CN109516589B - Process for treating coking wastewater by membrane method - Google Patents
Process for treating coking wastewater by membrane method Download PDFInfo
- Publication number
- CN109516589B CN109516589B CN201710852593.8A CN201710852593A CN109516589B CN 109516589 B CN109516589 B CN 109516589B CN 201710852593 A CN201710852593 A CN 201710852593A CN 109516589 B CN109516589 B CN 109516589B
- Authority
- CN
- China
- Prior art keywords
- wastewater
- membrane
- ozone
- treatment
- ammonia nitrogen
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 105
- 239000002351 wastewater Substances 0.000 title claims abstract description 82
- 239000012528 membrane Substances 0.000 title claims abstract description 80
- 230000008569 process Effects 0.000 title claims abstract description 53
- 238000004939 coking Methods 0.000 title claims abstract description 41
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 31
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical class C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000000919 ceramic Substances 0.000 claims abstract description 13
- 239000012510 hollow fiber Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000003921 oil Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 238000004042 decolorization Methods 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000004907 flux Effects 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000009615 deamination Effects 0.000 description 10
- 238000006481 deamination reaction Methods 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 239000010865 sewage Substances 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical compound CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000009287 sand filtration Methods 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000000813 microbial effect Effects 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000108 ultra-filtration 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
- C02F1/40—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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a process for treating coking wastewater by a membrane method, which comprises the following steps: 1) removing oil and suspended matter impurities in the coking wastewater by using a modified ceramic membrane; 2) removing ammonia nitrogen by using a composite hollow fiber membrane; 3) dephenolizing the modified PDMS film; 4) and (3) carrying out oxidation decoloration treatment on the wastewater after oil removal, ammonia nitrogen removal and phenol removal by using an ozone circulation oxidizer. The process of the invention carries out pipeline flow treatment on the coking wastewater, can effectively prevent the problem of easy transfer of pollutants, and solves the problems of poor membrane hydrophobicity, poor selectivity and low membrane flux in the membrane method ammonia nitrogen removal and membrane dephenolization processes.
Description
Technical Field
The invention belongs to the technical field of high ammonia nitrogen wastewater treatment, particularly relates to coking wastewater treatment, and particularly relates to a process for treating coking wastewater by a membrane method.
Background
The coking wastewater is industrial wastewater containing volatile components, polycyclic aromatic hydrocarbons, heterocyclic compounds such as oxygen, sulfur, nitrogen and the like, which is generated in the processes of high-temperature dry distillation, purification and byproduct recovery of coking and coal gas, and is industrial organic wastewater which has high COD, high phenol value and high ammonia nitrogen and is difficult to treat.
At present, most of coking wastewater treatment processes adopted by domestic coking plants are process flows taking traditional biological denitrification as a core, and generally comprise pretreatment, biochemical treatment and advanced treatment. Wherein, the pretreatment mainly adopts a physical and chemical method, such as oil removal, ammonia removal, extraction dephenolization and the like, and COD and ammonia nitrogen can be respectively reduced to below 3000mg/L and 300mg/L in the stage; the biochemical treatment process is mainly A/O, A2/O2After the biochemical treatment stage, the COD and the ammonia nitrogen can be further reduced to be below 100mg/L and 10mg/L respectively; the main processes of the advanced treatment include an activated carbon adsorption method, an activated carbon-biofilm method, an oxidation pond method and the like.
The technical current situation of the traditional pretreatment stage is as follows:
1.0 oil and impurity removing technology for traditional coking wastewater
Currently, air floatation and oil separation methods are mainly adopted to remove oil and impurities, in patent CN 105884142A, carbon filtration, sand filtration or multi-medium filtration is firstly adopted to remove impurities, and then nitrogen air floatation is adopted to remove oil from obtained clear liquid. However, because the content of cyclic organic matters in the coal tar is high, and partial components contain carboxyl and other groups with surface activity and are difficult to combine with bubbles, the oil content of the effluent after air floatation oil removal is also high, only dispersed oil with larger particle size can be intercepted by carbon filtration or sand filtration, the oil removal efficiency is low, the working period is short, and the backwashing frequency is high; in patent CN 105174558A, a combined process of 'heavy medium loading coagulation degreaser + circular air flotation tank + PTFE membrane microfiltration' is adopted to remove oil substances in gas making wastewater, but in the process, acid and demulsifier need to be added, and the related equipment has more and complicated processes and higher energy consumption.
