CN116425347A - Coal chemical wastewater treatment method, device and system and preparation method of supported metal oxide catalyst - Google Patents
Coal chemical wastewater treatment method, device and system and preparation method of supported metal oxide catalyst Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 82
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- 238000002360 preparation method Methods 0.000 title abstract description 4
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000008394 flocculating agent Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010431 corundum Substances 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
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- 238000007598 dipping method Methods 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- AQCHWTWZEMGIFD-UHFFFAOYSA-N metolazone Chemical compound CC1NC2=CC(Cl)=C(S(N)(=O)=O)C=C2C(=O)N1C1=CC=CC=C1C AQCHWTWZEMGIFD-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- B01J23/755—Nickel
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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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
- C02F1/52—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
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical 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
- C02F1/72—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The application discloses a coal chemical wastewater treatment method, a device and a system and a preparation method of a supported metal oxide catalyst. Adding flocculant and magnetic powder into coal chemical wastewater to be treated to form suspended pollutants into sediment; the flocculant comprises polyacrylamide or polyaluminum chloride or a combination thereof; removing sediment to obtain wastewater from which suspended pollutants are removed; and carrying out countercurrent contact on the wastewater from which the suspended pollutants are removed and ozone in the presence of a catalyst to carry out catalytic reaction, so as to obtain the treated water from which the impurities are removed. The coal chemical wastewater treatment method combines a magnetic coagulation sedimentation process of adding flocculant and magnetic powder sedimentation with an ozone catalytic oxidation process, so that the density of the suspended pollutants in the coal chemical wastewater and the floccules generated by flocculating the flocculant and the magnetic powder is higher and stronger, and the suspended pollutants are settled at a high speed; the wastewater is fully contacted with ozone in countercurrent and is further catalyzed and oxidized under the action of a catalyst, so that organic matters in the wastewater are removed, and the impurity-removed treated water is obtained.
Description
Technical Field
The application belongs to the technical field of coal chemical industry, and particularly relates to a coal chemical industry wastewater treatment method, a device and a system and a preparation method of a supported metal oxide catalyst.
Background
The common treatment method for the coal chemical wastewater mainly comprises three parts of pretreatment, biochemical treatment and advanced treatment. Wherein, the pretreatment mainly comprises degreasing, deacidification, deamination and extraction dephenolization; the biochemical treatment mainly comprises an air floatation tank, a hydrolytic acidification tank and a biochemical reaction tank; the advanced treatment mainly comprises coagulating sedimentation, membrane filtration or chemical oxidation. When the process conditions are changed, the wastewater quality fluctuates greatly, and the suspended matter content in the effluent water quality after the traditional coagulating sedimentation treatment is still higher, so that the subsequent advanced treatment is not facilitated; and the wastewater discharge standard is met, but the requirement of the quality of the circulating cooling water is difficult to be met.
The treatment method for advanced treatment after coagulating sedimentation comprises the following steps: the membrane filtration method has good separation effect, but when the water quality fluctuates greatly, the membrane is easy to be blocked. The Fenton oxidation method has the advantages of larger dosage, high cost and easy secondary pollution. The ultraviolet light absorption range of the photocatalytic oxidation method is narrow, the light energy utilization rate is low, and the catalytic effect is greatly influenced by the transmittance and the catalyst. Therefore, is not suitable for treating wastewater with high suspended matter content and high chromaticity. The main dilemma faced by the ozone oxidation technology is that the oxidation effect is limited; in addition, the low concentration and solubility of ozone and the poor mass transfer effect of the reactor result in generally low ozone utilization rate (< 40%), and most ozone molecules are discharged or decomposed in the form of tail gas.
Disclosure of Invention
The embodiment of the application provides a method for treating wastewater in coal chemical industry, which enables the quality of the effluent to meet the requirement of wastewater circulating cooling water through magnetic mixing precipitation and ozone catalytic oxidation.
In a first aspect, the present application provides a method for treating wastewater in coal chemical industry, the method comprising:
adding flocculant and magnetic powder into the coal chemical wastewater to be treated, so that the flocculant and the magnetic powder are combined with suspended pollutants in the coal chemical wastewater to be treated to form a sediment; wherein the flocculant comprises polyacrylamide or polyaluminum chloride or a combination thereof;
removing sediment to obtain wastewater from which suspended pollutants are removed;
and carrying out countercurrent contact on the wastewater from which the suspended pollutants are removed and ozone in the presence of a catalyst to carry out catalytic reaction, so as to obtain the treated water from which the impurities are removed.
In one embodiment of the present application, adding flocculant and magnetic powder to the coal chemical industry wastewater to be treated includes adding polyaluminum chloride as flocculant in an amount of 60mg to 110mg per 1 liter of coal chemical industry wastewater or polyacrylamide as flocculant in an amount of 40mg to 60mg per 1 liter of coal chemical industry wastewater, and adding magnetic powder in an amount of 0.5mg to 1.2mg per 1 liter of coal chemical industry wastewater.
