CN111822005A - Fenton reaction catalyst, preparation method, Fenton reactor based on catalyst and garbage leachate full-quantitative treatment method - Google Patents
Fenton reaction catalyst, preparation method, Fenton reactor based on catalyst and garbage leachate full-quantitative treatment method Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
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- 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
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
- B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
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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
- C02F1/722—Oxidation by peroxides
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- 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
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to a Fenton reaction catalyst, a preparation method, a Fenton reactor based on the catalyst and a full-quantitative treatment method of landfill leachate, and belongs to the field of sewage treatment. The catalytic active components of the Fenton reaction catalyst comprise: ZnS, PbS, Co3S4. The invention also provides a Fenton reactor based on the Fenton reaction catalyst and a full-quantitative treatment method of landfill leachate. The Fenton reaction catalyst, the Fenton reactor and the garbage leachate full-quantitative treatment method can efficiently reduceLow COD value in the landfill leachate.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a Fenton reaction catalyst, a preparation method of the Fenton reaction catalyst, a Fenton reactor based on the Fenton reaction catalyst, and a full-quantitative treatment method of landfill leachate.
Background
The full-quantitative treatment technology of the landfill leachate is a trend of future leachate treatment, and can effectively solve a series of problems caused by recharging membrane concentrated solution after the treatment of biochemical and membrane technologies and full-membrane technologies in the conventional technologies for a long time. Compared with the existing 'evaporation and solidification' process, the 'biochemical and Fenton' operation cost is lower.
Advanced Oxidation Processes (AOPs) mainly include a Fenton method and a Fenton-like method, and the Fenton method is a common Advanced Oxidation technology for biochemical treatment units of leachate, and can effectively remove organic pollutants in the leachate. In the Fenton reaction, H2O2Has a low decomposition efficiency even if Fe is added2+The decomposition efficiency is still low, so that a large amount of H is required2O2And catalysts, making their use on a large scale in wastewater treatment prohibitively expensive. In a practical industrial environment, large quantities are often requiredFe (b) of2 +And H2O2Sufficient concentration of OH can be generated. Furthermore, the Fenton reaction Fe3+To Fe2+Much lower than Fe2+To Fe3+The rate of conversion. Therefore, excessive Fe is generated3+Ions, leading to the formation of sludge (iron cement) and thus to catalyst poisoning. On the other hand, too much hydrogen peroxide used in AOP corrodes equipment and greatly increases operating costs.
By adding various materials as "promoters" to enhance the production of OH, although much effort has been made to optimize AOP, particularly to optimize Fe3+To Fe2+Efficiency of the conversion. However, almost all previous reports on the promoted AOP have focused on the use of organic compounds as promoters, which are prone to secondary pollution and difficult to completely mineralize organic molecules.
The Fenton method is an important part of common full-scale treatment technology of the percolate at present, but the traditional Fenton method has the problems of low efficiency, high iron mud yield and the like. In addition, the water quantity change of the percolate is large along with the change of seasons, and the traditional Fenton method is difficult to meet the treatment requirement of the percolate.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, and provide a Fenton reaction catalyst which can improve the Fenton reaction efficiency, reduce the dosage of a Fenton reagent, has few byproducts and does not produce exudation toxicity: the fixed hydrosulfuric acid modified metal mineral Fenton reaction catalyst also provides a preparation method of the fixed hydrosulfuric acid modified metal mineral Fenton reaction catalyst, which is simple in preparation process, easy in raw material obtaining and low in cost, and an application of the fixed hydrosulfuric acid modified metal mineral Fenton reaction catalyst in the aspect of strengthening the Fenton method for treating landfill leachate.
In order to solve the technical problems, the invention adopts the following technical scheme:
a Fenton reaction catalyst, characterized in that its catalytically active components comprise: ZnS, PbS, Co3S4。
The above-mentionedZnS, PbS, Co of3S4The mass ratio is 3-5: 1-2: 0.5, preferably 3: 1: 0.5;
because the Fenton treatment is arranged at the back end of the biochemical treatment, biochemical effluent can bring a small part of activated sludge, and the invention adopts minerals with different catalytic activities for proportioning, thereby not only playing a catalytic role, but also playing roles in adsorption and filtration.
From the catalytic effect of the individual substances, the catalytic effect: ZnS < PbS < Co3S4The content of the substances is reduced in sequence by combining the availability and the material cost of the raw materials; the catalyst has relatively poor catalytic effect, and can play a role in filling, so that the thickness of the filler layer can be ensured, and the filler layer has sufficient filtering and adsorbing effects.
