CN110918096B - Heterogeneous Fenton catalyst, application and wastewater treatment method - Google Patents
Heterogeneous Fenton catalyst, application and wastewater treatment method Download PDFInfo
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- CN110918096B CN110918096B CN201911298779.9A CN201911298779A CN110918096B CN 110918096 B CN110918096 B CN 110918096B CN 201911298779 A CN201911298779 A CN 201911298779A CN 110918096 B CN110918096 B CN 110918096B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 12
- 229910001710 laterite Inorganic materials 0.000 claims abstract description 61
- 239000011504 laterite Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000002351 wastewater Substances 0.000 claims abstract description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000006228 supernatant Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005189 flocculation Methods 0.000 claims abstract description 12
- 230000016615 flocculation Effects 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 230000003311 flocculating effect Effects 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 23
- 229920002401 polyacrylamide Polymers 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 239000008394 flocculating agent Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 description 55
- 239000000149 chemical water pollutant Substances 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 230000000694 effects Effects 0.000 description 22
- 239000002244 precipitate Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 239000010802 sludge Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003864 humus Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- CVOFKRWYWCSDMA-UHFFFAOYSA-N 2-chloro-n-(2,6-diethylphenyl)-n-(methoxymethyl)acetamide;2,6-dinitro-n,n-dipropyl-4-(trifluoromethyl)aniline Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl.CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O CVOFKRWYWCSDMA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 241000337007 Oceania Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 fe 2 O 3 Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009280 upflow anaerobic sludge blanket technology Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
-
- B01J35/39—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a heterogeneous Fenton catalyst, application and a wastewater treatment method. The catalyst is pretreated laterite. The wastewater treatment method comprises the following steps: (1) carrying out primary flocculation on the wastewater to obtain a supernatant; (2) Adjusting the supernatant obtained in the step (1) to be acidic, adding a catalyst and hydrogen peroxide, and irradiating by using ultraviolet light to obtain a treated treatment solution; (3) And (3) adjusting the treated liquid treated in the step (2) to be neutral, and flocculating again to obtain treated water. The catalyst and the treatment method provided by the invention are used for treating the wastewater, so that not only can pollutants in the wastewater be effectively removed, but also the treatment cost can be effectively reduced.
Description
Technical Field
The invention relates to a wastewater treatment method, in particular to a heterogeneous Fenton catalyst, application and a wastewater treatment method.
Background
The high pollutant wastewater has high pollutant concentration and complex components, so the treatment cost is generally higher and the process steps are complicated. For example, landfill leachate is regarded as high-pollutant wastewater which is difficult to treat, contains a large amount of heavy metals and organic pollutants which are difficult to biochemically degrade, and is difficult to discharge after being subjected to conventional biochemical treatment. As an advanced oxidation technology (AOPs), the Fenton method shows good degradation effect on pollutants which are difficult to be biochemically degraded in wastewater, and is a preferred method for advanced treatment of landfill leachate.
The heterogeneous fenton method generally refers to a fenton method in which iron is supported on a solid medium. Compared with the traditional homogeneous Fenton method, the heterogeneous Fenton method can not only improve the recovery rate and catalytic oxidation efficiency of the catalyst and reduce the generation of iron mud,the pH range of the reaction can also be broadened. Common heterogeneous Fenton catalysts include Fe, fe 2 O 3 ，Fe 3 O4，Al 2 O 3 And iron ore and the like.
As the prior art uses a synthesized heterogeneous fenton catalyst for sewage treatment, the catalyst is synthesized by using pure substances as raw materials, so the manufacturing cost is relatively high and the preparation steps are complicated.
Red soil is a soil developed under the vegetation of tropical and subtropical rainforests, seasonal rains or evergreen broadleaf forests, and is formed by weathering of carbonates or rocks containing other iron-rich aluminum oxides under humid climatic conditions. Laterite is abundant in earth, mainly distributed in low-latitude areas of africa, asia, oceania, south america and north america, and has the advantages of large reserves, convenient mining and relatively low cost.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a heterogeneous Fenton catalyst, application and a wastewater treatment method. The invention applies the pretreated laterite to wastewater treatment, and solves the problems of low utilization efficiency of the traditional Fenton method catalyst, high medicament cost and generation of a large amount of iron mud in the treatment process.
