CN117383717A - Method for removing phenol and aniline in coking nanofiltration concentrated water - Google Patents
Method for removing phenol and aniline in coking nanofiltration concentrated water Download PDFInfo
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- CN117383717A CN117383717A CN202210760096.6A CN202210760096A CN117383717A CN 117383717 A CN117383717 A CN 117383717A CN 202210760096 A CN202210760096 A CN 202210760096A CN 117383717 A CN117383717 A CN 117383717A
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- concentrated water
- nanofiltration concentrated
- aniline
- coking
- coking nanofiltration
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 114
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 96
- 238000004939 coking Methods 0.000 title claims abstract description 88
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 30
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000004744 fabric Substances 0.000 claims abstract description 32
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 27
- 230000003197 catalytic effect Effects 0.000 claims description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 10
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 10
- 230000014759 maintenance of location Effects 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000005539 carbonized material Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 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
- 238000012216 screening Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 description 20
- 239000010865 sewage Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a method for removing phenol and aniline in coking nanofiltration concentrated water, which comprises the following steps: (1) The coking nanofiltration concentrated water enters a cloth bag filter, the filtering precision of the cloth bag filter is 11-15 mu m, (2) after flowing out of the cloth bag filter, the coking nanofiltration concentrated water enters an ozone catalytic reaction tower, and the ozone catalytic reaction tower is internally provided withHas modified biochar catalyst with specific surface area of 678-735 m 2 Per gram, pore volume of 0.39-0.42 cm 3 /g; (3) After ozone catalytic reaction, the coking nanofiltration concentrated water is discharged or discharged into a zero-discharge evaporation system. The process for removing phenol and aniline in the coking nanofiltration concentrated water has low production and operation cost, adopts the biochar technology, reduces carbon dioxide emission to a certain extent, fully reflects the effects of energy conservation and emission reduction, and is an environment-friendly green production process.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for removing phenol and aniline in coking nanofiltration concentrated water, which is a technology and a method for deeply treating coking nanofiltration concentrated water.
Background
China is a large country of coke. Coking is a typical "two-high-cost" industry with high energy consumption, high pollution and resource. A large amount of wastewater can be discharged in the process of producing coke, and about 1 hundred million tons of coking wastewater are discharged annually in China.
The coking wastewater is wastewater formed in the high-temperature carbonization process of coal and the gas purification and chemical product refining processes, contains dozens of pollutants such as phenol, aniline, ammonia nitrogen, cyanide, benzene, pyridine, indole, quinoline and the like, has complex components, high organic pollutant concentration and sewage chromaticity, high toxicity and very stable properties, and is typical organic wastewater difficult to degrade.
The wastewater recycling is the final target of wastewater treatment, and is an implementation means for energy conservation and emission reduction of enterprises. The current simple coking wastewater recycling technology cannot meet the enterprise requirements, and the advanced treatment and recycling of the coking wastewater after biochemical treatment are a necessary trend.
The domestic coking wastewater advanced treatment technology adopts nanofiltration and reverse osmosis technology to carry out advanced treatment on the coking wastewater and then reuse the coking wastewater as circulating cooling water for iron and steel enterprises, but has the main problem of treating concentrated water generated by reverse osmosis. At present, many coking enterprises adopt ultrafiltration, nanofiltration and reverse osmosis to deeply treat coking wastewater.
Therefore, pollutants generated by the nanofiltration process are directly discharged if not treated, and the pollutants tend to be extremely harmful to the water environment.
The application number CN202111226262.6 specifically discloses a coking wastewater nanofiltration salt separation process, which comprises a primary nanofiltration unit, a secondary nanofiltration unit, a high-pressure reverse osmosis device and a concentrated water nanofiltration unit connected with the primary nanofiltration unit which are sequentially connected. The nano-filtration salt separation process for the coking wastewater has the beneficial effects that: by adopting the technical scheme, the strong brine of the coking wastewater is finally divided into two materials, one of the two materials is basically sodium chloride solution, wherein the sodium sulfate content is below 0.01%, the other material is mainly sodium sulfate, the nitrate ratio in the solution is about 10:1, and then the two materials respectively enter two sets of evaporation crystallization systems to separate out sodium chloride and sodium sulfate products, so that zero emission of the coking wastewater is realized, and the crystallization salt separation achieves the aim of industrial salt standard recycling.
