CN115304216B - Semi-coke wastewater treatment process - Google Patents
Semi-coke wastewater treatment process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000008569 process Effects 0.000 title claims abstract description 42
- 239000000571 coke Substances 0.000 title claims abstract description 40
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002351 wastewater Substances 0.000 claims abstract description 48
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 36
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000011084 recovery Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 230000020477 pH reduction Effects 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 19
- 238000004062 sedimentation Methods 0.000 claims abstract description 13
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000001112 coagulating effect Effects 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- XABJJJZIQNZSIM-UHFFFAOYSA-N azane;phenol Chemical compound [NH4+].[O-]C1=CC=CC=C1 XABJJJZIQNZSIM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- 230000015556 catabolic process Effects 0.000 claims abstract description 4
- 238000006731 degradation reaction Methods 0.000 claims abstract description 4
- 239000010802 sludge Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 11
- 239000011280 coal tar Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 208000005156 Dehydration Diseases 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- 230000001546 nitrifying effect Effects 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims 1
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000009615 deamination Effects 0.000 description 2
- 238000006481 deamination reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
-
- 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
- C02F1/048—Purification of waste water by evaporation
-
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
-
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
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- C02F3/02—Aerobic processes
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- C02F3/30—Aerobic and anaerobic processes
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Abstract
The invention discloses a semi-coke wastewater treatment process, which comprises a pretreatment stage, a biochemical treatment stage and a deep treatment stage, wherein the pretreatment stage comprises oil removal and phenol-ammonia recovery: the oil content of the deoiled wastewater is less than 800mg/L, and then enters a phenol ammonia recovery system; in the phenol-ammonia recovery system, wastewater is treated by a deacidification tower, an ammonia distillation tower, a phenol extraction tower, a solvent recovery tower, a stripping tower and an ammonia purification system in sequence and then is sent to a biochemical treatment stage, and the phenol-ammonia recovery system is used for preparing 20% ammonia water and crude phenol; in the biochemical treatment stage, wastewater is subjected to air floatation, hydrolytic acidification, two-stage A/O and coagulating sedimentation treatment in sequence, so that further oil removal, degradation of COD and ammonia nitrogen pollutants and suspended matters removal are realized; and in the advanced treatment stage, the wastewater in the biochemical treatment stage is sequentially subjected to multi-medium filtration, primary ozone catalytic oxidation, BAF, secondary ozone catalytic oxidation and active carbon filtration treatment, so that the discharged water reaches the discharge standard and can be recycled for coke quenching.
Description
Technical Field
The invention relates to a semi-coke wastewater treatment process.
Background
The semi-coke is a solid carbonaceous product with lower volatile matters, which is obtained by using long flame coal, non-sticky coal, weak sticky coal and the like through medium-low temperature carbonization pyrolysis. The semi-coke is used to replace metallurgical coke and is widely used in the production of calcium carbide, ferroalloy, ferrosilicon, silicon carbide and other products to become an irreplaceable carbon material.
The semi-coke is a product of low-temperature carbonization (about 550-650 ℃) in coal, and the wastewater in the production process mainly comes from the sewage of circulating water for washing coal gas. The semi-coke is a low-temperature carbonization product, and the semi-coke wastewater contains a large amount of pollutants which are not oxidized at high temperature, such as volatile phenol, ammonia nitrogen, polycyclic aromatic hydrocarbon, oxygen, sulfur, nitrogen and other heterocyclic compounds, the concentration of the semi-coke is much higher than that of coking wastewater, the semi-coke is more difficult to treat, and the environmental hazard is larger.
Water quality meter for common semi-coke wastewater
| Contaminants (S) | pH | Petroleum products | Ammonia nitrogen | COD | Sulfides | Total phenols |
| Eigenvalues | 8.5～10 | ＜4500 | 3000～5000 | 30000～45000 | ＜1000 | 10000～15000 |
Note that: the pH is dimensionless, and the unit of the rest pollutants is mg/L.
Semi-coke enterprises are generally located in areas with rich coal resources, and the problems of water resource shortage of different degrees exist. Along with the stricter environmental regulations in China and the official promulgation of 'ten water strips', the treatment of semi-coke wastewater faces more serious challenges.
