyst; the hydroxyl radicals then oxidize the sulfide ions or thiocyanates to sulfates.
The equation at this stage is as follows:
S2-+8HO·→SO4 2-+4H2O
the content of sulfur ions in water was analyzed by iodometry (HJT 60-2000).
The technique of the present invention is further illustrated by examples.
Example 1
Preparing a solution from ferric nitrate and cupric nitrate, and preparing 1 wt.% Fe1 wt.% Cu/Al by an isometric impregnation method2O3Soaking overnight, drying at 120 ℃ for 4h, and calcining at 500 ℃ for 4h to prepare the required catalyst Cat 1.
Reaction conditions are as follows: hydrogen peroxide according to molar ratio H2O2/S2-Adding the mixture at the reaction temperature of 25 ℃, the reaction pressure of normal pressure and the waste water liquid hourly space velocity LHSV of 1h-1. The evaluation results are shown in Table 1.
TABLE 1 Sulfur ion removal Effect at different hydrogen peroxide addition levels
Example 2
Preparation of 1 wt.% Fe1 wt.% Cu/Al by an equal volume impregnation method2O3Soaking overnight, drying at 120 ℃ for 4h, and calcining at 500 ℃ for 4h to prepare the required catalyst Cat 1.
Reaction conditions are as follows: hydrogen peroxide according to molar ratio H2O2/S2-Adding the mixture 8, reacting at 25 deg.C under normal pressure and LHSV 1h-1. The evaluation results are shown in Table 1.
Example 3
Preparation of 1 wt.% Fe1 wt.% Cu/Al by an equal volume impregnation method2O3Soaking overnight, drying at 120 ℃ for 4h, and calcining at 500 ℃ for 4h to prepare the required catalyst Cat 1.
Reaction conditions are as follows: hydrogen peroxide according to molar ratio H2O2/S2-Adding 12 portions of the mixture, reacting at 25 ℃, reacting at normal pressure and at space velocity LHSV of 1h-1. The evaluation results are shown in Table 1.
Example 4
Preparation of 1 wt.% Fe1 wt.% Cu/Al by an equal volume impregnation method2O3Soaking overnight, drying at 120 ℃ for 4h, and calcining at 500 ℃ for 4h to prepare the required catalyst Cat 1.
Reaction conditions are as follows: hydrogen peroxide according to molar ratio H2O2/S2-16 at 25 deg.C, normal pressure and space velocity LHSV of 1h-1. The evaluation results are shown in Table 1.
As can be seen from the results of the experiment shown in Table 1, the results are shown in H2O2/S2-The molar ratio is in the range of 4-16, the removal rate of the sulfur ions reaches over 90 percent, and the removal rate is along with H2O2/S2-The increase in molar ratio continues to increase the rate of removal of sulfur ions.
Example 5
Preparation of 1 wt.% Fe1 wt.% Cu/Al by an equal volume impregnation method2O3Soaking overnight, drying at 120 ℃ for 4h, and calcining at 500 ℃ for 4h to prepare the required catalyst Cat 2.
Reaction conditions are as follows: hydrogen peroxide according to molar ratio H2O2/S2-Adding 12 portions of the mixture, reacting at 25 ℃, reacting at normal pressure and at space velocity LHSV of 0.5h-1. The evaluation results are shown in Table 2.
TABLE 2 effect of removing sulfide ions at different water inlet airspeeds
Example 6
Preparation of 1 wt.% Fe1 wt.% C by an equal volume impregnation methodu/Al2O3Soaking overnight, drying at 120 ℃ for 4h, and calcining at 500 ℃ for 4h to prepare the required catalyst Cat 1.
Reaction conditions are as follows: hydrogen peroxide according to molar ratio H2O2/S2-Adding 12 deg.C, reaction temp. 25 deg.C, reaction pressure normal pressure and space velocity LHSV of 1.5h-1. The evaluation results are shown in Table 2.
Example 7
Preparation of 1 wt.% Fe1 wt.% Cu/Al by an equal volume impregnation method2O3Soaking overnight, drying at 120 ℃ for 4h, and calcining at 500 ℃ for 4h to prepare the required catalyst Cat 1.
Reaction conditions are as follows: hydrogen peroxide according to molar ratio H2O2/S2-Adding 12 portions of the mixture, reacting at 25 ℃, reacting at normal pressure and at the space velocity LHSV of 2.0h-1. The evaluation results are shown in Table 2.
As can be seen from the results of the experiment shown in Table 2, the results are shown in H2O2/S2-When the molar ratio is 12, the influence of LHSV is inspected, and the LHSV is followed for 0.5-2 h-1The range is gradually increased, the removal rate of the sulfur ions is reduced, and the LHSV is 2h-1In the process, the removal rate of the sulfide ions still reaches more than 90 percent.