From the comprehensive use effect, the technical embodiment of the invention is provided with two catalyst filler units (also equivalent to the filler layer), and a single catalyst filler unit contains 3 layers of catalysts (also equivalent to the filler) with different particle sizes, so that the effects of gradient filtration, layer-by-layer catalysis and full contact of the catalysts and wastewater are achieved, the filler blockage can be relieved, and the filler backwashing time is prolonged.
The ZnS that catalytic activity is low accounts for than big, because catalytic activity is low, can lean on increasing the quantity to reach the effect, bring certain filling effect when increasing the quantity, make the packing layer can possess ideal thickness, extension contact time and area of contact, the mineral that this catalytic activity is low is easily obtained, the source is relatively more extensive, otherwise do not add this material, full-purpose catalytic activity is good, the catalyst quantity is very low, packing layer thickness is not enough, not both reach better filter effect, can not play the effect of extension contact time again, on the contrary not so good effect.
Preferably, the ZnS is hydrosulfuric acid-modified sphalerite particles;
preferably, the PbS is a hydrosulfuric acid modified galena particles;
preferably, the Co3S4Is a cobaltite particle modified by hydrosulfuric acid;
preferably, the particle size of the hydrosulfuric acid modified sphalerite particles, the hydrosulfuric acid modified galena particles and the hydrosulfuric acid modified cobaltite particles is selected from 0.1 mm-4 mm.
The preparation method of the Fenton reaction catalyst is characterized in that ZnS, PbS and Co are mixed3S4And (4) mixing.
Mixing ZnS, PbS and Co3S4Mixing at a mass ratio of 3-5: 1-2: 0.5, preferably 3: 1: 0.5;
preferably, the galena, the sphalerite and the cobaltite are respectively subjected to modification by hydrosulfuric acid, flotation and sieving to obtain ZnS, PbS and Co3S4Mixing the granules again;
preferably, the galena, blende and skutterudite are newly produced raw ores of the mine.
Theoretically commercially available ZnS, PbS, Co3S4But also can play a role in catalysis, but because the components have high purity and high cost and are powdery, the addition amount is small, a packing layer with proper particle size and proper thickness cannot be obtained, the components cannot be loaded by particles with different particle sizes like the invention patent, not only can play a role in catalysis, but also can play a role in adsorption filtration, and can reduce the content of iron sludge and other suspended matters in Fenton effluent.
The effect of the modification with hydrogen sulfuric acid is to remove mainly other metal oxides entrained in the sulphide ores in the ore, so that the surface of the ore has a higher amount of metal sulphides.
Before the modification of the hydrosulfuric acid, the minerals need to be crushed;
preferably, the hydrosulfuric acid-modified flotation means: adding hydrogen sulfuric acid into the crushed minerals;
preferably, the minerals floated by the modification of the hydrogen sulfuric acid are respectively washed by absolute ethyl alcohol and pure water and then dried for 24 hours at the temperature of 50-80 ℃;
preferably, the dried mineral is sieved sequentially through 5 mesh, 18 mesh, 50 mesh and 140 mesh sieves to obtain the following 3 particle size ranges, respectively: 1mm to 4mm, 0.3 to 1mm and 0.1 to 0.3mm of ore particles;
preferably, the mixing refers to mixing three ore particles belonging to the same grain size range.
A fenton reactor comprising a catalyst packing unit located inside the reactor; the catalyst filler unit comprises an upper layer, a middle layer and a lower layer of 3 catalyst particle layers, and the particle size of each layer of catalyst particle is increased from top to bottom in sequence;
the catalyst comprises ZnS, PbS and Co3S4。
The particle size of the catalyst particles of the upper catalyst particle layer is 0.1-0.3 mm, the particle size of the catalyst particles of the middle catalyst particle layer is 0.3-1 mm, and the particle size of the catalyst particles of the lower catalyst particle layer is 1-4 mm;
preferably ZnS, PbS, Co3S4The mass ratio of (A) to (B) is as follows: 3-5: 1-2: 0.5, preferably 3: 1: 0.5;
the particle layers with different particle sizes are arranged, so that on one hand, the retention time of the percolate and the Fenton reagent in the mineral layer can be increased, and the contact area of the pollutants, the Fenton reagent and the sulfide minerals is increased so as to more efficiently treat the pollutants; on the other hand down to the arrangement that the particle size reduces in proper order, with rivers direction unanimity (the rivers direction is down advances upward out), played the effect of gradient filtration, can reduce the jam of packing layer like this, can reduce the content of the suspension of fenton play water through multilayer filtration.