1.1 traditional coking wastewater deamination technology
The traditional deamination method comprises an air stripping method, a chemical precipitation method, a breakpoint chlorination method and the like, and the patent CN205204859U provides a rapid degassing device which integrates aeration and degassing, can fully discharge ammonia blown out from wastewater by air, improves the purification efficiency, but has the problems of easy pollution transfer and low treatment efficiency in the aeration process; the patent CN 104261501A adopts an air stripping method to treat ammonia nitrogen in the municipal landfill leachate, the ammonia nitrogen stripping rate is more than 80%, but the air stripping method has the defects of high operation cost, easy corrosion of equipment, easy pollution transfer and the like; the patent CN 1493528A uses a chemical precipitation method to treat ammonia nitrogen wastewater, the ammonia nitrogen removal rate can reach more than 95 percent, but the technology generates a large amount of chemical precipitation sludge, the operation cost is high, and the industrial application is not facilitated; the patent CN 103011441A adopts a breakpoint chlorination method to treat ammonia nitrogen wastewater, but the technology has better treatment effect on low-concentration ammonia nitrogen wastewater, and the operation cost is increased due to the addition of an oxidant.
1.2 traditional coking wastewater dephenolization technology
Common dephenolizing technologies comprise steam dephenolization, active coke adsorption dephenolization, extraction dephenolization and the like, and patent CN 104998433A discloses a steam stripping dephenolization device and a steam stripping dephenolization method, wherein phenol-containing wastewater is fully contacted with steam to ensure that phenol enters a gas phase from a liquid phase to realize dephenolization treatment, but the method has higher energy consumption due to larger steam use; bikejun et al in the technical discussion of dephenolization of waste water from coal chemical industry of literature points out: when the active coke is used for recovering phenol, the colored substances are difficult to elute after being adsorbed, so that the service life of the active carbon is influenced, and meanwhile, the method is not suitable for high-concentration phenol-containing wastewater; the patent CN 105540969A discloses an efficient and economical extraction method of phenol-containing wastewater, which comprises the steps of adopting leaf oil alcohol as an extracting agent, firstly filling the leaf oil alcohol and the phenol-containing wastewater after impurity removal into an extraction container according to a certain proportion for extraction, and the solvent extraction method is suitable for high-concentration wastewater treatment, and the used equipment is large and large in dosage, and is easy to cause secondary pollution.
2.0 coking wastewater biochemical treatment technical current situation:
coking wastewater generally adopts different forms of A/O and A2/O2The biological denitrification process is used for further treating the ammonia nitrogen wastewater, and a corresponding process route is designed by the patent CN 1562806A by utilizing the biological denitrification technology, so that the treated ammonia nitrogen wastewater reaches the national specified discharge standard. The patent CN101549907A designs a membrane biological reaction device for treating high ammonia nitrogen industrial wastewater by utilizing a biological deamination method to treat ammonia nitrogen wastewater, and the biological denitrification process needs to use a large amount of microorganismsThe requirement on the quality of wastewater is high, the occupied area of equipment is large, and the operation conditions are harsh; in addition, the activity of the microorganisms is inhibited by high-concentration ammonia nitrogen, sulfide and cyanide, so that the biological denitrification effect is poor. (advanced treatment and recycle process and device for wastewater from specialized coking CN 104876403A)
3.0 coking wastewater advanced treatment State of the Art
The advanced treatment stage comprises two main types of aiming at standard discharge and system recycling, including an oxidation pond, an activated carbon adsorption method and the like. At present, the research on the advanced treatment of the coking wastewater is many, but most of the methods cannot be operated stably, for example, some coking plants adopt chemical agents such as fenton reagent or discharge the coking wastewater after high-efficiency coagulation, but the methods may cause secondary pollution and corrode equipment and pipelines.