Chinese patent application CN104724886a discloses a process for decarbonizing and total nitrogen removing of semi-coke wastewater, which comprises a pretreatment system, a biochemical treatment system and a deep treatment system. Wherein the pretreatment adopts an oil separation tank and two-stage air floatation, the biochemical treatment system adopts a combination of multifunctional deamination and aerobic anoxic and aerobic conditions, and the advanced treatment system adopts photocatalytic ozone oxidation and membrane separation. The biochemical treatment system is mainly added with a special microbial agent to realize removal of ammonia nitrogen and COD. The pretreatment system is simple, so that the biochemical treatment system has high load, high energy consumption and poor stability of treatment effect, the advanced treatment inflow water quality fluctuates, and the final outflow water of membrane separation is relied on, so that the running stability of membrane separation equipment is doubtful.
Chinese patent application CN104773930a discloses a semi-coke wastewater treatment system and process, including a physical and chemical treatment system, a biochemical treatment system and a deep treatment system. Wherein the physical and chemical treatment system adopts the combination of an oil separation tank, coagulating sedimentation, aeration Fe/C, fenton and flocculating sedimentation, the biochemical treatment system adopts hydrolysis, contact anaerobic and CBR (carrier transfer bed), and the advanced treatment system adopts ozone oxidation, fenton, activated carbon adsorption, CBR and flocculating decoloration. The pretreatment of physical and chemical treatment mainly comprises chemical oxidation, the Fe/C micro-electrolysis and Fenton mud amount are large, the advanced treatment process has long chain, the operation control difficulty is high, and the operation cost is uneconomical.
Chinese patent application CN105060628a discloses a method for treating semi-coke wastewater, which comprises a pretreatment system and a biochemical treatment system. Wherein the pretreatment adopts the combination of an oil separation tank, coagulation air flotation, phenol extraction and ammonia blowing, and the biochemical treatment system adopts the combination of hydrolytic acidification, anaerobism, A/O (powdered activated carbon) and an aeration biological filter tank. The pretreatment is better, the system load of the biochemical treatment system can be effectively reduced, but the powder activated carbon is added, the adding amount is larger, the sludge amount is greatly increased, and the sludge disposal difficulty is increased
Disclosure of Invention
Aiming at the problems in the related art, the invention provides a semi-coke wastewater treatment process method to solve and optimize the problems of complex system, high energy consumption, unstable operation, high operation cost, difficult achievement of treatment effect to emission standard and the like in the prior art.
The invention can be realized by the following technical scheme:
The semi-coke wastewater treatment process comprises a pretreatment stage, a biochemical treatment stage and a deep treatment stage, wherein the pretreatment stage comprises oil removal and phenol-ammonia recovery: the oil content of the deoiled wastewater is less than 800mg/L, and then enters a phenol ammonia recovery system; in the phenol-ammonia recovery system, wastewater is treated by a deacidification tower, an ammonia distillation tower, a phenol extraction tower, a solvent recovery tower, a stripping water tower and an ammonia purification system in sequence and then is sent to the biochemical treatment stage, and the phenol-ammonia recovery system is used for preparing 20% ammonia water and crude phenol; the biochemical treatment stage is characterized in that wastewater is sequentially subjected to air floatation, hydrolytic acidification, two-stage A/O and coagulating sedimentation treatment, so that further degradation of oil removal, COD and ammonia nitrogen pollutants and suspended matters removal are realized; and in the advanced treatment stage, wastewater from the biochemical treatment stage is subjected to multi-medium filtration, primary ozone catalytic oxidation, BAF, secondary ozone catalytic oxidation and active carbon filtration in sequence, so that the effluent reaches the direct emission limit value in the table 2 of the emission standard of pollutants in coking chemistry industry (GB 6171-2012) and can be reused for quenching.
Further, the deoiling is composed of two steps, and the semi-coke wastewater is firstly subjected to pre-separation of oil residues and heavy coal tar in a gravity settling tank and then is subjected to a multiphase flow high-efficiency oil separation device; the separated coal tar is collected and recovered separately.
Further, after acid gas and ammonia are separated out from the deacidification tower and the ammonia distillation tower, the acid gas and the ammonia are fed into a phenol extraction tower, an extract liquid is fed into a solvent recovery tower, an extractant is recovered, crude phenol after solvent recovery is fed into a crude phenol storage tank, raffinate is fed into a stripping tower, after the extractant is further recovered, the wastewater is cooled to below 40 ℃ and is fed into a biochemical treatment stage.