Example 8
Preparation of 1 wt.% Fe1 wt.% Cu/Al by an equal volume impregnation method2O3Dipping the mixture overnight, drying the mixture for 4 hours at 120 ℃, and calcining the dried mixture for 4 hours at 500 ℃ to prepare the required catalyst Cat 1; the same method was used to prepare 2 wt.% Fe/Al2O3、 1wt.％Fe1wt.％Mn/Al2O3、1wt.％Cu1wt.％Mn/Al2O3Catalysts, denoted Cat2, Cat3, Cat4, respectively.
Reaction conditions are as follows: hydrogen peroxide according to molar ratio H2O2/S2-Adding 12 portions of the mixture, reacting at 25 ℃, reacting at normal pressure and at space velocity LHSV of 1h-1. The evaluation results are shown in Table 3.
As can be seen from the results of the experiment shown in Table 3, the results are shown in H2O2/S2-The molar ratio is 12, and the space velocity LHSV is 1h-1Under the conditions, the removal effect of various catalysts on sulfur ions is examined. The result was catalyst Cat1(1 wt.% Fe1 wt.% Cu/Al)2O3) Has the best removal effect on the sulfur-containing wastewater.
TABLE 3 Sulfur ion removal Effect on different catalysts
Example 9
Preparation of 1 wt.% Fe1 wt.% Cu/Al by an equal volume impregnation method2O3Soaking overnight, drying at 120 ℃ for 4h, and calcining at 500 ℃ for 4h to prepare the required catalyst Cat 1.
Reaction conditions are as follows: hydrogen peroxide according to molar ratio H2O2/S2-12 at 25 deg.C, normal pressure and space velocity LHSV of 1h-1The continuous reaction was carried out, and the evaluation results are shown in FIG. 1.
As shown in FIG. 1, the catalyst Cat1(1 wt.% Fe1 wt.% Cu/Al)2O3) The removal effect on the sulfur-containing wastewater is good, the removal rate on sulfur ions reaches over 96 percent, and the activity is not attenuated after the stable operation for 168 hours.
Claims (6)
1. A catalytic oxidation treatment method for sulfur-containing wastewater is characterized by comprising the following steps:
mixing the sulfur-containing wastewater with a solution containing an oxidant, and carrying out contact reaction with a catalyst;
the catalyst is a supported catalyst and is made of Al2O3The carrier is loaded with M element;
wherein, the M element is selected from any one of Mn, Fe, Co, Ni, Cu and Zn;
the content of M element is Al2O30.2 to 5wt.% of the support.
2. The catalytic oxidation treatment method for sulfur-containing wastewater according to claim 1, wherein the sulfur ion concentration of the sulfur-containing wastewater is less than 500 mg/L.
3. The catalytic oxidation treatment method for sulfur-containing wastewater according to claim 1, wherein the oxidant is hydrogen peroxide.
4. The catalytic oxidation treatment method for sulfur-containing wastewater according to claim 3, wherein the mass fraction of the hydrogen peroxide is 20-30 wt.%, and the addition amount of the hydrogen peroxide is H2O2/S2-The molar ratio is 4-20.
5. The catalytic oxidation treatment method for sulfur-containing wastewater according to claim 1, wherein the reaction temperature is 20 to 40 ℃; the reaction pressure is normal pressure; the hourly space velocity of the sulfur-containing wastewater liquid is 0.5-2 h-1。
6. The catalytic oxidation treatment method of sulfur-containing wastewater according to claim 2, wherein the reaction temperature is 20 to 40 ℃, the reaction pressure is normal pressure, and the hourly space velocity of wastewater liquid is 0.5 to 2 hours-1Under the condition, the removal rate of the sulfur ions reaches over 90 percent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106107A (en) * | 2022-07-29 | 2022-09-27 | 湖北中圣科技有限公司 | Desulfurization catalyst and preparation method and application thereof |
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| CN104549275A (en) * | 2013-10-12 | 2015-04-29 | 王颖华 | Transition metal-doped solid catalyst, preparation method thereof and water treatment method |
| CN108160067A (en) * | 2017-12-15 | 2018-06-15 | 广东省石油与精细化工研究院 | A kind of sewage deodorizing catalyst and its preparation method and application |
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Patent Citations (4)
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|---|---|---|---|---|
| EP0362429A1 (en) * | 1988-10-06 | 1990-04-11 | FMC Corporation | Process for oxidizing a low-valent sulfur compound |
| US5380442A (en) * | 1993-11-18 | 1995-01-10 | Mobil Oil Corporation | Regeneration of used stretford solution for recycle |
| CN104549275A (en) * | 2013-10-12 | 2015-04-29 | 王颖华 | Transition metal-doped solid catalyst, preparation method thereof and water treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106107A (en) * | 2022-07-29 | 2022-09-27 | 湖北中圣科技有限公司 | Desulfurization catalyst and preparation method and application thereof |
| CN115106107B (en) * | 2022-07-29 | 2024-09-20 | 湖北中圣科技有限公司 | Desulfurization catalyst and preparation method and application thereof |
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