In one embodiment of the present application, the step of removing sediment further comprises filtering the wastewater from which suspended contaminants were removed by filtration.
In one embodiment of the present application, the step of removing the sediment further comprises recovering magnetic powder in the sediment.
In one embodiment of the present application, the step of countercurrently contacting the wastewater from which the suspended contaminants are removed with ozone in the presence of a catalyst to effect a catalytic reaction, and obtaining treated water from which the contaminants are removed, comprises flowing the wastewater from which the suspended contaminants are removed in a first direction and flowing ozone in a direction opposite to the first direction, such that the wastewater from which the suspended sludge contaminants are removed is countercurrently contacted with ozone.
In an embodiment of the present application, the wastewater from which the suspended contaminants are removed is counter-currently contacted with ozone in the presence of a catalyst to perform a catalytic reaction, and the first direction in the step of obtaining the treated water from which the contaminants are removed at least includes a vertical direction or a planar direction, so that the wastewater from which the suspended contaminants are removed is fully contacted with ozone to react, and the ozone utilization rate is improved.
In one embodiment of the present application, the step of countercurrent contacting the wastewater from which the suspended contaminants are removed with ozone in the presence of a catalyst to perform a catalytic reaction, and obtaining the treated water from which the contaminants are removed comprises flowing the wastewater from which the suspended contaminants are removed from top to bottom in a vertical direction, and countercurrent contacting the ozone with the wastewater from which the suspended contaminants are removed from bottom to top.
In one embodiment of the present application, the step of countercurrently contacting the wastewater from which the suspended contaminants are removed with ozone in the presence of a catalyst to effect a catalytic reaction to obtain treated water from which the contaminants are removed comprises catalytically reacting the wastewater from which the suspended contaminants are removed with ozone using a supported metal oxide catalyst.
In one embodiment of the present application, the catalyst is an oxide of at least one metal of manganese, cobalt, nickel supported on activated carbon foam.
In a second aspect, embodiments of the present application also provide a method for preparing a supported metal oxide catalyst, prepared according to the following method:
the active foam carbon is prepared by using long flame coal, pulverized coal, asphalt slag or a combination thereof as raw materials and performing foaming, carbonization, activation and molding;
immersing, drying and roasting the activated foam carbon in nitrate solution to prepare the carrier type bi-component metal oxide ozone catalyst, wherein the nitrate solution is selected from at least two nitrate solutions of manganese nitrate, cobalt nitrate and nickel nitrate.
In one embodiment of the present application, the step of preparing activated carbon foam from raw materials selected from the group consisting of long flame coal, pulverized coal, asphalt slag, and combinations thereof by foaming, carbonizing, activating, and molding comprises:
weighing raw materials and water according to a mass ratio of 8-15:1, and fully stirring to obtain mixed slurry;
placing the mixed slurry on a coal bed at a concentration of 1000N/m 2 ～1400N/m 2 Foaming is carried out to obtain a block foam carbon raw material;
carbonizing the block foam carbon raw material at 550-900 ℃ in an inert atmosphere for 45-75 minutes, and cooling to room temperature to obtain carbonized foam carbon;
placing carbonized foam carbon into a rotary tube furnace, and heating the furnace temperature of the rotary tube furnace to 700-950 ℃ at a heating rate of 6-13 ℃ per minute under an inert atmosphere of 400-600 mL/min;
introducing distilled water with the flow rate of 0.02-0.05 mL/min/g into a rotary tube furnace, and activating for 60-180 minutes to obtain activated foam carbon.
In the examples of the present application, the inert atmosphere is N 2 。
In one embodiment of the present application, immersing the activated carbon foam in the nitrate solution comprises mixing the activated carbon foam and the metal nitrate solution in a mass ratio of 1:15-20 under stirring, and immersing for 16-24 hours to obtain the catalyst slurry. The metal nitrate solution is a saturated nitrate solution.
In one embodiment of the present application, the rotational speed of the rotary tube furnace is 10r/min to 20r/min during the process of introducing distilled water into the rotary tube furnace.
In one embodiment of the present application, the steps of drying and calcining the catalyst slurry to produce the supported metal oxide catalyst include:
and removing liquid in the catalyst slurry, and drying and roasting to obtain the supported metal oxide catalyst.
In one embodiment of the present application, the supported metal oxide catalyst may be placed in a mold and molded on a pressure molding machine at a pressure of 5MPa to 10MPa to obtain a supported metal oxide catalyst having a desired shape.
In a third aspect, the present application provides a coal chemical industry wastewater treatment apparatus comprising:
the wastewater sedimentation device comprises a coagulation tank for sedimentation;
the countercurrent catalysis device comprises an ozone oxidation column and an oxygen supply mechanism, wherein the ozone oxidation column is connected with the coagulation tank so that the coagulation tank supplies wastewater to the ozone oxidation column; the oxygen supply mechanism is connected with the ozone oxidation column to supply oxygen to the ozone oxidation column, and is arranged at the far end of the wastewater inlet end in the ozone oxidation column.