Further, in the biochemical treatment stage, wastewater collected by a wastewater regulating tank is subjected to air floatation treatment, demulsification and coagulation agents (which are required to be determined actually) are added, further deoiling is carried out, then the wastewater enters hydrolysis acidification Chi Shuijie for acidification, a water distribution unit is arranged in the hydrolysis acidification tank, water discharged from the hydrolysis acidification tank automatically flows into a two-stage A/O reaction tank, and in the two-stage A/O reaction tank, COD and ammonia nitrogen pollutants are degraded through two-stage combination, nitrifying liquid backflow and full aeration oxygen supply; the effluent of the two-stage A/O reaction tank enters a coagulating sedimentation tank after passing through a secondary sedimentation tank, and is sent to a deep treatment stage after suspended matters are further removed.
Further, in the biochemical treatment stage, air floatation scum, coagulated sludge and biochemical excess sludge are respectively collected according to materialized sludge and biochemical sludge, and respectively subjected to sludge dehydration treatment.
Further, in the advanced treatment stage, effluent water after being filtered by a multi-medium filter enters an ozone catalytic oxidation contactor from a self-flow mode, ozone (40-80 mg/L) is added, and biochemical performance improvement and chromaticity removal are achieved under the synergistic effect of catalytic filler; and (3) the BAF effluent enters an ozone activated carbon process combining the secondary ozone catalytic oxidation and the activated carbon filtration, so that the effluent reaches the requirement of a direct discharge limit.
Further, after the acid gas and the ammonia are separated from the deacidification tower and the ammonia distillation tower, the ammonia nitrogen content in the wastewater is less than 300mg/L.
Furthermore, the extractant in the phenol extraction tower adopts methyl isobutyl ketone (MIBK), and the total phenol content after extraction is less than 650mg/L; after phenol extraction, the recovery of the crude phenol product is achieved.
Further, the hydrolytic acidification tank and the two-stage A/O reaction tank are designed with biological fillers.
The invention has the following beneficial effects:
1) The oil removing device uses gravity and multiphase flow to gather and remove oil, and the separated coal tar can create beneficial value;
2) Phenol-ammonia recovery pretreatment is selected, crude phenol and ammonia water are recovered, and wastewater is recycled, so that the difficulty of biochemical treatment is greatly improved, and products with economic value are recovered;
3) The full and effective pretreatment process method is adopted to create the optimal water inlet condition for the biochemical treatment section, so that the efficiency of the biochemical process is improved;
4) On the premise of high-efficiency pretreatment, the anaerobic process is abandoned, and the detoxification effect of the hydrolytic acidification process is fully utilized and then the anaerobic process directly enters the A/O process section. The biological filler is filled to form the combination of an activated sludge method and a biological membrane method, so that the microorganism concentration in the reaction tank is improved, the volume load in the reaction tank is improved, the utilization efficiency of aeration air is improved, the tank capacity is reduced, and the energy consumption is reduced;
5) The advanced treatment adopts the main process of ozone oxidation, and focuses on decolorization and chain breakage, so that the stability of the final effluent quality is ensured;
6) The process monomers adopted by the process scheme are convenient to combine, the monomer structures can be combined in a blocking manner, intensive arrangement is realized, the field is efficiently utilized, and the project occupation is saved;
7) Due to the economic value of coal tar, ammonia water and crude phenol, and the energy saving and consumption reduction of the overall process, the comprehensive treatment cost of the semi-coke wastewater treatment process disclosed by the invention is about 30-40 yuan/ton of water.
Drawings
FIG. 1 is a schematic diagram of a process according to the present invention;
FIG. 2 is a flow chart of the semi-coke wastewater treatment process of the invention.
Detailed Description
Other advantages and effects of the present invention will become readily apparent to those skilled in the art from the following disclosure, when considered in light of the following detailed description of the invention.