Application number CN202111124945.0. The invention discloses a coking wastewater and domestic sewage combined treatment system and a treatment method thereof, wherein the system comprises a collecting tank, a reaction sedimentation tank, an intermediate water tank, a pipeline mixer, a negative pressure stripping ammonia distillation tower, a comprehensive regulating tank, a coagulating sedimentation tank, a pH callback tank, an anaerobic tank, an anoxic tank, an aerobic tank and a secondary sedimentation tank which are sequentially communicated; the secondary sedimentation tank is also communicated with the anoxic tank; the coking wastewater is discharged into a collecting tank through a pipeline, and the domestic sewage is filtered by a grid and then is introduced into a comprehensive regulating tank. The treatment system of the negative pressure stripping ammonia still deamination plus A/A/O plus precipitation can synchronously treat coking wastewater and domestic sewage, and can recycle ammonia water, and the treatment system can lead the sewage of a coalification enterprise to reach the first-level discharge standard of the Integrated wastewater discharge Standard (GB 8978-1996).
The invention aims at coking nanofiltration concentrated water, however, a method for simultaneously removing phenol and aniline in the coking nanofiltration concentrated water is not available so far.
Disclosure of Invention
In order to solve the problem of environmental pollution of phenol and aniline in the coking nanofiltration concentrated water, the invention aims to provide a method for removing phenol and aniline in the coking nanofiltration concentrated water, and the method adopts an advanced treatment system of the coking nanofiltration concentrated water.
The technical scheme of the invention is as follows:
a method for removing phenol and aniline in coking nanofiltration concentrated water, wherein the water quality conductivity of the coking nanofiltration concentrated water is 19230-26780 mu S/cm, phenol is 231-301 mu g/L, aniline is 21-47 mu g/L, and suspended matters are 37-63 mg/L, and the method comprises the following steps:
(1) The coking nanofiltration concentrated water enters a cloth bag filter, the filtering precision of the cloth bag filter is 11-15 mu m, and after passing through the cloth bag filter, suspended matters in the coking nanofiltration concentrated water are 10-14 mg/L;
(2) After flowing out of the cloth bag filter, the coking nanofiltration concentrated water enters an ozone catalytic reaction tower, and a modified biochar catalyst is arranged in the ozone catalytic reaction tower; the modified biochar catalyst in the whole ozone catalytic tower accounts for 75-85% of the whole ozone catalytic tower volume; the specific surface area of the modified biochar catalyst is 678-735 m 2 Per gram, pore volume of 0.39-0.42 cm 3 /g；
(3) After ozone catalytic reaction, the coking nanofiltration concentrated water is discharged or discharged into a zero-discharge evaporation system.
Further, the retention time of the coking nanofiltration concentrated water in the step (1) in the cloth bag filter is 6-7 min.
Further, the modified biochar catalyst in the step (2) is prepared by aiming at the water quality characteristics of high conductivity of coking nanofiltration concentrated water, and specifically comprises the following steps: 1) Biological carbon raw material selection: taking waste vinasse as a biological carbon raw material, drying, cooling, grinding and screening; 2) Carbonizing material: placing the vinasse fine powder particles into a muffle furnace, heating to 415-435 ℃ at a speed of 3-5 ℃/min, keeping the temperature for 15-25 min, and cooling to form a vinasse biological carbon carbonized material; 3) Biochar: preparing a sodium chloride solution with the mass ratio of 3-6%, immersing the vinasse biological carbon carbonized material in the sodium chloride solution according to the liquid-solid ratio (volume ratio) (2-3): 1, filtering, airing, putting into a muffle furnace for roasting, and cooling to form the vinasse biological carbon; 4) Biochar catalyst: preparing 2-5% manganese nitrate solution and 7-13% ferric sulfate solution, and then mixing the two solutions according to a volume ratio of 1:1 preparing ferromanganese mixed solution, immersing lees biological carbon in the ferromanganese mixed solution according to the ratio of liquid to solid (volume ratio) (2-3): 1, immersing, airing, putting into a muffle furnace, roasting, and cooling to prepare the modified biological carbon catalyst.
