CN115304216A - Semi-coke wastewater treatment process - Google Patents
Semi-coke wastewater treatment process Download PDFInfo
- Publication number
- CN115304216A CN115304216A CN202210925410.1A CN202210925410A CN115304216A CN 115304216 A CN115304216 A CN 115304216A CN 202210925410 A CN202210925410 A CN 202210925410A CN 115304216 A CN115304216 A CN 115304216A
- Authority
- CN
- China
- Prior art keywords
- ammonia
- wastewater
- phenol
- stage
- tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000571 coke Substances 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title claims abstract description 42
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002351 wastewater Substances 0.000 claims abstract description 49
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 37
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 230000020477 pH reduction Effects 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 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
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 10
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000001112 coagulating effect Effects 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 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
- 230000015556 catabolic process Effects 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- 238000010791 quenching Methods 0.000 claims abstract description 4
- 230000000171 quenching effect Effects 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 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000005188 flotation Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 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
- 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
- 238000005345 coagulation Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 230000006872 improvement Effects 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 3
- 208000005156 Dehydration Diseases 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000006396 nitration reaction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000011027 product recovery Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000000356 contaminant Substances 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
- 230000000813 microbial effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- -1 Sulfide compound Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 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
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- 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]
-
- 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
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/308—Biological phosphorus removal
Abstract
The invention discloses a semi-coke wastewater treatment process, which comprises a pretreatment stage, a biochemical treatment stage and an advanced treatment stage, wherein the pretreatment stage comprises oil removal and phenol-ammonia recovery: the oil content of the wastewater after oil removal is less than 800mg/L, and then the wastewater enters a phenol ammonia recovery system; in the phenol-ammonia recovery system, the wastewater is sent to a biochemical treatment stage after being sequentially treated by a deacidification tower, an ammonia still, a phenol extraction tower, a solvent recovery tower, a stripping water tower and an ammonia purification system, and the phenol-ammonia recovery system is used for preparing 20% ammonia water and crude phenol; in the biochemical treatment stage, the wastewater is sequentially subjected to air floatation, hydrolytic acidification, two-stage A/O and coagulating sedimentation treatment to realize further oil removal, COD (chemical oxygen demand) and ammonia nitrogen pollutant degradation and suspended matter removal; and in the advanced treatment stage, the wastewater after the biochemical treatment stage is sequentially subjected to multi-medium filtration, primary ozone catalytic oxidation, BAF, secondary ozone catalytic oxidation and active carbon filtration, so that the effluent reaches an effluent standard and can be recycled for coke quenching.
Description
Technical Field
The invention relates to a semi-coke wastewater treatment process.
Background
Semi coke is a low volatile solid carbonaceous product obtained by performing low and medium temperature dry distillation and pyrolysis on long flame coal, non-sticky coal, weakly sticky coal and the like. The semi-coke is widely applied to the production of products such as calcium carbide, ferroalloy, ferrosilicon, silicon carbide and the like by gradually replacing metallurgical coke due to the characteristics of high fixed carbon, high specific resistance, high chemical activity, low ash content, low aluminum, low sulfur and low phosphorus, and becomes an irreplaceable carbon material.
Semi coke is a product of medium-low temperature dry distillation (about 550-650 ℃) of coal, and wastewater in the production process mainly comes from circulating water pollution discharge of washing coal gas. Semi coke is a product of low-temperature dry distillation, and 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 and nitrogen and other heterocyclic compounds, the concentration of the semi coke wastewater is much higher than that of coking wastewater, the semi coke wastewater is more difficult to treat, and the environmental hazard is larger.
Water quality meter for general semi-coke waste water
| Contaminants | pH | Petroleum products | Ammonia nitrogen | COD | Sulfide compound | Total phenols |
| Characteristic value | 8.5～10 | ＜4500 | 3000～5000 | 30000～45000 | ＜1000 | 10000～15000 |
Note: the pH is dimensionless and the remaining contaminants are in mg/L.
Semi coke enterprises are generally located in areas with abundant coal resources, and have the problem of water resource shortage in different degrees. Along with the stricter environmental protection regulations in China and the formal promulgation of ten water regulations, the treatment of semi-coke wastewater faces more serious challenges.