Preferably, the catalyst particles may be placed in a filter bag;
preferably, the filter bag is in a circular ring structure after being filled with catalyst particles;
preferably, the Fenton reactor is of a reaction tank structure with a hollow interior; a fixing component capable of fixing the catalyst particle layer is arranged in the reaction tank;
preferably, the fixing part is a fixing column arranged on the inner wall of the bottom of the reaction tank; the annular filter bag filled with the catalyst particles can be sleeved on the fixed column; the size and the shape of the circular filter bag filled with the catalyst particles are matched with the inner part of the reaction tank;
preferably, a clamping groove is formed in the center of the inner wall of the bottom of the reaction tank; the fixing column can be clamped in the clamping groove;
preferably, 3 circular filter bags filled with catalyst particles are arranged, and correspond to the upper, middle and lower 3 catalyst particle layers respectively;
preferably, the number of the catalyst packing units is 1, 2 or more;
preferably, a feed inlet and a discharge outlet are formed in the wall of the reaction tank, and the top of the reaction tank can be opened and is provided with a top cover capable of being opened and closed;
preferably, the height of the catalyst packing elements is from 5 to 20 cm.
The Fenton reaction catalyst and/or the Fenton reaction catalyst obtained by the preparation method and/or the application of the Fenton reactor in treating organic pollution.
The full-quantitative treatment method of the landfill leachate is characterized in that the Fenton reaction catalyst is adopted, and/or the Fenton reaction catalyst obtained by the preparation method is adopted, and/or the Fenton reactor is used for treating the landfill leachate.
The Fenton reaction reagent is FeSO4·7H2O and H2O2；
Preferably, the FeSO4·7H2O is 2-12mmol/L, H2O2Is 100-600 mmol/L;
more preferably, the reaction system has a pH of 3 to 5;
preferably, the addition amount of the catalyst particles in the catalyst packing unit is 6-10 g/L.
Comparative example 4 of the present invention shows that too few catalyst particles reduce the efficiency of Fenton degradation of COD. Too much is uneconomical and occupies space, and the catalyst can reach the standard when the concentration is 6-10g/L, namely the total amount of the catalyst particles of each liter of reaction reagent in each reaction system is 6-10 g.
Aiming at the defects or improvement requirements of the existing Fenton technology, the invention provides a Fenton technology enhancement method for full-quantitative treatment of landfill leachate, wherein the organic pollutants in the leachate can be efficiently degraded by the oxidation of the catalytic Fenton reaction through the preparation and layered immobilization of key hydrosulfuric acid modified metal particles. The method can effectively overcome the defects of slow reaction rate, large usage amount of Fenton reagent and large generation amount of iron mud in the prior art, not only can remarkably improve the Fenton reaction rate, but also can reduce the treatment cost of the percolate. In addition, the raw materials of the hydrogen sulfuric acid modified metal particles are easy to obtain, the cost is low, and the particle preparation process is very simple. Moreover, the catalyst is wrapped by a filter bag and fixed in a Fenton tank reaction area in a layered mode, so that the catalysis assisting effect can be effectively controlled to be exerted stably, and leaching toxicity is not generated. In addition, the prepared hydrosulfuric acid modified mineral particles have longer service life and do not need to be replaced frequently. In the invention, the organic pollutants in the leachate are degraded by using the hydrogen sulfuric acid modified metal particles to assist in catalysis, and an effective improvement way is provided for treating the leachate by a Fenton method.
In the prior art, iron ore coupled iron sulfide is used as a catalyst, but iron is used as a main catalytic action, but the iron is not mineral, the catalytic action of the invention completely depends on pure mineral, and the filtering catalytic effect is exerted to the optimum through reasonable proportion and particle size setting.
The data for the blank experiment, i.e. the control experiment without the addition of sulphide minerals, i.e. the conventional fenton process, show that: at the same time, the removal rate of COD was the lowest, which indicates that in order to achieve better removal effect of COD, the dosage of the agent is increased, and more iron sludge is generated.