The technical scheme is as follows: the invention provides a heterogeneous Fenton catalyst, wherein the catalyst is pretreated laterite, the pretreatment method comprises the steps of calcining laterite and then washing the calcined laterite, the calcining temperature is not lower than 400 ℃, and the calcining time is not lower than 30min.
Preferably the calcination temperature is 600-1000 deg.C, preferably the calcination time is 60-120 min.
The invention provides a preparation method of a heterogeneous Fenton catalyst, which is characterized in that laterite is calcined, the calcination temperature is not lower than 400 ℃, and the calcination time is not lower than 30min. The calcination time is not less than 30min, so that the laterite can be completely calcined, and organic matters such as humus in the laterite can be removed by calcination possibly.
Preferably the calcination temperature is 600-1000 deg.C, preferably the calcination time is 60-120 min.
In a third aspect of the invention, there is provided the use of a heterogeneous fenton catalyst as described above in the treatment of wastewater.
The wastewater in the invention is preferably high pollutant wastewater (COD is more than 500 mg/L), and the optimization means that the calcined laterite provided by the invention has high treatment efficiency on the high pollutant wastewater and has obvious treatment effect in a short time. The treatment efficiency of the invention to medium pollutant wastewater (COD 200-500 mg/L) is lower than that of high pollutant wastewater (COD is more than 500 mg/L), and the treatment effect of the invention to low pollutant wastewater (COD is less than 200 mg/L) is poorer. Therefore, the heterogeneous Fenton catalyst of the present invention is preferably applied to the treatment of wastewater with a COD content of more than 200mg/L, and more preferably to the treatment of wastewater with a COD content of more than 500 mg/L.
The fourth aspect of the present invention provides a wastewater treatment method using the above heterogeneous fenton catalyst, comprising the steps of:
(1) Performing primary flocculation on the wastewater to obtain supernatant of the wastewater;
(2) Adjusting the supernatant obtained in the step (1) to be acidic, adding the catalyst and hydrogen peroxide, and irradiating by using ultraviolet light to obtain treated treatment liquid;
(3) And (3) adjusting the treated treatment liquid obtained in the step (2) to be neutral, and flocculating again to obtain treated water.
In the step (1), the primary flocculation is to add a flocculating agent into the wastewater, wherein the flocculating agent is one or two of Polyacrylamide (PAM) and polyaluminium chloride (PAC).
Preferably, the amount of PAM added is 3 to 5ppm (1 ppm represents 1/1000000 of the mass of wastewater) and the amount of PAC added is 30 to 100ppm.
In the step (2), the catalyst is pretreated laterite, the pretreatment aims at removing organic matters such as humus in the laterite, and the pretreatment method is to calcine the laterite. The calcination temperature is preferably 600-1000 ℃, the calcination time is preferably 60-120 min, and the calcined laterite can be used as a heterogeneous Fenton catalyst. The catalyst is added into wastewater, and is washed with water to remove impurities (such as ash generated by calcination) after calcination, so that new impurities (such as suspended matters) are prevented from being introduced into the wastewater.
In the step (2), the step of adjusting the pH of the supernatant to be acidic means adjusting the pH of the supernatant to 3.0-5.0.
Preferably, the pH of the supernatant is adjusted in step (2) using sulfuric acid.
In the step (2), the input amount of the catalyst is 3.5 to 6 times of the total mass of the COD (chemical oxygen demand) of the wastewater, and the input amount of the hydrogen peroxide is 0.35 to 1.20 times of the total mass of the COD of the wastewater.
In the step (2), the irradiation intensity of the ultraviolet light is 6.0-50.0W/m 2 。
In the step (2), the irradiation time of the ultraviolet light is 0.5-4 h.
And (3) adding a flocculating agent for flocculation, wherein the flocculating agent is PAM.
Preferably, the amount of PAM added is 2 to 5ppm.
In the step (3), preferably, the treatment liquid is adjusted to be neutral with sodium hydroxide or calcium hydroxide.
In the step (2), the used catalyst laterite is recycled and reused.
The method for recovering the red soil comprises the following steps: firstly, carrying out alkali washing and then carrying out water washing, thereby eluting pollutants such as COD (chemical oxygen demand) and the like adsorbed in the laterite. And (3) adding the recovered catalyst into the step (2) for treatment, and reusing.
Preferably, the alkali used in the alkali washing for the laterite recovery is sodium hydroxide, and the concentration is 0.8-1.8 mol/L.