As shown in fig. 1 and 2, a semi-coke wastewater treatment process of the present invention includes a pretreatment stage, a biochemical treatment stage and a deep treatment stage,
Wherein the pretreatment stage comprises oil removal and phenol ammonia recovery;
The oil removal is to better realize phenol ammonia recovery. The deoiling is composed of two steps, the semi-coke wastewater is firstly subjected to the pre-separation of oil residue and heavy coal tar in a gravity settling tank, and then is subjected to a multiphase flow high-efficiency oil separating device;
the separated coal tar is collected and recycled independently, the oil content of the wastewater after oil removal is less than 800mg/L, and the wastewater enters a phenol ammonia recycling system;
The deoiled semi-coke wastewater can safely enter a phenol-ammonia recovery system, wherein the phenol-ammonia recovery system consists of a deacidification tower, an ammonia distillation tower, a phenol extraction tower, a solvent recovery tower, a stripping water tower and an ammonia purification system;
The deacidification tower and the ammonia distillation tower separate acid gas and ammonia firstly, and phenol extraction is performed after the acid gas and the ammonia are removed, so that the working condition of a subsequent phenol extraction working section is stable, the efficiency of an extractant is maximized, and the consumption and energy consumption of the extractant of a system are reduced; the extractant of the extraction tower adopts methyl isobutyl ketone (MIBK), and the total phenol content after extraction is less than 650mg/L, so that high-efficiency extraction is realized; the extraction liquid enters a solvent recovery tower, an extracting agent is recovered, the extracting agent is recycled, and crude phenol after solvent recovery enters a crude phenol storage tank; the raffinate enters a stripping water tower to further recover an extractant, so that the quality of wastewater entering a subsequent biochemical treatment stage is ensured;
The crude ammonia evaporated from the ammonia still is made into 20% ammonia water through an ammonia purification system;
The temperature of the wastewater after the water tower stripping is reduced to below 40 ℃ and is sent to a biochemical treatment stage;
Wherein the biochemical treatment stage comprises air floatation, hydrolytic acidification, two-stage A/O and coagulating sedimentation;
The pretreated effluent is collected by an adjusting tank, is subjected to air floatation treatment, is added with demulsification and coagulation agents, and enters a hydrolysis acidification tank after further deoiling;
the hydrolysis acidification tank is provided with a water distribution unit so as to ensure optimal operation parameters in the hydrolysis tank, and water discharged from the hydrolysis acidification tank automatically flows into the two-stage A/O reaction tank;
The two-stage A/O reaction tank is a main reaction zone in the biochemical treatment stage, design parameters are calculated according to the actual water quality of the inflow water, and the degradation of pollutants such as COD, ammonia nitrogen and the like is realized through measures such as two-stage combination, nitrifying liquid reflux, full aeration and oxygen supply and the like;
the effluent of the A/O reaction tank enters a coagulating sedimentation tank after passing through a secondary sedimentation tank, and is sent to a deep treatment stage after suspended matters are further removed;
The air floatation scum, the coagulated sludge and the biochemical excess sludge are respectively collected according to the materialized sludge and the biochemical sludge, and respectively carry out sludge dehydration treatment;
The advanced treatment stage comprises multi-medium filtration, primary ozone catalytic oxidation, BAF, secondary ozone catalytic oxidation and active carbon filtration;
The suspended matters of the coagulating sedimentation effluent are filtered by a multi-medium filter to meet the water inlet requirement of the ozone catalytic oxidation contactor;
The effluent of the multi-medium filter automatically flows into an ozone catalytic oxidation contactor, ozone is added, and under the synergistic effect of catalytic filler, refractory organic matters are oxidized and decomposed, and chromaticity molecules are destroyed, so that the improvement of biochemical performance and chromaticity removal are realized;
The combination of BAF and ozone catalytic oxidation can more effectively utilize biological treatment to degrade refractory organic matters;
The BAF effluent enters an ozone activated carbon process combining the two-stage ozone catalytic oxidation and the activated carbon filtration, the organic matter and chromaticity removal effect is consolidated and improved, and the BAF effluent stably reaches the direct emission limit value in the table 2 of the emission standard of pollutants in coking chemistry industry (GB 6171-2012) and can be recycled for quenching.