The method is characterized in that CN 105884089A is based on an oxidation pond method, domestic sewage of villages and towns is introduced into an oxidation pond, an aeration device and a microorganism attachment carrier which are arranged in the oxidation pond construct a technical system of a biological contact oxidation method, the advantages of the traditional oxidation pond method and the advantages of the biological contact oxidation method are combined, the treatment cost is reduced, the treatment efficiency is low, and pollution transfer is easy to generate; the patent CN 105884089A discloses a coking wastewater advanced treatment and recycling process, which comprises five stages of coagulating sedimentation, vortex air flotation, multi-medium filtration, ozone oxidation, activated carbon adsorption and double-membrane method desalination, and has the characteristics of stable operation, low cost, high operation elasticity and high impact resistance; patent CN 103466890A provides a coking wastewater advanced treatment and reuse and application method thereof, which adopts a multi-medium filter, an ultrafiltration device, a resin adsorption device and a reverse osmosis device in sequence, and the produced water obtained by using the method is directly used as make-up water to be reused in a production clean circulation system.
Second, background technological progress analysis
1. Development of coking wastewater pretreatment technology
In recent years, the membrane separation technology has the advantages of high separation efficiency, low energy consumption, no pollution, convenient operation, small occupied area and the like due to the functions of separation, concentration and purification, is applied to part of links in the pretreatment of the coking wastewater, and is expected to completely replace the processes of oil removal, ammonia removal, extraction dephenolization and the like in the traditional coking wastewater treatment.
In the aspect of membrane method oil removal: in patent CN 105174588A, a combined process of 'heavy medium loading coagulation degreaser + circular air flotation tank + PTFE membrane microfiltration' is adopted to remove oil in gas-making wastewater in a classified manner step by step, so that the oil removal rate is high; the application of a ceramic membrane filter in an ammonia water degreasing process reports that a filter material with a PT963 filter material is used for separating oil substances in residual ammonia water; in patent CN 103466656a, a membrane absorption method is used to remove oil in ammonia water, a membrane method is used to remove high-carbon oil, a chemical method is used to remove low-carbon oil, and a resin method is used to remove water-soluble oil. However, the flux of the PTFE membrane and ceramic membrane used in the above patents is insufficient, and thus cannot meet the requirements of industrial applications; patent CN 105819610A provides a method and device for removing oil by ammonia still, the residual ammonia water produced in coking process is once removed tar by air-float tar remover of air-cooling unit, filtered by ceramic filter and then enters ammonia still for ammonia still treatment, such oil removing process is tedious, and oil removing efficiency is low.
In the aspect of membrane deamination: in patent CN 104229937A, a PTFE heterogeneous hollow fiber membrane subjected to oleophobic modification is used as a membrane contactor to remove free ammonia; patent CN 205045930U is penetrated vacuum pump and multistage deamination membrane module with the help of water, provides the processing apparatus who contains ammonia waste water, and traditional acidic absorbent such as sulphuric acid has been abandoned to this patent, can not produce the dilute solution of a large amount of ammonium sulfate, can not cause secondary pollution. However, during the use process, because the membrane filaments are not highly hydrophobic, part of water can permeate the membrane along with free ammonia, and the separation effect is influenced.
In the aspect of membrane dephenolization: the patent CN 104258746A adopts organic modifier oleyl alcohol to modify a PDMS membrane to prepare an organic silicon dephenolization membrane, the membrane has higher selectivity, the adsorption effect of oleyl alcohol in feed liquid is avoided, and the operation stability of the membrane is ensured; in the research of treating phenolic wastewater by using the PDMS/PS composite hollow fiber membrane, the prepared silicone rubber/polysulfone composite hollow fiber membrane is used, and alkali liquor is used as an extracting agent to treat phenolic wastewater, so that a good effect is achieved. The removal effect of phenol can reach 99.9 percent and 96.9 percent; patent CN 101077799a discloses a pervaporation blending composite membrane for dephenolization of wastewater, which separates a feed stream into a retentate with low phenol content and a permeate with high phenol content with high selectivity in a wastewater dephenolization test; also, these membranes have a small flux and poor hydrophobicity, and are difficult to be applied to practical industrial production. 2. Technological development of biochemical method
In the aspect of biochemical treatment: the patent CN 104671410A further improves the traditional A/O process, invents a method suitable for further denitrification of high ammonia nitrogen wastewater, overcomes the bottleneck that the denitrification rate of the traditional process is limited by the reflux ratio, can achieve the denitrification rate, has high denitrification rate but relatively small treatment capacity, and cannot meet the treatment requirement of industrial wastewater; AAO is a sewage treatment process for realizing dephosphorization and denitrification and organic matter removal by utilizing microbial flora, and patent CN 106006975A utilizes the AAO sewage treatment process, and treated sewage respectively enters different sections for treatment according to different carbon-nitrogen ratios and carbon-phosphorus ratios, so that different carbon source requirements of each process section are realized, and the purposes of reducing treatment energy consumption and cost are realized while the dephosphorization and denitrification effects are ensured.