Further, in the step 1), the waste vinasse is placed in an oven at 115-125 ℃ for 3-5 hours, and the water is naturally cooled after being dried.
Further, the distillers 'grains in the step 1) are ground and screened to 200-300 meshes of distillers' grains fine powder particles.
Further, the soaking time in the step 3) is 2-3 hours, and the filter is carried out and then the air is dried; roasting in a muffle furnace, and heating to 725-775 ℃ at 2-3 ℃/min.
Further, the soaking time in the step 4) is 6 to 12 hours, and the vinasse biochar is taken out and dried; heating to 560-610 ℃ in a muffle furnace at a speed of 4-5 ℃/min, and roasting for 2-4 h at constant temperature.
According to the method for removing phenol and aniline in the coking nanofiltration concentrated water, further, the nanofiltration concentrated water in the step (2) enters the tower from the bottom of the ozone catalytic tower, flows out from bottom to top, and ozone generated by the ozone generator enters the catalytic tower from the bottom and then fills the whole catalytic tower;
further, the retention time of the nanofiltration concentrated water in the step (2) in the ozone catalytic reaction tower is 23-37 min.
Detailed description of the invention:
a system for removing phenol and aniline in coking nanofiltration concentrated water comprises a water inlet pump, a cloth bag filter, a lifting pump, an ozone catalytic reaction tower, a modified biological carbon catalyst and a water outlet pump.
The coking nanofiltration concentrated water has the water quality conductivity of 19230-26780 mu S/cm, the phenol of 231-301 mu g/L, the aniline of 21-47 mu g/L and the suspended matters of 37-63 mg/L.
And the coking nanofiltration concentrated water enters a cloth bag filter through a water inlet pump.
The nanofiltration concentrated water flows out after being filtered by a filter bag, and suspended matters are intercepted in a cloth bag. The filtering precision of the cloth bag filter is 11-15 mu m, the retention time is 6-7 min, and the suspended matters in the coking nanofiltration concentrated water are 10-14 mg/L after passing through the cloth bag filter.
After the coking nanofiltration concentrated water flows out of the cloth bag filter, the coking nanofiltration concentrated water enters an ozone catalytic reaction tower through a lifting pump, and a modified biochar catalyst is arranged in the ozone catalytic reaction tower. The nanofiltration concentrated water enters the ozone catalytic tower from the bottom of the tower and flows out from bottom to top. Ozone generated by the ozone generator enters the catalytic tower from the bottom and then fills the whole catalytic tower. The modified biochar catalyst in the whole ozone catalytic tower accounts for 75-85% of the whole ozone catalytic tower, and the retention time of nanofiltration concentrated water in the tower is 23-37 min. Ozone and the modified biochar catalyst are combined to generate hydroxyl free radicals, so that phenol and aniline can be efficiently and rapidly degraded.