A Fenton process enhancing method for full-quantitative treatment of landfill leachate comprises the following steps;
(1) preparation of the hydrosulfuric acid modified metal mineral particles: crushing galena, sphalerite and thiocobalite, adding a large amount of hydrosulfuric acid into the crushed minerals to perform hydrosulfuric acid modified flotation, respectively cleaning the crushed minerals by absolute ethyl alcohol and pure water, placing the cleaned minerals in an oven at 50-80 ℃ for drying for 24 hours, and cooling the cleaned minerals to obtain dried hydrosulfuric acid modified metal minerals; sieving the dried mineral with 5-mesh, 18-mesh, 50-mesh and 140-mesh sieves in sequence to obtain PbS, ZnS and Co with particle sizes of 1-4 mm, 0.3-1 mm and 0.1-0.3 mm respectively3S4Ore particles. Wherein the galena, the sphalerite and the thiocobalite are newly produced ores of the mine.
(2) Fixing deviceThe process of catalyzing the Fenton treatment leachate by using the hydrogen sulfide modified metal mineral comprises the following steps: uniformly mixing the three types of hydrosulfuric acid modified metal mineral particles with the same particle size obtained in the step (1) according to a proportion, wrapping the mixed mineral particles with each particle size by using a filter bag with a proper pore size, and fixing the mixed mineral particles in a reaction area in a Fenton reactor (5) in layers according to the particle size (the particle sizes are sequentially reduced from bottom to top). As shown in fig. 1, the mixed solution of leachate and fenton reagent is pumped through a water inlet pipe (1) of the reaction tank to enter the bottom of the fenton reactor, and then the mixed solution sequentially passes through a crude hydrogen sulfuric acid modified metal mineral layer (2), a medium hydrogen sulfuric acid modified metal mineral layer (3) and a fine hydrogen sulfuric acid modified metal mineral layer (4). The unsaturated S atoms on the surface of the metal hydrosulfuric acid modifier in the mineral particles can be used to capture protons to form H2S and exposing the metal active site with reducibility can greatly accelerate Fe3+/Fe2+The speed limiting step of the conversion enables hydroxyl free radicals to be generated more quickly, so that organic pollutants in the leachate are degraded quickly.
The solution after reaction is discharged through a water outlet (8). The hydrogen-sulfuric acid modified metal mineral layer wrapped by the filter bag is fixed on the central fixing column (6), and the central fixing column (6) is mechanically fixed in the fixing clamping groove (10). The reaction tank top cover (7) is movably arranged. The emptying pipe (9) is communicated with the outside.
The addition amount of the hydrosulfuric acid modified ore unit added in the step (2) is 6-10g/L, and FeSO in the Fenton reagent is added4·7H2O is 10 to 12mmol/L, H2O2Is 400 to 600 mmol/L.
In step (1), the crushed ore is subjected to hydrosulfuric acid modified flotation (hydrosulfuric acid), and after flotation, the crushed ore is washed by absolute ethyl alcohol and pure water respectively to remove some organic and inorganic impurities contained in the ore particles.
In the step (2), the mineral particles passing through the same grain are mixed according to the mass ratio of ZnS: PbS: co3S4= 3: 1: 0.5 are mixed uniformly.
In the step (2), the mixed minerals (from top to bottom, the grain sizes are from fine to coarse) with different grain sizes are fixed on a central fixed column (6) in the Fenton reaction tank layer by layer so as to increase the retention time of the mixed liquid in a fixed filler area and fully remove the organic pollutants in the percolate. Wherein the different particle size units are as follows by mass ratio (1 mm-4 mm): (0.10 mm-0.30 mm): (0.30 mm to 1 mm) = 3: 2: 1 is configured.
In the step (2), the three fixed layers of hydrosulfuric acid modified metal minerals with different particle sizes are as follows: the hydrogen sulfuric acid modified metal particles are wrapped by filter bags with different apertures (the wrapped mineral particles with corresponding particle sizes cannot leak out) to be flexibly fixed in a Fenton pot reaction area in a round cake shape. The upper part and the lower part of the round cake packing are divided into two layers (the number of the round cakes can be increased or decreased according to the conditions of water quality and water quantity).
Furthermore, the hydrogen-sulfuric acid modified metal minerals fixed in layers are mechanically fixed (detachable) on a central fixed column (6) in the reactor, and a cover plate (7) of the reaction tank is movably arranged, so that the minerals can be conveniently recovered and replaced.