Chinese patent application CN104724886A discloses a decarbonization and total nitrogen removal treatment process for semi-coke wastewater, which comprises a pretreatment system, a biochemical treatment system and an advanced treatment system. The pretreatment adopts an oil separation tank and two-stage air flotation, the biochemical treatment system adopts the combination of multifunctional deamination and aerobic-anoxic-aerobic treatment, and the advanced treatment system adopts photocatalytic ozonation and membrane separation. The biochemical treatment system is mainly added with a special microbial agent to realize the 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 quality of the advanced treatment inlet water fluctuates, and the stability of the operation of the membrane separation equipment is doubtful depending on the final outlet water of the membrane separation.
Chinese patent application CN104773930A discloses a semi-coke wastewater treatment system and a process, which comprises a physicochemical treatment system, a biochemical treatment system and an advanced treatment system. The physicochemical 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 moving bed), and the advanced treatment system adopts ozone oxidation, fenton, activated carbon adsorption, CBR and flocculating decoloration. The pretreatment of the physicochemical treatment is mainly chemical oxidation, the mud amount of Fe/C micro-electrolysis and Fenton is large, the process chain of the advanced treatment is long, the operation control difficulty is large, and the operation cost is not economical.
Chinese patent application CN105060628A discloses a semi-coke wastewater treatment method, which comprises a pretreatment system and a biochemical treatment system. The pretreatment adopts the combination of an oil separation tank, coagulation air flotation, phenol extraction and ammonia stripping, and the biochemical treatment system adopts the combination of hydrolytic acidification, anaerobism, A/O (powdered activated carbon) and an aeration biological filter. The pretreatment is better, the system load of a biochemical treatment system can be effectively reduced, but the powdery activated carbon is added, the adding amount is larger, the sludge amount is greatly increased, and the sludge treatment difficulty is increased
Disclosure of Invention
Aiming at the problems in the related art, the invention provides a semi-coke wastewater treatment process method, which aims to solve and optimize the problems of complex system, high energy consumption, unstable operation, high operation cost, difficult treatment effect reaching the 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 wastewater after oil removal is less than 800mg/L, and then the wastewater enters a phenol ammonia recovery system; in the phenol-ammonia recovery system, the wastewater is treated by a deacidification tower, an ammonia still, a phenol extraction tower, a solvent recovery tower, a stripping water tower and an ammonia purification system in sequence and then sent to the biochemical treatment stage, and the phenol-ammonia recovery system is used for preparing 20% ammonia water and crude phenol; in the biochemical treatment stage, the wastewater is sequentially subjected to air floatation, hydrolytic acidification, two-stage A/O and coagulating sedimentation treatment to realize further oil removal, COD (chemical oxygen demand) and ammonia nitrogen pollutant degradation and suspended matter removal; in the advanced treatment stage, the wastewater after the biochemical treatment stage is sequentially subjected to multi-medium filtration, primary ozone catalytic oxidation, BAF, secondary ozone catalytic oxidation and activated carbon filtration, so that the effluent reaches the direct emission limit value in table 2 of discharge Standard of pollutants for coking chemical industry (GB 6171-2012) for coke quenching.
Further, the oil removal comprises two steps, firstly, the semi-coke wastewater is subjected to pre-separation of oil residue and heavy coal tar in a gravity settling tank, and then enters a multiphase flow high-efficiency oil separation device; and (4) independently collecting and recovering the separated coal tar.
Further, after acid gas and ammonia are separated out by the deacidification tower and the ammonia distillation tower, the acidic gas and the ammonia are fed into a phenol extraction tower, extract liquid is fed into a solvent recovery tower to recover an extracting agent, crude phenol obtained after solvent recovery is fed into a crude phenol storage tank, raffinate is fed into a stripping tower, the temperature of wastewater is reduced to below 40 ℃ after the extracting agent is further recovered, and the wastewater is fed into a biochemical treatment stage.