Aiming at the water quality characteristic of high conductivity of coking nanofiltration concentrated water, the invention develops and prepares the modified biochar catalyst which has the function of simultaneously removing phenol and aniline in the nanofiltration concentrated water. Preparation of modified biochar catalyst: 1) Biological carbon raw material selection: taking waste vinasse as a biological carbon raw material, placing the waste vinasse in a baking oven at 115-125 ℃ for 3-5 hours, naturally cooling the waste vinasse after moisture is dried, grinding the dried vinasse into fine powder, and screening vinasse fine powder particles with 200-300 meshes. 2) Carbonizing material: placing the vinasse fine powder particles into a muffle furnace, heating to 415-435 ℃ at a speed of 3-5 ℃/min, keeping the temperature for 15-25 min, and naturally cooling to form the vinasse biological carbon carbonized material. 3) Biochar: preparing a sodium chloride solution with the mass ratio of 3-6%, immersing the vinasse biological carbon carbonized material in the sodium chloride solution according to the liquid-solid ratio (volume ratio) (2-3): 1 for 2-3 hours, filtering, airing, placing in a muffle furnace, heating to 725-775 ℃ at 2-3 ℃/min, and cooling to form the vinasse biological carbon. 4) Biochar catalyst: preparing 2-5% manganese nitrate solution and 7-13% ferric sulfate solution, and then mixing the two solutions according to a volume ratio of 1:1 preparing ferromanganese mixed solution, immersing the vinasse biochar in the ferromanganese mixed solution according to the ratio of liquid to solid (volume ratio) (2-3): 1 for 6-12 h, taking out the vinasse biochar, airing at room temperature, placing Ma Fulu, heating to 560-610 ℃ at 4-5 ℃/min, roasting at constant temperature for 2-4 h, and then naturally cooling to prepare the modified biochar catalyst. The specific surface area of the modified biochar catalyst is 678-735 m 2 Per gram, pore volume of 0.39-0.42 cm 3 /g。The modified biochar has the capability of catalyzing and degrading phenol and aniline under the action of ozone and also has the capability of adsorbing phenol and aniline.
After ozone catalytic reaction, the coking nanofiltration concentrated water has the conductivity of 19410-26990 mu S/cm, the phenol of 21-26 mu g/L, the aniline of 2-5 mu g/L and the suspended matters of 7-11 mg/L.
Then, the discharge pump discharges or discharges the treated coking nanofiltration concentrated water into a zero discharge evaporation system.
The beneficial technical effects of the invention are as follows:
after the treatment by the method, the electric conductivity of the coking nanofiltration concentrated water is 19410-26990 mu S/cm, the phenol is 21-26 mu g/L, the aniline is 2-5 mu g/L, and the suspended matters are 7-11 mg/L.
The process for removing phenol and aniline in the coking nanofiltration concentrated water has low production and operation cost, adopts the biochar technology, reduces carbon dioxide emission to a certain extent, fully reflects the effects of energy conservation and emission reduction, and is an environment-friendly green production process.
Drawings
Fig. 1: a system for removing phenol and aniline in coking nanofiltration concentrated water.
Wherein: the device comprises a water inlet pump-1, a cloth bag filter-2, a lift pump-3, an ozone catalytic reaction tower-4, a modified biochar catalyst-5 and a water outlet pump-6.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1:
a system for removing phenol and aniline in coking nanofiltration concentrated water comprises a water inlet pump, a cloth bag filter, a lifting pump, an ozone catalytic reaction tower, a modified biological carbon catalyst and a water outlet pump.
The coking nanofiltration concentrated water has the water quality conductivity of 25990 mu S/cm, phenol of 301 mu g/L, aniline of 45 mu g/L and suspended matters of 61mg/L.
And the coking nanofiltration concentrated water enters a cloth bag filter through a water inlet pump.
The nanofiltration concentrated water flows out after being filtered by a filter bag, and suspended matters are intercepted in a cloth bag. The filtering precision of the cloth bag filter is 11 mu m, the retention time is 7min, and the suspended matters in the coking nanofiltration concentrated water are 14mg/L after passing through the cloth bag filter.