Further, the pH value of the system is controlled to be 3-5.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a Fenton reaction catalyst: the fixed hydrosulfuric acid modified metal mineral Fenton reaction catalyst is prepared by carrying out hydrosulfuric acid modified flotation and sieving on galena, sphalerite and cobaltosite, and then carrying out ZnS: PbS: co3S4= 3: 1: 0.5 ratio of the mixture. Compared with the existing Fenton and the related technology thereof, the addition of the Fenton reaction catalyst-hydrosulfuric acid modified metal mineral particles can obviously accelerate Fe in the Fenton reaction3+To Fe2+Thereby greatly promoting the generation of hydroxyl radicals and reducing the dosage of Fenton reagent. In addition, due to Fe in the solution3+The concentration is obviously reduced, and the yield of the iron sludge is reduced. The Fenton reaction catalyst provided by the invention obviously promotes the efficiency of removing percolate by Fenton, saves Fenton medicaments, obviously reduces the treatment cost and has great value for the application of engineering practice.
(2) The invention also provides a preparation method of the Fenton reaction catalyst, which comprises the following steps: crushing the metal minerals, performing modified flotation of the hydrogen sulfuric acid, sieving and mixing. The organic pollutants in the leachate are degraded by directly utilizing the catalytic Fenton reaction assisted by the hydrosulfuric acid modified metal contained in the ores (such as galena, sphalerite and thiocobalite), the preparation method is simple, the processes of firing, loading and the like are not needed, a series of purification processes are not needed to prepare the high-purity hydrosulfuric acid modified metal, and the simple steps of crushing, grinding, hydrosulfuric acid modified flotation, drying, sieving and the like are only needed.
Although the mineral sources are wide and the preparation is simple, the hydrogen sulfuric acid modified metal mineral particles provided by the invention actually remarkably promote the efficiency of removing leachate by Fenton, save Fenton medicaments, obviously reduce the treatment cost and have great value for the application of engineering practice.
(3) According to the invention, the hydro-sulfuric acid modified metal particles are wrapped by the filter bag with a certain aperture and are fixed in the Fenton reactor in a layered manner, so that not only can the continuous catalysis assisting effect be achieved, but also the replacement and recovery treatment of the hydro-sulfuric acid modified metal are facilitated, and the leaching toxicity is not generated. The Fenton reaction solution can contact with the hydrosulfuric acid modified metal mineral particles through flowing, so that the continuous catalysis assisting effect is achieved. The mineral particles with different particle sizes are distributed in a layered mode, so that the contact time of the percolate and the mineral particles can be prolonged, and the removal efficiency is better.
(4) The method for improving Fenton treatment leachate by using the immobilized hydrosulfuric acid modified metal mineral solves the problems of low Fenton reaction efficiency and high iron mud yield. The reaction efficiency can be obviously improved due to the catalysis of the hydrogen sulfuric acid modified metal, the total retention time of the percolate in the Fenton reactor can be reduced, and the problem that the percolate is difficult to rapidly dispose due to the surge of water in rainy seasons is effectively prevented. The invention can make the COD of the effluent reach the standard within 60 minutes, reduce the retention time of the percolate in the reaction tank and treat more percolate in unit time, thereby solving the problem that the water quantity change of the percolate is greatly changed along with seasons.
Drawings
Fig. 1 is a schematic diagram of a reaction apparatus for catalytic fenton treatment of leachate according to one embodiment of the present invention. The labels in the figure are listed below: 1-a feed inlet (a water inlet pipe), 2-a lower catalyst particle layer, 3-a middle catalyst particle layer, 4-an upper catalyst particle layer, 5-the inside of a reaction tank, 6-a fixed column, 7-the top of the reaction tank, 8-a discharge outlet (a water outlet pipe), 9-a vent pipe and 10-a clamping groove.
FIG. 2 is a schematic diagram of the Fenton reaction catalyst of the present invention for catalyzing the Fenton reaction to treat leachate.
FIG. 3 is a diagram showing the effect of removing COD from leachate of different experimental examples and comparative examples of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the embodiments of the present invention and the accompanying drawings. The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
Example 1
The preparation method of the Fenton reaction catalyst comprises the following steps:
respectively putting the raw ores, galena, sphalerite and thiocobalite which are freshly produced from the mine into a crusher for crushing and grinding, adding a large amount of hydrosulfuric acid for hydrosulfuric acid modified flotation, respectively washing 3 times by absolute ethyl alcohol and pure water after flotation, and drying for 24 hours at 60 ℃. And after drying, sequentially sieving the mixture by using 5-mesh, 18-mesh, 50-mesh and 140-mesh sieves to obtain mineral particles with the particle sizes of 1-4 mm, 0.30-1 mm and 0.10-0.30 mm. Screening three different mineral particles with the same particle size according to the mass ratio of ZnS: PbS: co3S4= 3: 1: 0.5, and uniformly mixing. Three mixed catalysts with different particle sizes are obtained.