Furthermore, in the biochemical treatment stage, the wastewater collected by the wastewater adjusting tank is subjected to air flotation treatment, demulsifying and coagulating agents (which need to be actually determined) are added, the wastewater is further subjected to oil removal and then enters a hydrolysis acidification tank for hydrolysis acidification, the hydrolysis acidification tank is provided with a water distribution unit, the effluent of the hydrolysis acidification tank automatically flows into a two-section A/O reaction tank, and the degradation of COD and ammonia nitrogen pollutants is realized through two-section combination, nitration liquid backflow and full aeration oxygen supply in the two-section A/O reaction tank; and the effluent of the two-section A/O reaction tank enters a coagulating sedimentation tank after passing through a secondary sedimentation tank, and is sent to an advanced treatment stage after suspended matters are further removed.
Further, in the biochemical treatment stage, air flotation scum, coagulated sludge and biochemical excess sludge are respectively collected according to materialized sludge and biochemical sludge, and sludge dewatering treatment is respectively carried out.
Furthermore, in the advanced treatment stage, effluent filtered by a multi-medium filter and multi-media enters an ozone catalytic oxidation contactor in a self-flowing manner, ozone (40-80 mg/L) is added, and the biochemical performance improvement and chromaticity removal are realized under the synergistic action of catalytic filler; the BAF effluent enters an ozone activated carbon process combining secondary ozone catalytic oxidation and activated carbon filtration, so that the effluent meets the requirement of a direct emission limit value.
Furthermore, after the acid gas and the ammonia are separated out by the deacidification tower and the ammonia distillation tower, the content of ammonia nitrogen in the wastewater is less than 300mg/L.
Further, methyl isobutyl ketone (MIBK) is adopted as an extracting agent in the phenol extraction tower, and the total phenol content after extraction is less than 650mg/L; and after phenol extraction, the recovery of a crude phenol product is realized.
Furthermore, the hydrolysis acidification tank and the two-section A/O reaction tank are designed with biological fillers.
The invention has the following beneficial effects:
1) The oil removing device adopts gravity and multiphase flow to gather and remove oil, and the separated coal tar can create beneficial value;
2) The phenol-ammonia recovery pretreatment is selected, the crude phenol and the ammonia water are recovered, and the wastewater is recycled, so that the biochemical treatment difficulty is greatly improved, and the product with economic value is recovered;
3) The method adopts a sufficient and effective pretreatment process method to create an optimal water inlet condition for a biochemical treatment process so as to enable the efficiency of the biochemical process to be improved possibly;
4) Under the premise of high-efficiency pretreatment, an anaerobic process is abandoned, and the detoxication effect of a hydrolytic acidification process is fully utilized and then the treated water directly enters an A/O process section. By filling the biological filler, the combination of an activated sludge method and a biofilm method is formed, the microbial concentration in the reaction tank is improved, the volume load in the reaction tank is improved, and the utilization efficiency of aeration air is improved, so that the tank capacity is reduced, and the energy consumption is reduced;
5) The advanced treatment adopts a main process of ozone oxidation, emphasizes decolorization and chain scission, and ensures the stability of the final effluent quality;
6) The process monomers adopted by the process scheme are convenient to combine, and the monomer structures can be combined in a blocking manner, so that intensive arrangement is realized, the efficient utilization of the field is realized, and the project occupation is saved;
7) Due to the economic values of coal tar, ammonia water and crude phenol and the energy conservation 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 frame diagram of the process of the present invention;
FIG. 2 is a flow chart of the semi-coke wastewater treatment process of the invention.
Detailed Description
The following description is provided for illustrative purposes and is not intended to limit the invention to the particular embodiments disclosed.