In an embodiment of the application, the wastewater sedimentation device further comprises a filter connected with the coagulation tank, the filter is provided with a filter feeding end and a filter discharging end, the filter feeding end is connected with the coagulation tank, and the filter discharging end is connected with the wastewater inlet end of the ozone oxidation column.
In one embodiment of the present application, the oxygen supply mechanism comprises an ozone generator and a compressor connected in sequence, the compressor being connected to the ozone oxidation column so as to compress ozone generated by the ozone generator by the compressor and deliver the ozone to the ozone oxidation column.
In an embodiment of the present application, the ozone oxidation column at least comprises a first ozone oxidation column and a second ozone oxidation column connected in series, wherein the first ozone oxidation column arranged in advance is provided with an ozone recycling pipeline connected to a drainage end of the second ozone oxidation column arranged in the rear at the wastewater inlet end.
In an embodiment of the application, the inside of the ozone oxidation column is sequentially provided with liquid distributor and gas distributors at intervals along the flowing direction of the wastewater, and a catalyst is arranged between the liquid distributor and the gas distributors.
In an embodiment of the present application, the coal chemical industry wastewater treatment apparatus further includes:
a water receiving device connected with the water discharge end of the ozone oxidation column to receive the treated water;
and the tail gas decomposer is connected with the wastewater inlet end of the ozone oxidation column and is used for decomposing unreacted ozone.
In a third aspect, embodiments of the present application further provide a coal chemical industry wastewater treatment system, including the above-described coal chemical industry wastewater treatment device.
According to the coal chemical wastewater treatment method, the magnetic coagulation sedimentation technology of adding the flocculating agent and settling the magnetic powder is combined with the ozone catalytic oxidation technology, so that suspended pollutants in the coal chemical wastewater, the flocculating agent and the magnetic powder are flocculated and combined into a whole, the coagulation and flocculation effects are enhanced, the generated flocculation density is larger and stronger, the purpose of settling the suspended pollutants at a high speed is achieved, and the settled magnetic powder can be sucked out by using a magnet for recycling; the wastewater after magnetic coagulation precipitation is fully contacted with ozone in countercurrent to be further catalyzed and oxidized under the action of a catalyst, so that organic matters in the wastewater are removed, and treated water with impurities removed is obtained, namely clean water with water quality capable of being used for cooling water is obtained.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments of the present application will be briefly described, and it is possible for a person skilled in the art to obtain other drawings according to these drawings without inventive effort.
FIG. 1 is a schematic flow chart of a method for treating wastewater in coal chemical industry according to one embodiment of the present application;
fig. 2 is a schematic structural diagram of a coal chemical wastewater treatment apparatus according to another embodiment of the present application, and solid arrows in fig. 2 indicate a flow direction of liquid in an ozone oxidation column, and dashed arrows indicate a flow direction of ozone in the ozone oxidation column.
Reference numerals illustrate:
1. a wastewater sedimentation device; 100. a waste water tank; 101. a coagulation tank; 102. a filter; 102a, a filter feed end; 102b, a discharge end of the filter;
2. a reverse flow catalytic device; 200. an ozone oxidation column; 2001. a first ozone oxidation column; 2002. a second ozone oxidation column; 200a, a waste water inlet end; 200b, a drainage end; 201. an oxygen supply mechanism; 2011. an ozone generator; 2012. a compressor; 203. ozone recycling pipelines; 204. a liquid distributor; 205. a gas distributor; 206. a catalyst;
3. a filtered water tank;
4. a water receiving device; 5. a tail gas decomposer.
Detailed Description
Features and exemplary embodiments of various aspects of the present application are described in detail below to make the objects, technical solutions and advantages of the present application more apparent, and to further describe the present application in conjunction with the accompanying drawings and the detailed embodiments. It should be understood that the specific embodiments described herein are intended to be illustrative of the application and are not intended to be limiting. It will be apparent to one skilled in the art that the present application may be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the present application by showing examples of the present application.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other like elements in a process, method, article or apparatus that comprises the element.
As described in the background art, the content of suspended matters in the effluent water after the traditional coagulating sedimentation treatment is still higher, wherein the main components are biological floc fragments and free bacteria flowing out after the biochemical treatment, which is not beneficial to the subsequent advanced treatment and is difficult to meet the requirement of the quality of the circulating cooling water.
In order to solve the problems in the prior art, the embodiment of the application provides a coal chemical wastewater treatment method. The following first describes the method for treating wastewater in coal chemical industry provided in the examples of the present application.