Has the beneficial effects that: (1) According to the invention, through pretreatment, laterite can be used as a heterogeneous Fenton catalyst and can be reused, the laterite has the advantages of large storage capacity, convenience in mining and relatively low cost, the laterite pretreatment step is simple, the laterite can be applied in a large scale, and the problems of high cost and complicated preparation steps in the prior art are solved. (2) The invention adopts three flocculation processes of primary flocculation, laterite adsorption flocculation and secondary flocculation, and can effectively remove suspended matters (SS), COD and chromaticity in the wastewater. (3) The invention adopts laterite as the catalyst of the heterogeneous photo-Fenton method, and can non-selectively treat wasteVarious organic pollutants and inorganic pollutants in water are subjected to catalytic oxidation degradation, and meanwhile TiO in the red soil 2 Under the irradiation of ultraviolet light, the catalytic oxidation effect is further enhanced. (4) The wastewater treatment method adopted by the invention has wide reaction pH adaptation range, so that the dosage of acid, alkali and other medicaments is small. (5) According to the wastewater treatment method adopted by the invention, the catalyst laterite can be recycled for multiple times, the amount of iron mud generated after the reaction is finished is small, and the secondary pollution is small.
Drawings
Fig. 1 is a schematic view of a landfill leachate treatment apparatus used in an embodiment, a comparative example, and an application example of the present invention, in which 1 is a water inlet, 2 is a sludge discharge port, 3 is a sludge storage hopper, 4 is a water outlet, 5 is an ultraviolet lamp, and 6 is a stirring apparatus;
FIG. 2 is a graph showing the effect of adding calcined and washed red mud at different temperatures on the COD degradation of landfill leachate by the method described in example 1;
FIG. 3 is a comparison of laterites before (a) and after (b) pretreatment as used in example 1 of the present invention;
FIG. 4 is a diagram illustrating the effect of example 1-3 of the present invention on the COD degradation of landfill leachate;
FIG. 5 is a diagram showing the effect of COD degradation of landfill leachate treated by the method of example 3 according to the present invention;
FIG. 6 is a diagram showing the COD degradation effect of landfill leachate in comparative examples 1 to 5;
fig. 7 is the activity of the laterite recovered and recycled by the method provided by the invention, the activity is measured as COD removed in use, and the activity in initial use is recorded as 100%.
Detailed Description
To further illustrate the present invention, the following detailed description of the invention is given in conjunction with examples, comparative examples, application examples and the accompanying drawings:
1. raw material source and processing device
1.1 starting materials
(1) Laterite: the production place is 400 meshes in Hebei of China.
(2) Hydrogen peroxide: 30 percent of aqueous hydrogen peroxide solution by mass percentage.
(3) The source of the wastewater is as follows: the source of the waste water of the invention can be chemical industry and printing and dyeing waste water. However, chemical and printing wastewater is of various types and complicated components, and in order to avoid the above-mentioned disadvantages of wastewater, landfill leachate is used in this embodiment.
And (3) garbage leachate: the landfill leachate is taken from a certain landfill site in Jiangsu, is treated by UASB and two-stage SBR, and the COD of the landfill leachate after treatment is 983mg/L and is treated by the treatment method provided by the invention.
1.2 treatment plant
In order to further simplify the treatment steps, the landfill leachate treatment device shown in fig. 1 is adopted to treat the landfill leachate in the examples, the comparative examples and the application examples of the invention. This processing apparatus's major structure is the treatment tank, the volume of treatment tank can be selected according to actual need, upside side at the treatment tank is provided with the water inlet 1 that is used for untreated landfill leachate to send into, bottom at the treatment tank is provided with mud discharging port 2, treatment tank below sets up the sediment that is used for in the landfill leachate treatment process to send out and stores mud bucket 3, be provided with delivery port 4 in addition at treatment tank downside side, in order to realize ultraviolet irradiation, be provided with ultraviolet lamp 5 above the treatment tank, the treatment tank is provided with agitating unit 6 in addition.
2. Sample processing
2.1 Effect of laterite pretreatment on COD removal
Step 1: and (2) loading 20.0L of landfill leachate into a treatment device with an effective volume of 30.15L from a water inlet of the treatment device, starting a stirring device, stirring at the rotating speed of 150rpm, adding 10.0g of PAC solution with the mass fraction of 10% while stirring, then continuing to stir for 10min, stopping stirring, standing for precipitation for 90min, discharging the generated precipitation from a sludge discharge port at the bottom of the treatment device, and leaving supernatant for next-step treatment.