In addition, the biochemical treatment of coking wastewater requires consideration of wastewater Biodegradability (BOD)5And CODcrIs evaluated) and, in general, BOD5/CODcrThe larger the value, the better the biotreatability of the wastewater, when the BOD of the wastewater to be treated is5/CODcrValues less than 0.2 indicate that biochemical treatment is not suitable. BOD of coking wastewater in actual production process5/CODcrThe value is about 0.1, biochemical treatment is carried out after the biodegradability is improved by other auxiliary methods such as an ozone oxidation method, the process is complicated, and meanwhile, the use of an aeration tank in the biochemical treatment process can transfer gas-phase pollutants into the air to generate secondary pollution.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a coking wastewater treatment process adopting a full-membrane method, non-biochemical treatment and whole-process pipelining, which has the following thought: firstly, removing impurities such as oil, suspended matters and the like in the coking wastewater by using a modified ceramic membrane, then removing ammonia nitrogen by using a composite hollow fiber membrane, then performing dephenolization treatment by using a modified PDMS membrane, finally performing ozone oxidation decoloration treatment on the wastewater after oil removal, deamination and dephenolization by using an ozone circulation oxidizer, removing organic matters in the wastewater to obtain treated water which can reach the standard discharge, and also being used as supplementary circulating water after RO membrane treatment.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a process for treating coking wastewater by a membrane method is characterized by comprising the following steps:
1) removing impurities such as oil, suspended matters and the like in the coking wastewater by using a modified ceramic membrane;
2) ammonia nitrogen removed by using a composite hollow fiber membrane;
3) dephenolizing the modified PDMS film;
4) carrying out oxidation and decoloration treatment on the wastewater after oil removal, ammonia nitrogen removal and phenol removal by using an ozone circulation oxidizer, further removing organic pollutants in the wastewater, achieving the aim of decoloring the wastewater and obtaining treated water which can directly reach the discharge standard, wherein in actual use, the sequence of the step 2) and the step 3) can be adjusted according to requirements;
further, the modified ceramic membrane is prepared by using alumina and zirconia as main raw materials, using ZSM-5 molecular sieve nanoparticles as a hydrophobic modifier and using starch as a pore-foaming agent and firing the raw materials at a high temperature, wherein the proportion of each component is 30-55% of the alumina and the zirconia, 0.5-8% of the ZSM-5 and 5-30% of the starch, and the content of suspended matters can be reduced to 25-40 mg/L after the modified ceramic membrane is filtered by the membrane.
Further, the composite hollow fiber membrane is a composite membrane which is prepared by mixing polypropylene (PP) and polyvinylidene fluoride (PVDF) in any proportion as base membrane materials and modifying the base membrane materials by calcium chloride, silicon dioxide nano particles and carbon nano tube hydrophobic substances. The addition amount of the hydrophobic substance is 0.1-30% of the weight of the substrate membrane material, and the ammonia nitrogen content can be reduced to below 35-100 mg/L after the membrane filtration.
Furthermore, TiO is added into the PDMS membrane casting solution in the preparation process of the modified PDMS dephenolized membrane2Nanoparticles to enhance the hydrophobicity of the membrane, PDMS and TiO2The mass ratio of the nano particles is 15:1, and after the nano particles are filtered by the membrane, the content of volatile phenol can be reduced to be below 0.01-0.03 mg/L.
Furthermore, the ozone circulation oxidizer is characterized in that when in operation, wastewater to be treated enters the ozone circulation oxidizer through a sewage inlet of the ozone circulation oxidizer, ozone is sucked into the ejector through the ozone inlet, the ozone and the ejector are fully mixed in the oxidation chamber, after full reaction, a part of liquid after decoloration treatment is discharged through a liquid outlet, and the other part of wastewater which is not fully decolored is pumped back into the oxidation chamber through the circulating pump to continue the reaction.