Fig. 1 shows a schematic flow chart of a coal chemical wastewater treatment method according to an embodiment of the present application. As shown in fig. 1, the coal chemical wastewater treatment method comprises:
s1, adding flocculant and magnetic powder into coal chemical wastewater to be treated, so that the flocculant and the magnetic powder are combined with suspended pollutants in the coal chemical wastewater to be treated to form a sediment; wherein the flocculant comprises polyacrylamide or polyaluminum chloride or a combination thereof;
s2, removing sediments to obtain wastewater from which suspended pollutants are removed;
s3, carrying out countercurrent contact on the wastewater from which the suspended pollutants are removed and ozone in the presence of a catalyst to carry out catalytic reaction, so as to obtain the treated water from which the impurities are removed.
According to the coal chemical wastewater treatment method, the magnetic coagulation sedimentation technology of adding the flocculating agent and the magnetic powder sedimentation is combined with the ozone catalytic oxidation technology to the coal chemical wastewater to be treated, so that suspended pollutants in the coal chemical wastewater and the flocculating agent and the magnetic powder are flocculated and combined into a whole, the effects of coagulation and flocculation are enhanced, the generated floc density is higher and stronger, the purpose of settling the suspended pollutants at a high speed is achieved, and the settled magnetic powder can be sucked out by using a magnet for recycling; the wastewater after magnetic coagulation precipitation is fully contacted with ozone in countercurrent to be further catalyzed and oxidized under the action of a catalyst, so that organic matters in the wastewater are removed, and treated water with impurities removed is obtained, namely clean water with water quality capable of being used for cooling water is obtained.
In one embodiment of the present application, adding flocculant and magnetic powder to the coal chemical industry wastewater to be treated includes adding polyaluminum chloride as flocculant in an amount of 60mg to 110mg per 1 liter of coal chemical industry wastewater or polyacrylamide as flocculant in an amount of 40mg to 60mg per 1 liter of coal chemical industry wastewater, and adding magnetic powder in an amount of 0.5mg to 1.2mg per 1 liter of coal chemical industry wastewater.
Exemplary, the addition amounts of polyaluminum chloride are 60mg, 65mg, 68mg, 70mg, 71mg, 75mg, 76mg, 78mg, 80mg, 83mg, 86mg, 89mg, 91mg, 94mg, 97mg, 98mg, 102mg, 106mg, 108mg per liter of coal chemical industry wastewater to be treated. The addition amount of the polyacrylamide is 41mg, 43mg, 46mg, 47mg, 48mg, 51mg, 52mg, 54mg, 56mg, 57mg and 59mg per liter of coal chemical wastewater to be treated.
In one embodiment of the present application, the step of removing sediment further comprises filtering the wastewater from which the suspended contaminants are removed by filtration to further remove the suspended contaminants that may be contained therein, resulting in treated water from which the suspended contaminants are filtered.
In an embodiment of the present application, the step of removing the sediment further includes recovering the magnetic powder in the sediment, so as to reuse the magnetic powder, thereby saving cost.
In one embodiment of the present application, the step of countercurrently contacting the wastewater from which the suspended contaminants are removed with ozone in the presence of a catalyst to effect a catalytic reaction, and obtaining treated water from which the contaminants are removed, comprises flowing the wastewater from which the suspended contaminants are removed in a first direction, and flowing ozone in a direction opposite to the first direction, such that the wastewater from which the suspended contaminants are removed is countercurrently contacted with ozone, and effecting a sufficient reaction under the influence of the catalyst.
In an embodiment of the application, the wastewater from which the suspended pollutants are removed is contacted with ozone in countercurrent under the condition of existence of a catalyst for catalytic reaction, and the first direction in the step of obtaining the treated water from which the impurities are removed at least comprises a vertical direction or a plane direction, so that the wastewater from which the suspended pollutants are removed is fully contacted with the ozone for reaction, organic matters contained in the wastewater are further removed, and the utilization rate of the ozone is improved.
In one embodiment of the present application, as shown in fig. 2, the step of counter-currently contacting the wastewater from which the suspended contaminants are removed with ozone in the presence of a catalyst to perform a catalytic reaction, and obtaining the treated water from which the impurities are removed, comprises flowing the wastewater from which the suspended contaminants are removed from top to bottom in a vertical direction, and counter-currently contacting the ozone with the wastewater from which the suspended contaminants are removed from bottom to top.
In one embodiment of the present application, the step of countercurrently contacting the wastewater from which the suspended contaminants are removed with ozone in the presence of a catalyst to effect a catalytic reaction to obtain treated water from which the contaminants are removed comprises catalytically reacting the wastewater from which the suspended contaminants are removed with ozone using a supported metal oxide catalyst.
In one embodiment of the present application, the catalyst is an oxide of at least one metal of manganese, cobalt, nickel supported on activated carbon foam.
The metal oxide catalyst loaded by the activated foam carbon has the adsorption effect on organic matters and the catalytic ozone oxidation effect, and can be used for treating the organic matters in the coal chemical wastewater more cleanly.