Example 2
The application of the Fenton reaction catalyst obtained by the preparation method of embodiment 1 of the invention in the aspect of strengthening the Fenton method for treating landfill leachate.
The Fenton reaction catalyst is PbS, ZnS and Co with particle size of 0.1-0.3 mm, 0.3-1 mm and 1-4 mm3S4Ore particles;
the Fenton reaction catalyst is prepared by mixing ore particles with the same particle size according to the particle size, wrapping the mixture into a plurality of ore units by using filter bags with proper pore diameters, and fixing the ore units in a Fenton reactor in a layered manner;
the layered fixing is that the grain diameter is from small to large from top to bottom; the Fenton reaction catalyst is fixed on a central fixed column of the reactor in a round cake shape.
The effective volume of the Fenton reactor is 8m3The reaction reagent of the Fenton method is FeSO4·7H2O and H2O2(ii) a The FeSO4·7H2O is 2-12mmol/L, H2O2Is 100-600 mmol/L; the pH value of the reaction system is 3-5; the addition amount of the hydrosulfuric acid modified ore unit is 6-10g/L
The mineral particles with the same particle size are prepared from ZnS: PbS: co3S4= 3: 1: 0.5 mixing;
the unit with different particle diameters is characterized by comprising the following components in percentage by mass (1 mm-4 mm): (0.10 mm-0.30 mm): (0.30 mm to 1 mm) = 3: 2: 1 is configured.
Experimental example 1
The Fenton reaction catalyst in the embodiment 1 and the embodiment 2 of the invention is adopted to degrade the effluent of a biochemical treatment section of the percolate in a certain landfill. Initial parameters of leachate are shown in table 1 below:
TABLE 1 effluent from percolate treatment biochemical section of certain refuse landfill
| Parameter(s) | COD | Ammonia nitrogen | Suspended matter | pH |
| Unit of | mg/L | mg/L | mg/L | / |
| Numerical value | 2043 | 12 | 120 | 3.5 |
In the experiment, leachate and a Fenton reagent (a reaction reagent of the Fenton method in reference example 2) are mixed in a Fenton dosing tank for 30s, then a mixed solution enters a Fenton reactor from a water inlet at the bottom through a pump, the mixed solution slowly and upwards contacts with a mineral particle filler, and COD in the leachate is rapidly degraded by the aid of a mineral particle catalytic Fenton reaction.
The experimental result shows that the COD removal rate in 5 minutes reaches 53.2 percent, and the COD removal rate in 30 minutes is 95.7 percent. The blank test (non-hydrosulfuric acid modified ore unit, i.e., the catalyst packing unit of the present invention) had a 5 minute COD removal of 14.6% and a 30 minute removal of 58%.
Comparative example 1: the experimental procedure was substantially the same as in experimental example 1. The difference lies in that: three different mineral particles of the same size are obtained by mass ratio ZnS: PbS: co3S4= 5: 1: 0.5. the experimental result shows that the COD removal rate in 5 minutes reaches 36.6 percent, and the COD removal rate in 30 minutes is 88.8 percent.
Comparative example 2: the experimental procedure was substantially the same as in experimental example 1. The difference lies in that: three different mineral particles with the same particle size are respectively mixed according to the mass ratio of ZnS: PbS: co3S4= 5: 2: 0.5. the experimental result shows that the COD removal rate in 5 minutes reaches 44.1 percent, and the COD removal rate in 30 minutes is 90.7 percent.
Comparative example 3: the experimental procedure was substantially the same as in experimental example 1. The difference lies in that: the difference lies in that: the sulfurized minerals are not modified. The experimental result shows that the COD removal rate in 5 minutes reaches 32.2 percent, and the COD removal rate in 30 minutes is 88.2 percent.
Experimental example 2
The preparation method of the fenton reaction catalyst used was substantially the same as in experimental example 1, except that: the drying temperature in the preparation process of the material is 50 ℃. The effective volume of the Fenton reactor is 8m3Added FeSO4·7H2O concentration of 10mmol/L, H2O2200mmol/L, and the total concentration of the mixed mineral particles is 6 g/L. The experimental result shows that the COD removal rate in 5 minutes reaches 52.1 percent, and the COD removal rate in 30 minutes is 95.3 percent.