Further, the volume ratio of ozone to wastewater to be treated is 50: 1 when the ozone circulation oxidizer works, the retention time of the wastewater is 1-2 h, and the circulation amount of the centrifugal pump accounts for 30-50% of the feeding amount.
The invention has the beneficial effects that: the membrane method is adopted to treat the coking wastewater in the whole process, the pipelining process can effectively prevent the problems of easy transfer of pollution and the like in the treatment process of the traditional coking wastewater, and solves the problems of poor membrane hydrophobicity, poor selectivity and low membrane flux in the membrane method ammonia nitrogen removal and membrane method dephenolization processes.
Drawings
FIG. 1 is a process flow diagram of coking wastewater treatment by the membrane method of the invention.
FIG. 2 is a schematic diagram of the operation of an ozone circulation oxidizer in the process for treating coking wastewater by a membrane method.
In the figure: 1 sewage inlet, 2 ozone inlet, 3 ejector, 4 oxidation chamber, 5 liquid outlet, 6 circulating pump.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1, the modified ceramic membrane degreasing and impurity removing process of the invention:
under the conditions that the temperature is 25 ℃, the operating pressure is 0.10MPa and the cross flow speed is 2.5m/s, the modified ceramic membrane is adopted to carry out oil removal and impurity removal treatment on the coking wastewater, and the content of suspended matters in the treatment solution after the treatment of the modified ceramic membrane can be reduced to 31 mg/l.
Example 2, the deamination process of the composite hollow fiber membrane of the present invention:
performing deamination treatment on a treatment solution after oil removal and impurity removal by adopting a composite hollow fiber membrane deamination process, adding sodium hydroxide to adjust the pH value of the treatment solution to 11.00 in the operation process to ensure that ammonia nitrogen in wastewater mainly exists in a free state, then filtering by using a composite hollow fiber membrane, controlling the temperature of the treatment solution to be 45 ℃, the filtering pressure to be 0.1Mpa, and performing NH treatment on the obtained treatment solution3The content of-N was 12.68 mg/l.
Example 3, dephenolation process of modified PDMS of the present invention:
and (3) under the conditions that the temperature is 25 ℃, the operation pressure is 0.10MPa and the cross flow speed is 2.5m/s, a modified PDMS dephenolizing process is adopted to dephenolize the deaminated treatment liquid, and the volatile phenol content in the treatment liquid treated by the modified PDMS dephenolizing process can be reduced to 0.02 mg/l.
Example 4, the ozone loop oxidation decoloration process of the invention:
the wastewater after oil removal, deamination and dephenolization is decolorized by adopting an ozone circulation oxidizer, the wastewater to be treated enters the ozone circulation oxidizer through a sewage inlet 1 of the ozone circulation oxidizer, ozone is sucked into an ejector 3 through an ozone inlet 2, the ozone and the ejector are fully mixed in an oxidation chamber 4, and after full reaction, a part of the wastewater which is not fully decolorized is pumped back into the oxidation chamber 4 through a circulating pump 6 for continuous reaction. The wastewater after the decolorization treatment is clear and transparent, is discharged through a liquid outlet 5 and is measuredCOD, BOD of the discharge water567.00 and 15.00mg/l, respectively.
The index content of water quality before and after treatment and the national first-class discharge standard in the above examples are shown in Table 1, wherein GB 11901-89 'gravimetric method for measuring water suspended matters' is adopted for measuring suspended matters in the examples; COD is detected according to a rapid digestion spectrophotometry HJ/T399-; BOD5Detection is performed according to HJ 505-; the volatile phenol is determined according to 4-aminoantipyrine spectrophotometry HJ 503-2009; NH (NH)3The determination of-N is based on the Nessler reagent spectrophotometry HJ 535-2009.
TABLE 1 Water quality index content before and after treatment and national first-class discharge Standard
As can be seen from Table 1, after the coking wastewater is treated by the process provided by the invention, various pollution indexes in the wastewater are effectively treated and all meet the national primary wastewater discharge standard.