In a second aspect, embodiments of the present application also provide a method for preparing a supported metal oxide catalyst, prepared according to the following method:
using long flame coal, pulverized coal, asphalt or asphalt slag or a combination thereof as raw materials, and preparing the active foam carbon through foaming, carbonization, activation and molding;
immersing, drying and roasting the activated foam carbon in nitrate solution to prepare the carrier type bi-component metal oxide ozone catalyst, wherein the nitrate solution is selected from at least two nitrate solutions of manganese nitrate, cobalt nitrate and nickel nitrate.
The supported metal oxide catalyst provided by the embodiment of the application takes long flame coal, pulverized coal, asphalt slag or a combination thereof as raw materials to prepare the supported metal oxide catalyst, so that low-value resources are utilized with high value, and waste materials such as the pulverized coal, the asphalt slag and the like are further utilized.
In one embodiment of the present application, the steps of foaming, carbonizing, activating and forming the long flame coal, pulverized coal, asphalt or asphalt slag or a combination thereof to obtain the activated foam carbon comprise:
weighing raw materials and water according to a mass ratio of 8-15:1, and fully stirring to obtain mixed slurry;
placing the mixed slurry on a coal bed at a concentration of 1000N/m 2 ～1400N/m 2 Foaming is carried out to obtain a block foam carbon raw material;
carbonizing the block foam carbon raw material at 550-900 ℃ in an inert atmosphere for 45-75 minutes, and cooling to room temperature to obtain carbonized foam carbon;
placing carbonized foam carbon into a rotary tube furnace, and heating the furnace temperature of the rotary tube furnace to 700-950 ℃ at a heating rate of 6-13 ℃ per minute under an inert atmosphere of 400-600 mL/min;
introducing distilled water with the flow rate of 0.02-0.05 mL/min/g into a rotary tube furnace, and activating for 60-180 minutes to obtain activated foam carbon.
In the examples herein, the purpose of carbonization is to remove volatiles as well as moisture from the raw foam char. The unit of distilled water is that the inflow rate of distilled water corresponding to each gram of foam carbon is 0.02 mL/min-0.05 mL/min.
In one embodiment of the present application, the mixed slurry is placed on a coal bed at 1000N/m 2 ～1400N/m 2 The step of foaming to obtain a block of foamed carbon raw material comprises the following steps:
weighing raw materials selected from long flame coal, pulverized coal, asphalt slag or a combination thereof and distilled water according to the mass ratio of 8-15:1, fully stirring in a beaker, placing the mixture on a corundum crucible after uniform stirring, and giving 1000N/m 2 ～1400N/m 2 As foaming pressure;
then the corundum crucible is put into a muffle furnace for foaming, so that the foam has a cell structure, and a block-shaped foam carbon raw material is obtained.
In the examples of the present application, the inert atmosphere is N 2 。
In one embodiment of the present application, immersing the activated carbon foam in the nitrate solution comprises mixing the activated carbon foam and the metal nitrate solution in a mass ratio of 1:15-20 under stirring, and immersing for 16-24 hours to obtain the catalyst slurry. Wherein the metal nitrate solution is a saturated metal nitrate solution.
In one embodiment of the present application, the rotational speed of the rotary tube furnace is 10r/min to 20r/min during the process of introducing distilled water into the rotary tube furnace.
In one embodiment of the present application, the steps of drying and calcining the catalyst slurry to produce the supported metal oxide catalyst include:
and removing liquid in the catalyst slurry, and drying and roasting to obtain the supported metal oxide catalyst.
In one embodiment of the present application, the supported metal oxide catalyst may be placed in a metal mold and molded on a pressure molding machine at a pressure of 5MPa to 10MPa to obtain a supported metal oxide catalyst having a desired shape, which means that the shape of the catalyst is any one of a block, a sheet, a sphere, and a pellet.
Fig. 2 shows a schematic structural diagram of a coal chemical wastewater treatment device provided in an embodiment of the present application.
In a third aspect, the present application provides a coal chemical industry wastewater treatment apparatus comprising:
a wastewater sedimentation device 1 including a coagulation tank 101 for performing sedimentation;
a countercurrent catalytic apparatus 2 including an ozone oxidation column 200 and an oxygen supply mechanism 201, the ozone oxidation column 200 being connected to the coagulation tank 101 so that the coagulation tank 101 supplies wastewater to the ozone oxidation column 200; the oxygen supply mechanism 201 is connected with the ozone oxidation column 200 to supply oxygen to the ozone oxidation column 200, and the oxygen supply mechanism 201 is arranged at the far end of the wastewater inlet end 200a in the ozone oxidation column 200.
