CN105692995A - Recycling treatment method of amino acid wastewater - Google Patents
Recycling treatment method of amino acid wastewater Download PDFInfo
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- CN105692995A CN105692995A CN201610093769.1A CN201610093769A CN105692995A CN 105692995 A CN105692995 A CN 105692995A CN 201610093769 A CN201610093769 A CN 201610093769A CN 105692995 A CN105692995 A CN 105692995A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 32
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 24
- 238000004064 recycling Methods 0.000 title claims abstract description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 19
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 19
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 6
- 239000011833 salt mixture Substances 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012530 fluid Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 229960000355 copper sulfate Drugs 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract 2
- 235000001014 amino acid Nutrition 0.000 description 21
- 230000000694 effects Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- 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
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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)
- Catalysts (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention relates to a recycling treatment method of amino acid wastewater. The recycling treatment method includes steps of (1), catalytic wet oxidation: using air or oxygen as an oxidizer, adding a multi-component soluble transition metal salt mixture into wastewater under conditions of 200-280 DEG C and 2-8 Mpa for wet oxidation to obtain treatment liquid 1; (2), steam stripping: subjecting the treatment liquid 1 after being oxidized to steam stripping to obtain an ammonium hydrogen carbonate solution, and obtaining ammonium hydrogen carbonate solid through cold separation. By adopting the recycling treatment method, through catalytic wet oxidation and steam stripping separation, COD removal rate of the wastewater reaches higher than 90%, high-purity ammonium hydrogen carbonate can be obtained, and the recycling treatment method is environment friendly and free of secondary pollution.
Description
(1) technical field
The present invention relates to the recycling processing method of a kind of amino acid wastewater。
(2) background technology
In the industry production such as chemical industry, pharmacy, food, often giving off a large amount of containing amino acid whose waste water, the acidity making water, in acidity, is changed by this waste water, and the self-purification capacity of water body reduces, and the growth of microorganism in water is hindered, serious environment pollution。And aminoacid is the key component of protein, being widely used in food industry, feed industry, medical industry etc., the discharge capacity containing amino acid wastewater is big。Accordingly, it would be desirable to thoroughly solve the pollution problem of amino acid wastewater。
The domestic and international treatment technology to this kind of waste water, mainly includes biochemical process and membrane separation process at present。
Wherein bioanalysis curb environmental pollution be research focus。It is low that it has expense, does not produce the advantages such as secondary pollution, and especially the application in amino acid wastewater processes has caused global concern, there is problems of this method and is not suitable for processing high-purity amino acid waste water。
And membrance separation rule is devoted in waste water amino acid whose recycling, mainly include the method such as electrodialysis, ultrafiltration。Membrane technology, due to advantages such as efficient, practical, adjustable, energy-conservation and simple process, has been widely used, and has created high economic benefit。While the satisfactorily resolving of environmental problem, more effective achieving the utilization of resources, membrane technology has the development prospect of light。Now existing many membrane separation techniques obtain large-scale application, and such as microfiltration, reverse osmosis, ultrafiltration, nanofiltration, electrodialysis, reverse osmosis etc., and the application that film is in amino acid wastewater processes is also very extensive。But major obstacle is in membrane process reality: investment and running cost are high, easily block, it is necessary to the process problem of high-caliber pretreatment and regular Chemical cleaning and concentrate, be easily generated secondary pollution, and the amino acid whose quality reclaimed is not high, it is impossible to effectively utilize。
How effectively to process high-purity amino acid waste water, do not produce secondary pollution, the comprehensive utilization of resource can be realized again, be always up those skilled in the art's problem demanding prompt solution。
(3) summary of the invention