Experimental example 3
The preparation method of the fenton reaction catalyst used was substantially the same as in experimental example 1, except that: the drying temperature in the preparation process of the material is 80 ℃. The effective volume of the Fenton reactor is 8m3Added FeSO4·7H2O concentration of 12mmol/L, H2O2300mmol/L, and the total concentration of the mixed mineral particles is 10 g/L. The experimental result shows that the COD removal rate in 5 minutes reaches 57.4 percent, and the COD removal rate in 30 minutes is 96.3 percent.
Comparative example 4: the experimental procedure was substantially the same as in experimental example 3. The difference from Experimental example 3 is that the total concentration of the mixed mineral particles was 4 g/L. The experimental result shows that the COD removal rate in 5 minutes reaches 39.4 percent, and the COD removal rate in 30 minutes is 89.4 percent.
The experimental results of each example and comparative example are shown in fig. 3. The addition of the mixed particles of the metal minerals modified by the hydrogen sulfuric acid obviously accelerates the Fenton removal of COD in the leachate. Within the range of the best implementation conditions, the leachate discharge standard in GB16889-2008 is achieved within 30 minutes. Although the effect of each proportion is reduced, the efficiency of degrading COD is obviously higher than that of the traditional Fenton process.
The invention removes the leachate by using the immobilized hydrosulfuric acid modified metal mineral to assist in catalyzing the Fenton reaction, so that three hydrosulfuric acid modified metal ores are effectively utilized, the efficiency of Fenton treatment of the leachate is remarkably accelerated, and the yield of iron sludge is reduced. The mixed cocatalyst is economical and applicable, has good stability, effectively provides a high-added-value recycling mode of the hydrogen sulfuric acid modified metal mineral, and also provides a good choice for the efficient treatment of the actual leachate.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A Fenton reaction catalyst, characterized in that its catalytically active components comprise: ZnS, PbS and Co with the mass ratio of 3-5: 1-2: 0.53S4。
2. A fenton reaction catalyst according to claim 1, wherein ZnS, PbS, Co3S4The mass ratio of the components is 3: 1: 0.5;
preferably, the ZnS is hydrosulfuric acid-modified sphalerite particles;
preferably, the PbS is a hydrosulfuric acid modified galena particles;
preferably, the Co3S4Is a cobaltite particle modified by hydrosulfuric acid;
preferably, the particle size of the hydrosulfuric acid modified sphalerite particles, the hydrosulfuric acid modified galena particles and the hydrosulfuric acid modified cobaltite particles is selected from 0.1 mm-4 mm.
3. The preparation method of the Fenton reaction catalyst is characterized in that ZnS, PbS and Co are mixed3S4Mixing according to the mass ratio of 1-3: 1-2: 0.5-1.
4. A method for preparing a Fenton reaction catalyst according to claim 3, wherein ZnS, PbS, Co are mixed3S4According to the mass ratio of 3Mixing the components in a ratio of 1: 0.5;
preferably, the galena, the sphalerite and the cobaltite are respectively subjected to modification by hydrosulfuric acid, flotation and sieving to obtain ZnS, PbS and Co3S4Mixing the granules again;
preferably, the galena, blende and skutterudite are newly produced raw ores of the mine.
5. A method for preparing a Fenton reaction catalyst according to claim 4, wherein before the modification with hydrogen sulfuric acid, the mineral is pulverized;
preferably, the hydrosulfuric acid-modified flotation means: adding hydrogen sulfuric acid into the crushed minerals;
preferably, the minerals floated by the modification of the hydrogen sulfuric acid are respectively washed by absolute ethyl alcohol and pure water and then dried for 24 hours at the temperature of 50-80 ℃;
preferably, the dried mineral is sieved sequentially through 5 mesh, 18 mesh, 50 mesh and 140 mesh sieves to obtain the following 3 particle size ranges, respectively: 1mm to 4mm, 0.3 to 1mm and 0.1 to 0.3mm of ore particles;
preferably, the mixing refers to mixing three ore particles belonging to the same grain size range.