The utility model provides a coal industry effluent treatment plant utilizes wastewater settling device to subside the coal industry effluent after the biochemical treatment earlier, gets rid of the suspended pollutant in the coal industry effluent of waiting to handle, obtains getting rid of the waste water of suspended pollutant, then utilizes countercurrent catalytic unit to carry out ozone catalytic oxidation to the waste water of getting rid of suspended pollutant and handles, further gets rid of the organic matter wherein, obtains the circulating cooling water that accords with the requirement.
As shown in fig. 2, the wastewater sedimentation device 1 further comprises a filter 102 connected to the coagulation tank 101, the filter 102 is provided with a filter feed end 102a and a filter discharge end 102b, the filter feed end 102a is connected to the coagulation tank 101, and the filter discharge end 102b is connected to the wastewater inlet end 200a of the ozone oxidation column 200. To further remove suspended pollutants possibly contained in the wastewater through the filtration treatment of the filter 102 to obtain the treated water for filtering the suspended pollutants
As shown in fig. 2, the oxygen supply mechanism 201 includes an ozone generator 2011 and a compressor 2012 connected in sequence, and the compressor 2012 is connected to the ozone oxidation column 200 so as to compress ozone generated by the ozone generator 2011 by the compressor 2012 and deliver the ozone to the ozone oxidation column 200.
In the embodiment of the present application, the ozone oxidation column 200 includes at least a first ozone oxidation column 2001 and a second ozone oxidation column 2002 connected in series as shown in fig. 2, and the first ozone oxidation column 2001 disposed in advance is provided with an ozone recycling line 203 connected to a drain end 200b of the second ozone oxidation column 2002 disposed in the rear at a wastewater inlet end 200 a.
In an embodiment of the present application, the liquid distributor 204 and the gas distributor 205 are sequentially arranged in the ozone oxidation column 200 at intervals along the flowing direction of the wastewater, and a catalyst 206 is arranged between the liquid distributor 204 and the gas distributor 205. As shown in fig. 2, the first ozone oxidation column 2001 and the second ozone oxidation column 2002 are disposed in the middle of the liquid distributor 204 and the gas distributor 205, and a black three-stage catalyst 206 is disposed in the ozone oxidation column 200 by means of a carrier or a bracket to catalyze the oxidation reaction of ozone and wastewater from which suspended pollutants are removed, and further remove organic matters in the wastewater, so that the standard of the wastewater in the coal chemical industry reaches the use standard of circulating cooling water.
In an embodiment of the present application, the coal chemical industry wastewater treatment apparatus further includes:
a water receiving means 4 connected to the water discharge end 200b of the ozone oxidation column 200 to receive the treated water;
the tail gas decomposer 5 is connected with the wastewater inlet end 200a of the ozone oxidation column 200 and is used for decomposing unreacted ozone.
In a third aspect, embodiments of the present application further provide a coal chemical wastewater treatment system, including the above-mentioned coal chemical wastewater treatment device, the coal chemical wastewater treatment system can further process the coal chemical wastewater after biochemical treatment, and the circulating cooling water meeting the requirements is obtained.
Examples
The technical scheme and advantages of the present application are further described below by means of specific examples.
The water discharged from the biochemical reaction tank, namely, the coal chemical wastewater to be treated which is subjected to biochemical treatment enters the wastewater tank 100, so that the coal chemical wastewater to be treated is provided for the coal chemical wastewater treatment device through the wastewater tank 100, and the coal chemical wastewater treatment device and the coal chemical wastewater treatment method of the embodiment of the application are used for treatment.
Wherein, the selection and the dosage of the flocculant are shown in Table 1, and the catalyst is prepared by the following method:
fully stirring a long flame coal raw material and distilled water in a mass ratio of 15:1 in a beaker, uniformly stirring, placing the mixture on a corundum crucible, and giving 1200N/m 2 As the foaming pressure;
the block foam carbon raw material is processed at 800 ℃ and N 2 Carbonizing in an inert atmosphere for 60 minutes, and cooling to room temperature to obtain carbonized foam carbon;
the carbonized foam carbon is placed in a rotary tube furnace and is N at 500mL/min 2 Heating the furnace temperature of the rotary tube furnace to 900 ℃ at a heating rate of 10 ℃/min under an inert atmosphere;
introducing distilled water with the flow rate of 0.03mL/min/g into a rotary tube furnace, and activating for 75 minutes to obtain activated foam carbon;
dipping activated carbon foam in a nitrate solution, namely stirring and mixing the activated carbon foam and a saturated metal manganese nitrate solution in a mass ratio of 1:20, and dipping for 24 hours to obtain catalyst slurry;
removing liquid from the catalyst slurry, drying and roasting to obtain the supported manganese oxide catalyst;
the catalyst was pressed into a sheet shape having a side length x thickness=5 mm x 2mm using a metal mold at a pressure of 10MPa and placed in a first ozone oxidation column and a second ozone oxidation column, each of which was provided with three layers of the catalyst of the present example, 12 sheets each.