Claims (3)
1. A process for treating coking wastewater by a membrane method is characterized by comprising the following steps:
1) removing oil and suspended matter impurities in the coking wastewater by using a modified ceramic membrane;
2) removing ammonia nitrogen by using a composite hollow fiber membrane;
3) dephenolizing the modified PDMS film;
4) carrying out oxidation decoloration treatment on the wastewater after oil removal, ammonia nitrogen removal and phenol removal by using an ozone circulation oxidizer;
wherein the sequence of the step 2) and the step 3) can be adjusted;
the modified ceramic membrane is prepared by using alumina and zirconia as main raw materials, using ZSM-5 molecular sieve nano particles as a hydrophobic modifier and starch as a pore-foaming agent and sintering at high temperature, wherein the proportion of each component is 30-55% of each of the alumina and the zirconia, 50.5-8% of the ZSM and 5-30% of the starch;
the composite hollow fiber membrane is a composite membrane which is prepared by mixing polypropylene and polyvinylidene fluoride in any proportion as a base membrane material and modifying the base membrane material by calcium chloride, silicon dioxide nano particles and carbon nano tube hydrophobic substances, wherein the addition amount of the hydrophobic substances is 0.1-30% of the weight of the base membrane material;
in the preparation process of the modified PDMS dephenolized membrane, TiO is added into PDMS membrane casting solution2Nanoparticles, said PDMS and TiO2The mass ratio of the nanoparticles was 15: 1.
2. The process as claimed in claim 1, wherein the oxidation and decolorization treatment using the ozone circulation oxidizer is carried out by introducing the wastewater to be treated into the ozone circulation oxidizer through a wastewater inlet, sucking ozone into the ejector through the ozone inlet, mixing and reacting the wastewater and ozone in the oxidation chamber, and discharging the decolorized wastewater through a liquid outlet.
3. The process as claimed in claim 2, wherein the volume ratio of the ozone to the wastewater is 50: 1, the retention time of the wastewater is 1-2 h, and the circulation amount of a centrifugal pump of the ozone circulation oxidizer accounts for 30-50% of the wastewater feeding amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710852593.8A CN109516589B (en) | 2017-09-20 | 2017-09-20 | Process for treating coking wastewater by membrane method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710852593.8A CN109516589B (en) | 2017-09-20 | 2017-09-20 | Process for treating coking wastewater by membrane method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109516589A CN109516589A (en) | 2019-03-26 |
| CN109516589B true CN109516589B (en) | 2020-11-17 |
Family
ID=65767794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710852593.8A Expired - Fee Related CN109516589B (en) | 2017-09-20 | 2017-09-20 | Process for treating coking wastewater by membrane method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109516589B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921927A (en) * | 2019-12-30 | 2020-03-27 | 杨咪咪 | Advanced oxidation treatment process method for coking wastewater |
| CN114538649A (en) * | 2021-12-31 | 2022-05-27 | 南京万德斯环保科技股份有限公司 | Kitchen biogas slurry treatment method |
| CN115557574A (en) * | 2022-10-20 | 2023-01-03 | 徐州水处理研究所 | Process for recycling ammonium sulfate and ammonium chloride wastewater by full membrane method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10139559A1 (en) * | 2001-08-10 | 2003-02-20 | Creavis Tech & Innovation Gmbh | Hybrid membranes including a polymer separation layer and a ceramic support material useful nanofiltration, reverse osmosis, ultrafiltration, and microfiltration and in pressure membrane processes |
| CN101525191A (en) * | 2009-04-27 | 2009-09-09 | 河南洁源膜分离科技有限公司 | Coking wastewater membrane method treating process |
| CN102849875A (en) * | 2012-10-12 | 2013-01-02 | 中国矿业大学(北京) | System for deep treatment of coking wastewater by means of catalytic ozonation-ceramic membrane filtration |
| CN105417868A (en) * | 2015-12-07 | 2016-03-23 | 上海森松化工成套装备有限公司 | Circulating-type sewage treatment combined device |
| CN106669440A (en) * | 2017-01-03 | 2017-05-17 | 中国石油天然气股份有限公司 | Modification method of ceramic membrane and modified ceramic membrane |