6. A fenton reactor comprising a catalyst packing unit located inside the reactor; the catalyst filler unit comprises an upper layer, a middle layer and a lower layer of 3 catalyst particle layers, and the particle size of each layer of catalyst particle is increased from top to bottom in sequence;
the catalyst comprises ZnS, PbS and Co with the mass ratio of 3-5: 1-2: 0.53S4。
7. A Fenton reactor according to claim 6, wherein the particle size of the catalyst particles in the upper catalyst particle layer is 0.1 to 0.3mm, the particle size of the catalyst particles in the middle catalyst particle layer is 0.3 to 1mm, and the particle size of the catalyst particles in the lower catalyst particle layer is 1 to 4 mm;
preferably ZnS, PbS, Co3S4The mass ratio of the components is 3: 1: 0.5;
preferably, the catalyst particles may be placed in a filter bag;
preferably, the filter bag is in a circular ring structure after being filled with catalyst particles;
preferably, the Fenton reactor is of a reaction tank structure with a hollow interior; a fixing component capable of fixing the catalyst particle layer is arranged in the reaction tank;
preferably, the fixing part is a fixing column arranged on the inner wall of the bottom of the reaction tank; the annular filter bag filled with the catalyst particles can be sleeved on the fixed column; the size and the shape of the circular filter bag filled with the catalyst particles are matched with the inner part of the reaction tank;
preferably, a clamping groove is formed in the center of the inner wall of the bottom of the reaction tank; the fixing column can be clamped in the clamping groove;
preferably, 3 circular filter bags filled with catalyst particles are arranged, and correspond to the upper, middle and lower 3 catalyst particle layers respectively;
preferably, the number of the catalyst packing units is 1, 2 or more;
preferably, a feed inlet and a discharge outlet are formed in the wall of the reaction tank, and the top of the reaction tank can be opened and is provided with a top cover capable of being opened and closed;
preferably, the height of the catalyst packing elements is from 5 to 20 cm.
8. A fenton reaction catalyst according to claim 1 or 2, and/or a fenton reaction catalyst obtained by the method according to any one of claims 3 to 5, and/or a fenton reactor according to claim 7 or 8 for use in treating organic contamination.
9. A method for fully treating landfill leachate, which is characterized in that the fenton reaction catalyst according to claim 1 or 2, and/or the fenton reaction catalyst obtained by the preparation method according to any one of claims 3 to 5, and/or the fenton reactor according to claim 7 or 8 is used for treating the landfill leachate.
10. The method of claim 9, wherein the Fenton reaction reagent is FeSO4·7H2O and H2O2；
Preferably, the FeSO4·7H2O is 2-12mmol/L, H2O2Is 100-600 mmol/L;
more preferably, the reaction system has a pH of 3 to 5;
preferably, the addition amount of the catalyst particles in the catalyst packing unit is 6-10 g/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113976145A (en) * | 2021-11-23 | 2022-01-28 | 中国科学院合肥物质科学研究院 | Sulfur-modified iron-cobalt oxide nanosheet Fenton catalyst and preparation method and application method thereof |
| CN114988609A (en) * | 2022-06-15 | 2022-09-02 | 西安瑞美德水业科技有限公司 | Hydroxyl radical initiator and method for treating organic wastewater by using same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559656A (en) * | 2004-02-19 | 2005-01-05 | 上海交通大学 | Preparation method of nucleous-shell type nanometer composite particle of magnetic micro particle and quantum point |
| CN107983272A (en) * | 2016-10-26 | 2018-05-04 | 中国科学院化学研究所 | Sulfide encapsulated particles and preparation method and application |
| CN109317167A (en) * | 2018-10-30 | 2019-02-12 | 东北师范大学 | The nanoparticle and its preparation method and application of metal chalcogenide complex cladding |
| CN109772370A (en) * | 2019-03-01 | 2019-05-21 | 华东理工大学 | A kind of water purification beaded catalyst and its preparation method and application |
-
2020
- 2020-09-15 CN CN202010964857.0A patent/CN111822005B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559656A (en) * | 2004-02-19 | 2005-01-05 | 上海交通大学 | Preparation method of nucleous-shell type nanometer composite particle of magnetic micro particle and quantum point |
| CN107983272A (en) * | 2016-10-26 | 2018-05-04 | 中国科学院化学研究所 | Sulfide encapsulated particles and preparation method and application |
| CN109317167A (en) * | 2018-10-30 | 2019-02-12 | 东北师范大学 | The nanoparticle and its preparation method and application of metal chalcogenide complex cladding |
| CN109772370A (en) * | 2019-03-01 | 2019-05-21 | 华东理工大学 | A kind of water purification beaded catalyst and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113976145A (en) * | 2021-11-23 | 2022-01-28 | 中国科学院合肥物质科学研究院 | Sulfur-modified iron-cobalt oxide nanosheet Fenton catalyst and preparation method and application method thereof |
| CN114988609A (en) * | 2022-06-15 | 2022-09-02 | 西安瑞美德水业科技有限公司 | Hydroxyl radical initiator and method for treating organic wastewater by using same |
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