The water quality of the wastewater treated by the coal chemical wastewater treatment method according to the embodiment of the application is detected according to the test standard GB/T19923-2005 of cooling water, and the test results are shown in tables 1 and 2:
TABLE 1 comparison of precipitation time and dosage for the treatment of the present application and the prior treatment
It can be seen from table 1 that after the treatment method of the coal chemical wastewater of the application is used, the sedimentation time of the biologically treated coal chemical wastewater is shortened to 4.16% -16.67% of the original sedimentation time, and the addition amount of the agent is also reduced to 16.67% -55.00% of the original sedimentation time.
TABLE 2 Performance test results of treated Water
Note that: the "-" in table 2 indicates that the item of data was not detected.
As can be seen from Table 2, the wastewater from the biochemical reaction tank is treated by the device and the method for treating wastewater in coal chemical industry, so that the concentration of suspended pollutants in the wastewater is greatly reduced.
The coal chemical wastewater treatment device and the method take waste as an innovation idea, utilize long flame coal, pulverized coal, asphalt or asphalt slag as raw materials in a recycling way, and at least one of manganese nitrate, cobalt nitrate and nickel nitrate as impregnating solution to prepare the supported bi-component metal ozone catalyst, so that the supported bi-component metal ozone catalyst is applied to wastewater treatment, has an adsorption effect, also has an ozone oxidation catalytic effect, realizes high-value utilization of low-value resources, and overcomes the defect that the wastewater treatment process in the prior art can only reach wastewater discharge standards and cannot be recycled, thereby realizing the recycling of water resources in the coal fractional classification production process.
In the foregoing, only the specific embodiments of the present application are described, and it will be clearly understood by those skilled in the art that, for convenience and brevity of description, the specific working process described above may refer to the corresponding process in the foregoing method embodiment, which is not repeated herein. It should be understood that the scope of the present application is not limited thereto, and any person skilled in the art can easily conceive various equivalent modifications or substitutions within the technical scope of the present application, which are intended to be included in the scope of the present application.
Claims (19)
1. A method for treating wastewater in coal chemical industry, which is characterized by comprising the following steps:
adding a flocculating agent and magnetic powder into the coal chemical wastewater to be treated, so that the flocculating agent and the magnetic powder are combined with suspended pollutants in the coal chemical wastewater to be treated to form a sediment; wherein the flocculant comprises polyacrylamide or polyaluminum chloride or a combination thereof;
removing the sediment to obtain wastewater from which suspended pollutants are removed;
and carrying out countercurrent contact on the wastewater from which the suspended pollutants are removed and ozone in the presence of a catalyst to carry out catalytic reaction, so as to obtain the treated water from which the impurities are removed.
2. The method for treating coal chemical industry wastewater according to claim 1, wherein the adding of the flocculant and the magnetic powder to the coal chemical industry wastewater to be treated comprises adding polyaluminium chloride as the flocculant in an amount of 60mg to 110mg/1 liter of the coal chemical industry wastewater to be treated or adding polyacrylamide as the flocculant in an amount of 40mg to 60mg/1 liter of the coal chemical industry wastewater to be treated, and adding the magnetic powder in an amount of 0.5mg to 1.2mg/1 liter of the coal chemical industry wastewater to be treated.
3. The method of treating coal chemical industry wastewater according to claim 1, wherein the step of removing the sediment further comprises filtering wastewater from which suspended contaminants are removed by filtration.
4. The method for treating wastewater in coal chemical industry according to claim 1, wherein the magnetic powder has an average particle diameter D 50 Fe of 10-20 microns 3 O 4 。
5. The method of treating wastewater from coal chemical industry according to claim 1, wherein the step of countercurrent contacting the wastewater from which suspended contaminants are removed with ozone in the presence of a catalyst to perform a catalytic reaction, and obtaining treated water from which impurities are removed comprises flowing the wastewater from which suspended contaminants are removed in a first direction, and flowing ozone in a direction opposite to the first direction, so that the wastewater from which suspended contaminants are removed and ozone are countercurrent contacted.
6. The method for treating wastewater in coal chemical industry according to claim 5, wherein the first direction in the step of obtaining the treated water from which impurities are removed includes at least a vertical direction or a planar direction by carrying out a catalytic reaction by countercurrent contact of wastewater from which suspended contaminants are removed with ozone in the presence of a catalyst, so that the wastewater from which suspended contaminants are removed is sufficiently contacted with ozone.
7. The method for treating wastewater in coal chemical industry according to claim 1, wherein the step of carrying out the catalytic reaction of wastewater from which suspended contaminants are removed with ozone in countercurrent contact in the presence of a catalyst to obtain treated water from which impurities are removed comprises the step of carrying out the catalytic reaction of wastewater from which suspended contaminants are removed with ozone using a supported metal oxide catalyst.
8. The method for treating wastewater in coal chemical industry according to any one of claims 1 to 7, wherein the catalyst is an oxide of at least one metal of manganese, cobalt and nickel supported on activated carbon foam.