In the invention, the deacidification and deamination can be respectively removed by selecting double towers, and can be synchronously removed by selecting a single tower, and the ammonia nitrogen content in the wastewater can be less than 300mg/L after the two processes are processed, so that the overall goal of the semi-coke wastewater process scheme is not affected; the air floatation in the biochemical treatment stage can be selected to be common air floatation or nitrogen air floatation, and the two air floatation can possibly cause the change of water chromaticity in the subsequent process, but the final water chromaticity is not affected due to the arrangement of advanced treatment two-stage ozone catalytic oxidation, so that the overall goal of the semi-coke wastewater process scheme is not affected; the water distribution area is arranged for hydrolysis acidification, so that the treatment performance of hydrolysis acidification is effectively improved; the hydrolytic acidification tank and the two-stage A/O reaction tank are designed with biological filler, so that the volume load of the reaction tank is improved, the tank capacity of the reaction tank is reduced, and the investment cost is favorably controlled; the advanced treatment adopts an ozone catalytic oxidation process and the combination with BAF or active carbon, which is helpful for fully utilizing ozone, reducing ozone consumption and reducing system energy consumption; the advanced treatment adopts an ozone oxidation process, is specially set for the chromaticity problem of the semi-coke wastewater, and the selection of the multistage ozone process depends on the effluent quality requirement, so that the overall goal of the semi-coke wastewater process scheme is not affected; the materialized sludge and the biochemical sludge are respectively collected and treated, so that the disposal difficulty of the tail sludge is reduced.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. A semi-coke wastewater treatment process comprises a pretreatment stage, a biochemical treatment stage and a deep treatment stage, and is characterized in that,
The pretreatment stage comprises oil removal and phenol-ammonia recovery:
the oil content of the deoiled wastewater is less than 800mg/L, and then enters a phenol ammonia recovery system;
In the phenol-ammonia recovery system, wastewater is treated by a deacidification tower, an ammonia distillation tower, a phenol extraction tower, a solvent recovery tower, a stripping water tower and an ammonia purification system in sequence and then is sent to the biochemical treatment stage, and the phenol-ammonia recovery system is used for preparing 20% ammonia water and crude phenol;
the biochemical treatment stage is characterized in that wastewater is sequentially subjected to air floatation, hydrolytic acidification, two-stage A/O and coagulating sedimentation treatment, so that further degradation of oil removal, COD and ammonia nitrogen pollutants and suspended matters removal are realized;
The advanced treatment stage is characterized in that wastewater in the biochemical treatment stage is sequentially subjected to multi-medium filtration, primary ozone catalytic oxidation, BAF, secondary ozone catalytic oxidation and active carbon filtration treatment, so that effluent reaches the direct emission limit value in the table 2 of the emission standard of pollutants in coking chemistry industry (GB 16171-2012); in the biochemical treatment stage, wastewater collected by a wastewater regulating tank is subjected to air floatation treatment, demulsification and coagulation medicaments are added, further deoiling is carried out, then the wastewater enters hydrolysis acidification Chi Shuijie for acidification, a water distribution unit is arranged in the hydrolysis acidification tank, water discharged from the hydrolysis acidification tank automatically flows into a two-stage A/O reaction tank, and in the two-stage A/O reaction tank, COD and ammonia nitrogen pollutants are degraded through two-stage combination, nitrifying liquid backflow and full aeration oxygen supply; the effluent of the two-stage A/O reaction tank enters a coagulating sedimentation tank after passing through a secondary sedimentation tank, and is sent to a deep treatment stage after suspended matters are further removed.
2. The semi-coke wastewater treatment process according to claim 1, wherein the process comprises the following steps: the deoiling is composed of two steps, the semi-coke wastewater is firstly subjected to pre-separation of oil residue and heavy coal tar in a gravity settling tank, and then is subjected to a multiphase flow high-efficiency oil separation device; the separated coal tar is collected and recovered separately.
3. The process for treating semi-coke wastewater according to claim 1, wherein the deacidification tower and the ammonia distillation tower separate acid gas and ammonia first, then enter a phenol extraction tower, extract liquid enters a solvent recovery tower, extractant is recovered, crude phenol after solvent recovery enters a crude phenol storage tank, raffinate enters a stripping tower, and wastewater is cooled to below 40 ℃ after extractant is further recovered and is sent to a biochemical treatment stage.
4. The process for treating semi-coke wastewater according to claim 1, wherein in the biochemical treatment stage, air floatation scum, coagulated sludge and biochemical surplus sludge are collected according to materialized sludge and biochemical sludge respectively, and sludge dehydration treatment is performed respectively.
5. The semi-coke wastewater treatment process according to claim 1, wherein in the advanced treatment stage, effluent water after being filtered by a multi-medium filter enters an ozone catalytic oxidation contactor automatically, and under the synergistic effect of catalytic filler, biochemical performance improvement and chromaticity removal are realized by adding 40-80 mg/L ozone; and (3) the BAF effluent enters an ozone activated carbon process combining the secondary ozone catalytic oxidation and the activated carbon filtration, so that the effluent reaches the direct emission limit requirement.
6. A process for treating semi-coke wastewater according to claim 3, wherein the ammonia nitrogen content in the wastewater is less than 300mg/L after the acid gas and the ammonia are separated from the deacidification tower and the ammonia distillation tower.
7. A process for treating semi-coke wastewater according to claim 3, wherein the extractant in the phenol extraction tower is methyl isobutyl ketone (MIBK), and the total phenol content after extraction is less than 650mg/L; after phenol extraction, the recovery of the crude phenol product is achieved.
8. The process for treating semi-coke wastewater according to claim 4, wherein the hydrolytic acidification tank and the two-stage A/O reaction tank are provided with biological fillers.
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