As shown in figures 1 and 2, 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 removal is to better realize phenol ammonia recovery. The oil removal comprises two steps, wherein the semi-coke wastewater is firstly subjected to pre-separation of oil residue and heavy coal tar in a gravity settling tank and then enters a multiphase flow high-efficiency oil separation device;
the separated coal tar is separately collected and recovered, the oil content of the wastewater after oil removal is less than 800mg/L, and the wastewater enters a phenol ammonia recovery system;
the deoiled semi-coke wastewater can safely enter a phenol-ammonia recovery system, and the phenol-ammonia recovery system consists of an deacidification tower, an ammonia still, a phenol extraction tower, a solvent recovery tower, a stripping water tower and an ammonia purification system;
the acid gas and the ammonia are separated out by the deacidification tower and the ammonia still, and after the acid gas and the ammonia are removed, phenol extraction is carried out, so that the working condition of a subsequent phenol extraction section is stable, the efficiency of an extracting agent is maximized, and the using amount and the energy consumption of the extracting agent of the system are reduced; the extracting agent of the extraction tower adopts methyl isobutyl ketone (MIBK), the total phenol content after extraction is less than 650mg/L, and high-efficiency extraction is realized; the extract liquid enters a solvent recovery tower, an extracting agent is recovered and recycled, and the crude phenol after solvent recovery enters a crude phenol storage tank; the raffinate enters a stripping tower, an extracting agent is further recovered, and the water quality of the wastewater entering a subsequent biochemical treatment stage is ensured;
the crude ammonia gas evaporated from the ammonia still is made into 20% ammonia water through an ammonia purification system;
cooling the waste water stripped by the water tower to below 40 ℃, and sending the waste water to a biochemical treatment stage;
wherein, the biochemical treatment stage comprises air floatation, hydrolytic acidification, two-stage A/O and coagulating sedimentation;
collecting the pretreated effluent through a regulating tank, then performing air flotation treatment, adding a demulsification and coagulation agent, further removing oil, and then feeding the water into a hydrolysis acidification tank;
the hydrolysis acidification tank is provided with a water distribution unit to ensure the optimal operation parameters in the hydrolysis tank, and the effluent of the hydrolysis acidification tank automatically flows into the two-section type A/O reaction tank;
the two-section A/O reaction tank is a main reaction area in a biochemical treatment stage, design parameters are calculated according to the actual inflow water quality, and the degradation of pollutants such as COD (chemical oxygen demand), ammonia nitrogen and the like is realized through measures such as two-section 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 an advanced treatment stage after suspended matters are further removed;
air flotation scum, coagulated sludge and biochemical excess sludge are respectively collected according to materialized sludge and biochemical sludge, and sludge dehydration treatment is respectively carried out;
the advanced treatment stage comprises multi-medium filtration, primary ozone catalytic oxidation, BAF, secondary ozone catalytic oxidation and active carbon filtration;
the suspended matters in the coagulating sedimentation effluent need to be filtered by a multi-medium filter, so that the water inlet requirement of the ozone catalytic oxidation contactor can be met;
the effluent of the multi-media filter automatically flows into an ozone catalytic oxidation contactor, ozone is added, organic matters which are difficult to degrade are oxidized and decomposed under the synergistic action of catalytic fillers, and chromaticity molecules are destroyed, so that the improvement of biodegradability and the removal of chromaticity 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 secondary ozone catalytic oxidation and activated carbon filtration, the organic matter and chromaticity removal effect is consolidated and improved, and the direct emission limit value in Table 2 of coking chemical industry pollutant emission Standard (GB 6171-2012) can be stably reached for recycling and quenching.
In the invention, the deacidification and the deamination can be respectively removed by double towers or synchronously removed by a single tower, the ammonia nitrogen content in the wastewater can be less than 300mg/L after the two processes are carried out, and the overall target of the semi-coke wastewater process scheme is not influenced; the air flotation in the biochemical treatment stage can be ordinary air flotation or nitrogen air flotation, which can cause the change of water quality and chromaticity in the subsequent process, but the final effluent chromaticity is not influenced due to the arrangement of advanced treatment two-stage ozone catalytic oxidation, and the overall target of the semi-coke wastewater process scheme is not influenced; a water distribution area is arranged for hydrolytic acidification, so that the treatment performance of hydrolytic acidification is effectively improved; biological fillers are designed in the hydrolysis acidification tank and the two-section A/O reaction tank, 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 is combined with BAF or activated carbon, which is beneficial to fully utilizing ozone, reducing ozone consumption and reducing system energy consumption; the advanced treatment adopts an ozone oxidation process which is specially set for the problem of chromaticity of the semi-coke wastewater, and the selection of a multi-stage ozone process is determined according to the requirement of effluent quality, so that the overall target of the semi-coke wastewater process scheme is not influenced; the materialized sludge and the biochemical sludge are respectively collected and treated, so that the treatment difficulty of the tail end sludge is reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The 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 wastewater after oil removal is less than 800mg/L, and then the wastewater enters a phenol ammonia recovery system;
in the phenol-ammonia recovery system, the wastewater is sent to the biochemical treatment stage after being sequentially 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, and the phenol-ammonia recovery system is used for preparing 20% ammonia water and crude phenol;
in the biochemical treatment stage, the wastewater is sequentially subjected to air floatation, hydrolytic acidification, two-stage A/O and coagulating sedimentation treatment to realize further oil removal, COD (chemical oxygen demand) and ammonia nitrogen pollutant degradation and suspended matter removal;
in the advanced treatment stage, the wastewater after the biochemical treatment stage is sequentially subjected to multi-medium filtration, primary ozone catalytic oxidation, BAF, secondary ozone catalytic oxidation and activated carbon filtration, so that the effluent reaches the direct emission limit value in table 2 of discharge Standard of pollutants for coking chemical industry (GB 6171-2012) for coke quenching.