9. A method for preparing a supported metal oxide catalyst, which is characterized by comprising the following steps:
the active foam carbon is prepared by using long flame coal, pulverized coal, asphalt slag or a combination thereof as raw materials and performing foaming, carbonization, activation and molding;
dipping activated foam carbon in nitrate solution to obtain catalyst slurry;
and drying and roasting the catalyst slurry to obtain the supported metal oxide catalyst, wherein the nitrate solution is selected from at least one metal nitrate solution of manganese nitrate, cobalt nitrate and nickel nitrate.
10. The method for preparing the supported metal oxide catalyst according to claim 9, wherein the step of preparing the activated carbon foam by foaming, carbonizing, activating and molding the raw material selected from the group consisting of long flame coal, pulverized coal, asphalt slag and combinations thereof comprises the steps of:
weighing raw materials and water according to a mass ratio of 8-15:1, and fully and uniformly stirring to obtain mixed slurry;
placing the mixed slurry on a corundum crucible at a concentration of 1000N/m 2 ～1400N/m 2 Foaming is carried out to obtain a block foam carbon raw material;
carbonizing the block foam carbon raw material at 550-900 ℃ in an inert atmosphere for 45-75 minutes, and cooling to room temperature to obtain carbonized foam carbon;
placing the carbonized foam carbon into a rotary tube furnace, and heating the furnace temperature of the rotary tube furnace to 700-950 ℃ at a heating rate of 6-13 ℃ per minute under an inert atmosphere with a flow rate of 400-600 mL/min;
introducing distilled water with the flow rate of 0.02-0.05 mL/min/g into the rotary tube furnace, and activating for 60-180 minutes to obtain activated foam carbon.
11. The method for preparing a supported metal oxide catalyst according to claim 9 or 10, wherein the immersing the activated carbon foam in the nitrate solution comprises stirring and mixing the activated carbon foam and the metal nitrate solution in a mass ratio of 1:15-20, and immersing for 16-24 hours to obtain a catalyst slurry.
12. The method for preparing a supported metal oxide catalyst according to claim 9 or 10, wherein the step of drying and calcining the catalyst slurry to prepare the supported metal oxide catalyst comprises the steps of:
and removing liquid in the catalyst slurry, drying and roasting to obtain the supported metal oxide catalyst.
13. A coal chemical industry wastewater treatment device, characterized in that the device comprises:
a wastewater sedimentation device (1) comprising a coagulation tank (101) for sedimentation of wastewater;
a countercurrent catalytic apparatus (2) comprising an ozone oxidation column (200) and an oxygen supply mechanism (201), the ozone oxidation column (200) being connected to the coagulation tank (101) so that the coagulation tank (101) supplies wastewater to the ozone oxidation column (200); the oxygen supply mechanism (201) is connected with the ozone oxidation column (200) to supply oxygen to the ozone oxidation column (200), and the oxygen supply mechanism (201) is arranged at the far end of a wastewater inlet end (200 a) in the ozone oxidation column (200).
14. The coal chemical industry wastewater treatment device according to claim 13, characterized in that the wastewater sedimentation device (1) further comprises a filter (102) connected to the coagulation tank (101), the filter (102 a) is provided with a filter feed end (102 a) and a filter discharge end (102 b), the filter feed end (102 a) is connected to the coagulation tank (101), and the filter discharge end (102 b) is connected to the wastewater inlet end (200 a).
15. The coal chemical wastewater treatment apparatus according to claim 13, wherein the oxygen supply mechanism (201) comprises an ozone generator (2011) and a compressor (2012) connected in sequence, the compressor (2012) being connected to the ozone oxidation column (200).
16. The coal chemical wastewater treatment apparatus according to claim 13, wherein the ozone oxidation column (200) comprises at least a first ozone oxidation column (2001) and a second ozone oxidation column (2002) connected in series, the first ozone oxidation column (2001) provided in advance being provided with an ozone recycling pipe (203) connected to a drain end (200 b) of the second ozone oxidation column (2002) provided in the subsequent stage at the wastewater inlet end (200 a).
17. The coal chemical industry wastewater treatment device according to any one of claims 13 to 16, characterized in that a liquid distributor (204) and a gas distributor (205) are sequentially arranged in the ozone oxidation column (200) at intervals along the wastewater flow direction, and a catalyst is arranged between the liquid distributor (204) and the gas distributor (205).
18. The coal chemical industry wastewater treatment apparatus according to any one of claims 13 to 16, further comprising:
a water receiving device (4) connected with the water discharge end (200 b) of the ozone oxidation column (200) to receive the treated water;
and the tail gas decomposer (5) is connected with the wastewater inlet end (200 a) of the ozone oxidation column (200) and is used for decomposing unreacted ozone.
19. A coal chemical industry wastewater treatment system comprising the coal chemical industry wastewater treatment apparatus of any one of claims 13-18.
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