After the coking nanofiltration concentrated water flows out of the cloth bag filter, the coking nanofiltration concentrated water enters an ozone catalytic reaction tower through a lifting pump, and a modified biochar catalyst is arranged in the ozone catalytic reaction tower. The nanofiltration concentrated water enters the ozone catalytic tower from the bottom of the tower and flows out from bottom to top. Ozone generated by the ozone generator enters the catalytic tower from the bottom and then fills the whole catalytic tower. The modified biochar catalyst in the whole ozone catalytic tower accounts for 75-85% of the whole ozone catalytic tower, and the retention time of nanofiltration concentrated water in the tower is 31min. Ozone and the modified biochar catalyst are combined to generate hydroxyl free radicals, so that phenol and aniline can be efficiently and rapidly degraded.
Aiming at the water quality characteristic of high conductivity of coking nanofiltration concentrated water, the invention develops and prepares the modified biochar catalyst which has the function of simultaneously removing phenol and aniline in the nanofiltration concentrated water. Preparation of modified biochar catalyst: 1) Biological carbon raw material selection: taking waste vinasse as a biological carbon raw material, placing the waste vinasse in a 125 ℃ oven for 5 hours, naturally cooling the waste vinasse after drying the waste vinasse by moisture, grinding the dried vinasse into fine powder, and screening the fine powder particles of the vinasse with 300 meshes. 2) Carbonizing material: placing the vinasse fine powder particles into a muffle furnace, heating to 435 ℃ at 5 ℃/min, keeping the temperature for 25min, and naturally cooling to form the vinasse biological carbon carbonized material. 3) Biochar: preparing a sodium chloride solution with the mass ratio of 6%, immersing the vinasse biological carbon carbonized material in the sodium chloride solution according to the ratio of 3:1 of the liquid-solid ratio (volume ratio) for 3 hours, filtering, airing, putting into a muffle furnace, heating to 775 ℃ at 3 ℃/min, and cooling to form the vinasse biological carbon. 4) Biochar catalyst: preparing a manganese nitrate solution with the mass ratio concentration of 5% and a ferric sulfate solution with the mass ratio concentration of 13%, preparing a ferromanganese mixed solution by the two solutions according to the volume ratio of 1:1, immersing the vinasse biochar in the ferromanganese mixed solution according to the ratio of 3:1 of the liquid-solid ratio (volume ratio), immersing for 12 hours, taking out the vinasse biochar, airing at room temperature, putting in Ma Fulu, and heating to 5 ℃/minRoasting at 610 ℃ for 4 hours, and then naturally cooling to prepare the modified biochar catalyst. The specific surface area of the modified biochar catalyst is 712m 2 Per gram, pore volume of 0.39cm 3 And/g. The modified biochar has the capability of catalyzing and degrading phenol and aniline under the action of ozone and also has the capability of adsorbing phenol and aniline.
After the ozone catalytic reaction, the electric conductivity of the coking nanofiltration concentrated water is 26130 mu S/cm, the phenol is 23 mu g/L, the aniline is 4 mu g/L, and the suspended matter is 11mg/L.
Then, the discharge pump discharges or discharges the treated coking nanofiltration concentrated water into a zero discharge evaporation system.
Example 2
A system for removing phenol and aniline in coking nanofiltration concentrated water comprises a water inlet pump, a cloth bag filter, a lifting pump, an ozone catalytic reaction tower, a modified biological carbon catalyst and a water outlet pump.
The coking nanofiltration concentrated water has the water quality conductivity of 21340 mu S/cm, the phenol of 255 mu g/L, the aniline of 32 mu g/L and the suspended matter of 45mg/L.
And the coking nanofiltration concentrated water enters a cloth bag filter through a water inlet pump.
The nanofiltration concentrated water flows out after being filtered by a filter bag, and suspended matters are intercepted in a cloth bag. The filtering precision of the cloth bag filter is 15 mu m, the retention time is 7min, and the suspended matters in the coking nanofiltration concentrated water are 12mg/L after passing through the cloth bag filter.