2. The semi-coke wastewater treatment process according to claim 1, characterized in that: the oil removal comprises two steps, firstly, the semi-coke wastewater is subjected to pre-separation of oil residue and heavy coal tar in a gravity settling tank, and then enters a multiphase flow high-efficiency oil separation device; and (4) independently collecting and recovering the separated coal tar.
3. The semi-coke wastewater treatment process according to claim 1, wherein the acid gas and ammonia are separated in the deacidification tower and the ammonia still, the acidic gas and ammonia are fed into the phenol extraction tower, the extract liquid is fed into the solvent recovery tower, the extractant is recovered, the crude phenol after the solvent recovery is fed into the crude phenol storage tank, the raffinate is fed into the stripping tower, the extractant is further recovered, and the wastewater is cooled to below 40 ℃ and is fed into the biochemical treatment stage.
4. The semi-coke wastewater treatment process according to claim 1, wherein in the biochemical treatment stage, wastewater collected by a wastewater adjusting tank is subjected to air floatation treatment, demulsification and coagulation agents are added, the wastewater further subjected to oil removal enters a hydrolysis acidification tank for hydrolysis acidification, the hydrolysis acidification tank is provided with a water distribution unit, effluent of the hydrolysis acidification tank automatically flows into a two-section A/O reaction tank, and COD and ammonia nitrogen pollutants are degraded in the two-section A/O reaction tank through two-section combination, nitration liquid reflux and full aeration oxygen supply; and the effluent of the two-section A/O reaction tank enters a coagulating sedimentation tank after passing through a secondary sedimentation tank, and is sent to an advanced treatment stage after suspended matters are further removed.
5. The semi-coke wastewater treatment process according to claim 4, wherein in the biochemical treatment stage, the air flotation scum, the coagulation sludge and the biochemical excess sludge are collected respectively according to materialized sludge and biochemical sludge, and are subjected to sludge dehydration treatment respectively.
6. The semi-coke wastewater treatment process according to claim 1, wherein in the advanced treatment stage, effluent filtered by a multi-media filter and multiple media enters an ozone catalytic oxidation contactor in a self-flowing manner, and is added with 40-80 mg/L of ozone, so that biochemical performance improvement and chromaticity removal are realized under the synergistic effect of catalytic filler; and the BAF effluent enters an ozone activated carbon process combining secondary ozone catalytic oxidation and activated carbon filtration, so that the effluent meets the requirement of the direct emission limit value.
7. The semi-coke wastewater treatment process according to claim 3, wherein the acid gas and the ammonia are separated from the acid gas and the ammonia by the deacidification tower and the ammonia distillation tower, and the ammonia nitrogen content in the wastewater is less than 300mg/L.
8. The semi-coke wastewater treatment process as claimed in 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; and after phenol extraction, crude phenol product recovery is realized.