Step 2: turning on a stirring device, stirring at the rotating speed of 150rpm, adding sulfuric acid to adjust the pH value of the landfill leachate to 4.0, then adding 68.8g of uncalcined and washed laterite into a treatment device, adding 22.9g of hydrogen peroxide, turning on an ultraviolet lamp, and irradiating with the irradiation intensity of 50w/m 2 Irradiation ofAnd (3) 120min, after the reaction is finished, closing the ultraviolet lamp and the stirring device, and standing and precipitating for 90min. The precipitate containing the red mud is recovered from a mud discharge port at the bottom of the treatment apparatus, and the supernatant (treatment liquid) is left for further treatment.
And step 3: and (3) opening a stirring device, stirring at a rotating speed of 250rpm, adding sodium hydroxide to adjust the pH of the treatment solution to about 7.5, adding 60g of PAM solution with the mass fraction of 1 thousandth, continuously stirring for 5min, stirring at a rotating speed of 150rpm for 5min, stopping stirring, standing for precipitation for 120min, discharging generated precipitate from a sludge discharge port, wherein the supernatant is the effluent treated by the treatment device. As shown in fig. 2, direct treatment of sewage landfill leachate with uncalcined laterite has limited COD removal. In order to solve the problem of laterite application, laterite is calcined and washed at different temperatures, and as a result, it is found that when calcined and washed laterite is used for landfill leachate treatment, COD in landfill leachate can be effectively removed.
The effect of laterite treatment on final COD removal is shown in figure 2, the result of figure 2 being the use of the method of example 1, except that: the laterite used in the step 2 is calcined at 200, 400, 600, 800, 1000 and 1200 ℃ for 120min without calcination, and the calcined laterite is washed with water. The result shows that when the calcination temperature of the laterite is 600-1000 ℃, the laterite has a good COD degradation effect on the landfill leachate.
As shown in fig. 3, fig. 3a is uncalcined laterite, and fig. 3b is laterite calcined at 600 ℃ for 120min and washed and dried. After the laterite is calcined, the appearance of the laterite is not changed, but the laterite is changed from original red to yellow due to color difference, and the laterite can be used for landfill leachate treatment due to the fact that organic matters such as humus in the laterite can be removed through high temperature provided by calcination.
2.2 landfill leachate treatment
Example 1: the process of example 1 is substantially the same as that of part 2.1, except that laterite calcined at 600 ℃ and washed with water is added, with the following specific steps:
step 1: and (2) loading 20.0L of landfill leachate into a treatment device with an effective volume of 30.15L from a water inlet of the treatment device, starting a stirring device, stirring at the rotating speed of 150rpm, adding 10.0g of PAC solution with the mass fraction of 10% while stirring, then continuing to stir for 10min, stopping stirring, standing for precipitation for 90min, discharging the generated precipitation from a sludge discharge port at the bottom of the treatment device, and leaving supernatant for next-step treatment.
Step 2: placing the red clay into a muffle furnace, calcining for 120min at the temperature of 600 ℃, washing for 3 times by using distilled water, and drying at the temperature of 103-105 ℃.
And step 3: turning on a stirring device, stirring at a rotating speed of 150rpm, adding sulfuric acid to adjust the pH value of the landfill leachate to 4.0, then adding 68.8g of the laterite pretreated in the step 2 into a treatment device, adding 22.9g of hydrogen peroxide, turning on an ultraviolet lamp, and irradiating with an irradiation intensity of 50w/m 2 And irradiating for 120min, after the reaction is finished, closing the ultraviolet lamp and the stirring device, and standing and precipitating for 90min. The precipitate containing the red mud is recovered from a mud discharge port at the bottom of the treatment apparatus, and the supernatant (treatment liquid) is left for further treatment.
And 4, step 4: and (3) opening a stirring device, stirring at a rotating speed of 250rpm, adding sodium hydroxide to adjust the pH of the treatment solution to about 7.5, adding 60g of PAM solution with the mass fraction of 1 thousandth, continuously stirring for 5min, stirring at a rotating speed of 150rpm for 5min, stopping stirring, standing for precipitation for 120min, discharging generated precipitate from a sludge discharge port, wherein the supernatant is the effluent treated by the treatment device. As shown in FIG. 4, the COD of the effluent was 302mg/L, and the COD removal rate was 69.3%.