After the coking nanofiltration concentrated water flows out of the cloth bag filter, the coking nanofiltration concentrated water enters an ozone catalytic reaction tower through a lifting pump, and a modified biochar catalyst is arranged in the ozone catalytic reaction tower. The nanofiltration concentrated water enters the ozone catalytic tower from the bottom of the tower and flows out from bottom to top. Ozone generated by the ozone generator enters the catalytic tower from the bottom and then fills the whole catalytic tower. The modified biochar catalyst in the whole ozone catalytic tower accounts for 75% of the whole ozone catalytic tower, and the retention time of nanofiltration concentrated water in the tower is 25min. Ozone and the modified biochar catalyst are combined to generate hydroxyl free radicals, so that phenol and aniline can be efficiently and rapidly degraded.
The invention aims at the water quality special for the high conductivity of the coking nanofiltration concentrated waterThe modified biochar catalyst is developed and prepared, and has the function of simultaneously removing phenol and aniline in nanofiltration concentrated water. Preparation of modified biochar catalyst: 1) Biological carbon raw material selection: taking waste vinasse as a biological carbon raw material, placing the waste vinasse in a 115 ℃ oven for 3-5 hours, naturally cooling the waste vinasse after moisture is dried, grinding the dried vinasse into fine powder, and screening vinasse fine powder particles with 200 meshes. 2) Carbonizing material: placing the vinasse fine powder particles into a muffle furnace, heating to 415 ℃ at a speed of 3 ℃/min, keeping the temperature for 15min, and naturally cooling to form the vinasse biological carbon carbonized material. 3) Biochar: preparing a sodium chloride solution with the mass ratio of 3%, immersing the vinasse biological carbon carbide material in the sodium chloride solution according to the ratio of 2:1 of the liquid-solid ratio (volume ratio) for 3 hours, filtering, airing, putting into a muffle furnace, heating to 725 ℃ at 2 ℃/min, and cooling to form the vinasse biological carbon. 4) Biochar catalyst: preparing a manganese nitrate solution with the mass ratio concentration of 2% and a ferric sulfate solution with the mass ratio concentration of 9%, preparing a ferromanganese mixed solution by the two solutions according to the volume ratio of 1:1, immersing the vinasse biochar in the ferromanganese mixed solution according to the ratio of 2:1, immersing for 7 hours, taking out the vinasse biochar, airing at room temperature, putting into a Markov furnace, heating to 565 ℃ at the speed of 4 ℃/min, roasting for 2 hours at constant temperature, and then naturally cooling to prepare the modified biochar catalyst. The specific surface area of the modified biochar catalyst is 689m 2 Per gram, pore volume of 0.41cm 3 And/g. The modified biochar has the capability of catalyzing and degrading phenol and aniline under the action of ozone and also has the capability of adsorbing phenol and aniline.
After the ozone catalytic reaction, the electric conductivity of the coking nanofiltration concentrated water is 21760 mu S/cm, the phenol is 23 mu g/L, the aniline is 3 mu g/L, and the suspended matter is 8mg/L.
In conclusion, the process for removing phenol and aniline in the coking nanofiltration concentrated water has low production and operation cost, adopts the biochar technology, reduces carbon dioxide emission to a certain extent, fully reflects the effects of energy conservation and emission reduction, and is an environment-friendly green production process.
It will of course be appreciated by those skilled in the art that the above-described embodiments are provided for illustration only and not as limitations of the present invention, and that variations and modifications of the above-described embodiments will fall within the scope of the appended claims.
Claims (10)
1. The method for removing phenol and aniline in the coking nanofiltration concentrated water is characterized by comprising the following steps of:
(1) The coking nanofiltration concentrated water enters a cloth bag filter, the filtering precision of the cloth bag filter is 11-15 mu m, and after passing through the cloth bag filter, suspended matters in the coking nanofiltration concentrated water are 10-14 mg/L;
(2) After flowing out of the cloth bag filter, the coking nanofiltration concentrated water enters an ozone catalytic reaction tower, and a modified biochar catalyst is arranged in the ozone catalytic reaction tower; the modified biochar catalyst in the whole ozone catalytic tower accounts for 75-85% of the whole ozone catalytic tower volume; the specific surface area of the modified biochar catalyst is 678-735 m 2 Per gram, pore volume of 0.39-0.42 cm 3 /g；
(3) After ozone catalytic reaction, the coking nanofiltration concentrated water is discharged or discharged into a zero-discharge evaporation system.