9. The semi-coke wastewater treatment process according to claim 4, wherein the hydrolysis acidification tank and the two-stage A/O reaction tank are designed with biological fillers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210925410.1A CN115304216A (en) | 2022-08-03 | 2022-08-03 | Semi-coke wastewater treatment process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210925410.1A CN115304216A (en) | 2022-08-03 | 2022-08-03 | Semi-coke wastewater treatment process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115304216A true CN115304216A (en) | 2022-11-08 |
Family
ID=83858959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210925410.1A Pending CN115304216A (en) | 2022-08-03 | 2022-08-03 | Semi-coke wastewater treatment process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115304216A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104724888A (en) * | 2015-03-24 | 2015-06-24 | 浙江汉蓝环境科技有限公司 | Decarbonization and total nitrogen removal treating process for semi-coking wastewater |
| CN104724886A (en) * | 2015-03-24 | 2015-06-24 | 浙江汉蓝环境科技有限公司 | Decarbonization and total nitrogen removal treating process for semi-coking wastewater |
| CN105060628A (en) * | 2015-08-04 | 2015-11-18 | 重庆杰润科技有限公司 | Semi-coke wastewater treatment method |
-
2022
- 2022-08-03 CN CN202210925410.1A patent/CN115304216A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104724888A (en) * | 2015-03-24 | 2015-06-24 | 浙江汉蓝环境科技有限公司 | Decarbonization and total nitrogen removal treating process for semi-coking wastewater |
| CN104724886A (en) * | 2015-03-24 | 2015-06-24 | 浙江汉蓝环境科技有限公司 | Decarbonization and total nitrogen removal treating process for semi-coking wastewater |
| CN105060628A (en) * | 2015-08-04 | 2015-11-18 | 重庆杰润科技有限公司 | Semi-coke wastewater treatment method |
Non-Patent Citations (1)
| Title |
|---|
| 李兵兵等: "兰炭废水处理技术", 《燃料与化工》, vol. 48, no. 2, pages 50 - 52 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108147612B (en) | Method for treating coal carbonization wastewater | |
| CN103553269A (en) | Method and device for treating and recycling semi-coke wastewater | |
| CN109437454B (en) | Enhanced physicochemical treatment method and device for refined high-salt high-ammonia special oily sewage | |
| CN109020090A (en) | A kind of high concentration hard-degraded organic waste water processing unit and method | |
| CN104773930A (en) | Semi-coke waste water treatment system and technology | |
| CN112624466A (en) | Coal chemical industry wastewater pretreatment method | |
| CN110894125A (en) | Sewage treatment process for recycling N-methyl pyrrolidone | |
| CN207362005U (en) | A kind of Zero-discharge coked wastewater treatment system | |
| CN112939352B (en) | Treatment method of comprehensive sewage of industrial park | |
| CN112851053A (en) | Wastewater treatment system and method | |
| CN101921046B (en) | New process for treating coal gasification wastewater with active coke | |
| CN113444546A (en) | Purification treatment method for coke oven crude gas and tar ammonia water mixture | |
| CN107902829B (en) | Cold rolling oil-containing and emulsion wastewater recycling process and device thereof | |
| CN105601055A (en) | Semi-coke wastewater multi-level treatment technology | |
| CN112079524B (en) | Oily sewage treatment system and treatment process | |
| CN104944691A (en) | Semicoke wastewater treatment and regeneration and resource reclamation device based on membrane concentration | |
| CN104071918B (en) | A kind of pretreating process of Coal Chemical Industry high-concentration sewage | |
| CN115304216A (en) | Semi-coke wastewater treatment process | |
| CN214990975U (en) | Wastewater treatment system | |
| CN107082521B (en) | Pretreatment system for treating high-salt high-concentration organic wastewater | |
| CN104860490A (en) | Device for treating and regenerating semi-coke wastewater and recycling resources | |
| CN217996985U (en) | Semi-coke wastewater treatment system | |
| CN216472731U (en) | Blue charcoal waste water resourceful treatment device | |
| CN209193733U (en) | A kind of high concentration hard-degraded organic waste water processing unit | |
| CN109399856A (en) | A kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Yinhui Inventor after: Li Feng Inventor after: Qi Jiawei Inventor after: Shen Caihong Inventor after: Zhou Hua Inventor after: Qian Jin Inventor after: Wang Hongxia Inventor before: Chen Yinhui Inventor before: Li Feng Inventor before: Qi Jiawei Inventor before: Shen Caihong Inventor before: Zhou Hua Inventor before: Qian Jin Inventor before: Wang Hongxia |