And 5: recovering the precipitate containing laterite in step 3: placing the sediment containing the laterite into a sodium hydroxide solution of 2000mL1.2mol/L, stirring at the rotating speed of 300rpm for 60min, standing for 120min, taking out the sediment, washing with distilled water for 5 times, and drying at 103-105 ℃.
Example 2: the method for treating landfill leachate based on laterite in the embodiment comprises the following specific steps:
step 1: and (2) loading 20.0L of landfill leachate into a treatment device with an effective volume of 30.15L from a water inlet of the treatment device, opening a stirring device, stirring at the rotating speed of 150rpm, adding 10.0g of PAC solution with the mass fraction of 10% and 80.0g of PAM solution with the mass fraction of 1 thousandth while stirring, then continuing stirring for 10min, stopping stirring, standing for precipitating for 90min, discharging the generated precipitate from a sludge outlet at the bottom of the treatment device, and leaving the supernatant for next treatment.
Step 2: placing the red clay into a muffle furnace, calcining for 120min at 800 ℃, washing for 3 times by using distilled water, and drying at 103-105 ℃.
And 3, step 3: turning on a stirring device, stirring at a rotating speed of 150rpm, adding sulfuric acid to adjust the pH value of the landfill leachate to 4.0, then adding 98.3g of the laterite pretreated in the step 2 into a treatment device, adding 52.4g of hydrogen peroxide, turning on an ultraviolet lamp 5, and controlling the irradiation intensity to be 50w/m 2 Irradiating for 120min, after the reaction is finished, closing the ultraviolet lamp and the stirring device, and standing and precipitating for 90min. The precipitate containing the red mud is recovered from a mud discharge port at the bottom of the treatment apparatus, and the supernatant (treatment liquid) is left for further treatment.
And 4, step 4: and (3) opening a stirring device, stirring at a rotating speed of 250rpm, adding sodium hydroxide to adjust the pH of the treatment solution to about 7.5, adding 80g of PAM solution with the mass fraction of 1 thousandth, continuing stirring for 5min, stirring at a rotating speed of 150rpm for 5min, stopping stirring, standing for precipitation for 120min, discharging generated precipitate from a sludge discharge port, wherein the supernatant is the effluent treated by the treatment device. As shown in FIG. 4, the COD of the effluent was 208mg/L, and the COD removal rate was 78.8%.
And 5: and (4) recovering the precipitate containing the red soil in the step (3): putting the precipitate containing the laterite into a 3000mL1.5mol/L sodium hydroxide solution, stirring at the rotating speed of 300rpm for 60min, standing for 120min, taking out the precipitate, washing with distilled water for 5 times, and drying at the temperature of 103-105 ℃.
Example 3: the method for treating landfill leachate based on laterite in the embodiment comprises the following specific steps:
step 1: loading 20.0L of landfill leachate into a treatment device with an effective volume of 30.15L from a water inlet of the treatment device, opening the stirring device, stirring at a rotating speed of 200rpm, adding 15.0g of PAC solution with a mass fraction of 10% and 80.0g of PAM solution with a mass fraction of 1 ‰whilestirring, then continuing stirring for 10min, stopping stirring, standing for 90min, discharging the generated precipitate from a sludge discharge port at the bottom of the treatment device, and leaving the supernatant for next treatment.
Step 2: placing laterite in a muffle furnace, calcining at 800 ℃ for 120min, washing with distilled water for 3 times, and drying at 103-105 ℃.
And step 3: turning on a stirring device, stirring at a rotating speed of 150rpm, adding sulfuric acid to adjust the pH value of the landfill leachate to 3.0, then adding 118.0g of the laterite pretreated in the step 2 into a treatment device, adding 65.5g of hydrogen peroxide, turning on an ultraviolet lamp, and irradiating with an irradiation intensity of 50w/m 2 And irradiating for 150min, after the reaction is finished, closing the ultraviolet lamp and the stirring device, and standing and precipitating for 90min. The precipitate containing the red mud is recovered from a mud discharge port at the bottom of the treatment apparatus, and the supernatant (treatment liquid) is left for further treatment.