2. The method for removing phenol and aniline from the coking nanofiltration concentrated water according to claim 1, wherein the coking nanofiltration concentrated water in the step (1) has a retention time of 6-7 min in a cloth bag filter.
3. The method for removing phenol and aniline from coking nanofiltration concentrated water according to claim 1, wherein the modified biochar catalyst in the step (2) is prepared by aiming at the water quality characteristics of high conductivity of the coking nanofiltration concentrated water, and specifically comprises the following steps: 1) Biological carbon raw material selection: taking waste vinasse as a biological carbon raw material, drying, cooling, grinding and screening; 2) Carbonizing material: placing the vinasse fine powder particles into a muffle furnace, heating to 415-435 ℃ at a speed of 3-5 ℃/min, keeping the temperature for 15-25 min, and cooling to form a vinasse biological carbon carbonized material; 3) Biochar: preparing a sodium chloride solution with the mass ratio of 3-6%, immersing the vinasse biological carbon carbonized material in the sodium chloride solution according to the liquid-solid ratio (volume ratio) (2-3): 1, filtering, airing, putting into a muffle furnace for roasting, and cooling to form the vinasse biological carbon; 4) Biochar catalyst: preparing 2-5% manganese nitrate solution and 7-13% ferric sulfate solution, and then mixing the two solutions according to a volume ratio of 1:1 preparing ferromanganese mixed solution, immersing lees biological carbon in the ferromanganese mixed solution according to the ratio of liquid to solid (volume ratio) (2-3): 1, immersing, airing, putting into a muffle furnace, roasting, and cooling to prepare the modified biological carbon catalyst.
4. The method for removing phenol and aniline in coking nanofiltration concentrated water according to claim 3, wherein in the step 1), the waste vinasse is placed in an oven at 115-125 ℃ for 3-5 hours, and the water is naturally cooled after being dried.
5. The method for removing phenol and aniline from coking nanofiltration concentrated water according to claim 3, wherein the distillers 'grains in step 1) are ground and screened to 200-300 mesh distillers' grains fine powder particles.
6. The method for removing phenol and aniline in coking nanofiltration concentrated water according to claim 3, wherein the soaking time in the step 3) is 2-3 h, and the coking nanofiltration concentrated water is dried after filtration; roasting in a muffle furnace, and heating to 725-775 ℃ at 2-3 ℃/min.
7. The method for removing phenol and aniline in coking nanofiltration concentrated water according to claim 3, wherein the soaking time in the step 4) is 6-12 h, taking out the distillers' grains biological carbon, and airing; heating to 560-610 ℃ in a muffle furnace at a speed of 4-5 ℃/min, and roasting for 2-4 h at constant temperature.
8. The method for removing phenol and aniline from coking nanofiltration concentrated water according to claim 1, wherein the nanofiltration concentrated water in the step (2) enters the ozone catalytic tower from the bottom, flows out from bottom to top, and ozone generated by the ozone generator enters the catalytic tower from the bottom and fills the whole catalytic tower;
9. the method for removing phenol and aniline from coking nanofiltration concentrated water according to claim 1, wherein the retention time of the nanofiltration concentrated water in the ozone catalytic reaction tower in the step (2) is 23-37 min.
10. The method for removing phenol and aniline from coking nanofiltration concentrated water according to claim 1, wherein after ozone catalytic reaction, the coking nanofiltration concentrated water has a conductivity of 19410-26990 μs/cm, phenol of 21-26 μg/L, aniline of 2-5 μg/L and suspended matter of 7-11 mg/L.
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