| CN106823835A (en) * | 2016-12-07 | 2017-06-13 | 清华大学 | A kind of ammonolysis inhale film and preparation method thereof |
-
2017
- 2017-09-20 CN CN201710852593.8A patent/CN109516589B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10139559A1 (en) * | 2001-08-10 | 2003-02-20 | Creavis Tech & Innovation Gmbh | Hybrid membranes including a polymer separation layer and a ceramic support material useful nanofiltration, reverse osmosis, ultrafiltration, and microfiltration and in pressure membrane processes |
| CN101525191A (en) * | 2009-04-27 | 2009-09-09 | 河南洁源膜分离科技有限公司 | Coking wastewater membrane method treating process |
| CN102849875A (en) * | 2012-10-12 | 2013-01-02 | 中国矿业大学(北京) | System for deep treatment of coking wastewater by means of catalytic ozonation-ceramic membrane filtration |
| CN105417868A (en) * | 2015-12-07 | 2016-03-23 | 上海森松化工成套装备有限公司 | Circulating-type sewage treatment combined device |
| CN106823835A (en) * | 2016-12-07 | 2017-06-13 | 清华大学 | A kind of ammonolysis inhale film and preparation method thereof |
| CN106669440A (en) * | 2017-01-03 | 2017-05-17 | 中国石油天然气股份有限公司 | Modification method of ceramic membrane and modified ceramic membrane |
Non-Patent Citations (3)
| Title |
|---|
| PDMS渗透蒸发膜的制备及其处理含酚废水的研究;马克;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20100815(第8期);第67-68页 * |
| 一种高效陶瓷膜用于焦化废水除油的中试研究;沈廷万;《四川化工》;20161231;第9-11页 * |
| 水处理陶瓷膜制备与应用技术研究进展;胡晓勇等;《城镇供水》;20170228;第78-80页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109516589A (en) | 2019-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9656895B2 (en) | Method for treating a waste stream using a bioreactor and a membrane filter | |
| CN103288309B (en) | Coal gasification wastewater zero-emission treatment method, and application thereof | |
| CN203568944U (en) | Coking wastewater reuse treatment system | |
| CN103803752B (en) | Treatment method of wastewater with high salinity and high organic matters | |
| US20110253624A1 (en) | Anaerobic digester-membrane bioreactor for treating a waste stream | |
| CN103288310B (en) | Slack coal pressure gasification wastewater treatment method and treatment system as well as application | |
| CN107857438B (en) | Zero-emission process for wastewater treatment of chemical enterprises and parks | |
| CN105016577A (en) | Advanced treatment system for process sewage and advanced treatment method for sewage | |
| CN109516589B (en) | Process for treating coking wastewater by membrane method | |
| CN110723870A (en) | Treatment and resource utilization method of phenol wastewater | |
| CN104386881B (en) | A kind of Coal Chemical Industry production wastewater treatment and high power reuse technology and dedicated system thereof | |
| CN210764701U (en) | Domestic waste leachate pretreatment device based on deamination membrane component | |
| CN203360192U (en) | Treatment device for difficultly degradable industrial wastewater | |
| KR102100991B1 (en) | Liquefied fertilizer purification apparatus using porous ceramic membrane | |
| CN108358395B (en) | Treatment process of pesticide production wastewater | |
| CN111115661B (en) | Nitric acid wastewater treatment system and method | |
| CN107129081B (en) | 2B acid acidification wastewater treatment and resource recovery process | |
| CN104944691A (en) | Semicoke wastewater treatment and regeneration and resource reclamation device based on membrane concentration | |
| CN105884142A (en) | Coal chemical industry waste water treatment process and device | |
| CN110642382A (en) | Anaerobic and aerobic composite biological treatment desalting method | |
| CN104860490A (en) | Device for treating and regenerating semi-coke wastewater and recycling resources | |
| KR20200000056A (en) | The method and apparatus for treatment of livestock manure, livestock wastewater or livestock washing water using ceramic membrane | |
| CN113772881A (en) | Oxidation treatment method of phenol-cyanogen wastewater | |
| CN211770810U (en) | Coking wastewater treatment system for recycling ammonia nitrogen and fresh water based on membrane process | |
| CN207792957U (en) | A kind of crushed coal pressure gasifying wastewater treatment and reclaiming system |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201117 Termination date: 20210920 |