And 4, step 4: and (3) opening a stirring device, stirring at a rotating speed of 250rpm, adding sodium hydroxide to adjust the pH of the treatment solution to about 7.5, adding 100g of PAM solution with the mass fraction of 1 thousandth, continuously stirring for 5min, stirring at a rotating speed of 150rpm for 5min, stopping stirring, standing for precipitation for 120min, discharging generated precipitate from a sludge discharge port, wherein the supernatant is the effluent treated by the treatment device. As shown in FIG. 4, the COD of the effluent was 163mg/L, and the COD removal rate was 83.4%.
And 5: and (4) recovering the precipitate containing the red soil in the step (3): placing the sediment containing the laterite into a 3000mL1.2mol/L sodium hydroxide solution, stirring at the rotating speed of 300rpm for 60min, standing for 120min, taking out the sediment, washing with distilled water for 5 times, and drying at 103-105 ℃.
In order to further study the COD reduction result of each step of treatment, COD detection is carried out on the effluent treated in the step 1, the step 3 and the step 4 in the example 3, the detection result is shown in figure 5, after the landfill leachate is treated in the step 1, the COD is reduced to 750mg/L from 983mg/L, after the landfill leachate is treated in the step 3, the COD is reduced to 292mg/L, and after the landfill leachate is treated in the step 4, the COD is further reduced to 163mg/L.
2.3 Effect of each treatment on COD removal
In order to study the effect of different treatment methods on COD treatment, the following experiments were set up using the method of example 1:
comparative example 1: the process as described in example 1, except that: in step 1, no PAC is added to flocculate the landfill leachate.
Comparative example 2: the process as described in example 1, except that: in step 3, no catalyst laterite was added.
Comparative example 3: the process as in example 1, except that: in step 3, no hydrogen peroxide was added.
Comparative example 4: as described in example 1, except that: in step 3, no ultraviolet lamp was used for irradiation.
Comparative example 5: as described in example 1, except that: in step 4, no PAM was added.
As shown in FIG. 6, the degradation effect of the landfill leachate COD by the comparative examples 1 to 5 is known, the method of the present invention has the best degradation effect on the landfill leachate COD, and the degradation effect of the landfill leachate COD can be effectively improved by performing primary flocculation, adding the catalyst laterite, adding the hydrogen peroxide, performing ultraviolet irradiation and performing secondary flocculation.
Application example 1: the used catalyst laterite in the example 1 is recovered and recycled again according to the method in the example 1. The activity of the laterites was measured as COD removed at time of use and the activity at first time of use was recorded as 100% and the results are shown in figure 7. As can be seen from fig. 7, the laterite can retain over 50% activity in 6 cycles in the present invention.
Claims (8)
1. A method for wastewater treatment using a heterogeneous fenton catalyst, comprising the steps of:
(1) Performing primary flocculation on the wastewater to obtain a supernatant;
(2) Adjusting the supernatant obtained in the step (1) to be acidic, adding a heterogeneous Fenton catalyst and hydrogen peroxide, and irradiating by using ultraviolet light to obtain a treated treatment solution; the heterogeneous Fenton catalyst is preprocessed laterite, the preprocessing method is to calcine laterite, the calcination temperature is 600-1000 ℃, and the calcination time is 60-120 min;
(3) And (3) adjusting the treated liquid treated in the step (2) to be neutral, and flocculating again to obtain treated water.
2. The method according to claim 1, wherein in the step (1), the primary flocculation is to add a flocculating agent into the wastewater, and the flocculating agent is one or both of polyacrylamide and polyaluminium chloride.
3. The method according to claim 1, wherein in step (2), the heterogeneous Fenton catalyst is washed with water.
4. The method according to claim 1, wherein the step (2) of adjusting the supernatant to be acidic means adjusting the pH of the supernatant to 3.0 to 5.0.
5. The method according to claim 1, wherein in the step (2), the ultraviolet irradiation intensity is 6.0-50.0W/m 2 。
6. The method according to claim 1, wherein in the step (2), the used heterogeneous Fenton catalyst is recycled by performing alkali washing and then water washing on the heterogeneous Fenton catalyst.
7. Use of the method according to claim 1 for the removal of COD from waste water with a COD content of > 200mg/L.
8. The use according to claim 7, wherein the heterogeneous Fenton catalyst is added in an amount of 3.5 to 6.0 times the total mass of COD in the wastewater, and the hydrogen peroxide is added in an amount of 0.35 to 1.2 times the total mass of COD in the wastewater.
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