Overcoming the deficiencies in the prior art, it is provided that the recycling processing method of a kind of amino acid wastewater, the pollutant such as the aminoacid in waste water can be thoroughly degraded to free ammonia by the method, and generate ammonium hydrogen carbonate with carbanion, can do fertilizer application after ammonium hydrogen carbonate is separated。Achieving while waste water treatment, reclaimed utility and non-secondary pollution, investment is low with operating cost, it is adaptable to industrialization runs continuously。
The technical solution used in the present invention is:
A kind of recycling processing method of amino acid wastewater, described method includes:
(1) CWO: waste water 200～280 DEG C, 2～8Mpa when, with air or oxygen for oxidant, add multicomponent soluble transition metal salt-mixture carry out wet oxidation reaction as catalyst, the treatment fluid 1 obtained；The described low transition metal salt-mixture two or more mixture in bivalence or trivalent iron salt, cupric salt, divalent nickel salt, manganous salt, divalent zinc salt, divalent cobalt, dosage is 0.1 ‰～5 ‰ (w/w accounts for wastewater quality percentage ratio)；
(2) stripping: the treatment fluid 1 after oxidation processes is obtained ammonium bicarbonate aqueous solution through stripping, obtains ammonium hydrogen carbonate solid then through cold analysis。
Step (1) and (2) reaction are preferably successive reaction, first flow through heat exchanger after waste water and compression air or oxygen mixing to heat up, enter back into reactor and carry out CWO reaction, the treatment fluid flowed out enters gas-liquid separator separates after heat exchanger is lowered the temperature, treatment fluid after separation enters back into stripping knockout tower device continuously, and described continuous stripping knockout tower device is made up of discharging pump, overhead condenser, tower top cooler at the bottom of feed pump, stripper, reboiler, tower。
Step (2) stripping parameter is preferably as follows: control tower top temperature 70～100 DEG C, overhead condenser leaving water temperature 70～100 DEG C, backflow temperature 70～100 DEG C, tower top leaving water temperature 70～100 DEG C；Stripper column bottom temperature 100～130 DEG C, leaving water temperature 100～130 DEG C at the bottom of tower, temperature controller can be set in stripper to control temperature easily。
For reaching the effect of energy-saving and emission-reduction, described reboiler can adopt step (1) treatment fluid to do thermal source at the used heat obtained when heat exchange is lowered the temperature。
Described catalyst is preferably two or more mixture following: copper sulfate, nickel sulfate, manganese sulfate, zinc sulfate, more preferably the mixture of copper sulfate and nickel sulfate。
Containing a large amount of organic amines and inorganic ammonia in amino acid wastewater, separating through CWO and stripping, waste water COD clearance reaches more than 90%, also can obtain highly purified ammonium hydrogen carbonate。
The inventive method can process the waste water containing amino acids pollutant, including the waste water etc. produced in amino acids production waste water and aminoacid use procedure。
Compared with prior art, the beneficial effects are mainly as follows:
(1) catalyst activity is high, and cheap and easy to get, consumption is little, and industrial applications prospect is big；
(2) high treating effect, under test conditions, amino acid whose clearance can reach 99%；
(3) continuous wet oxidation reaction technological process is adopted, without ammonium hydrogen carbonate clogging, it is easy to realization of industrialization；
(4) continuous print steam-stripping separating device, recyclable highly purified ammonium hydrogen carbonate, it may be achieved the resource of waste water are adopted；
(5) the inventive method environmental friendliness, does not produce secondary pollution。
(4) accompanying drawing explanation
Fig. 1 is the process chart that amino acid wastewater of the present invention processes；In figure: 1 is high-pressure metering pump, 2 is heat exchanger A, and 3 is reactor, and 4 is heat exchanger B, and 5 is gas-liquid separator, and 6 is liquid pump, and 7 is heat exchanger C, and 8 is stripper, and 9 is condenser, and 10 is cooler, and 11 is plate filter。
(5) detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to that:
Embodiment 1:
The COD recording glycin waste water is about 58760mg/L, total nitrogen is about 8253mg/L, ammonia nitrogen is about 410mg/L, organic nitrogen is about 7843mg/L。
In glycin waste water, add 0.2 ‰ copper sulfate and 0.1 ‰ nickel sulfate, stirring and dissolving, send into heat exchanger A (2), wastewater flow 0.3L/h through high-pressure metering pump (1)；Oxygen pressure 3MPa is regulated by air relief valve, quality controller controls oxygen flow 0.3L/min, mix heat exchanger B (2) is front with waste water, send into reactor (3) after being heated to 220 DEG C by temperature automatically controlled electric heater unit and carry out CWO reaction, the waste water time of staying in reactor is 3h, and the gas-liquid mixture after process cools down through heat exchanger C (4), gas-liquid separator (5) is discharged after separating respectively；Then waste water pump (6) is squeezed into stripper (8) and is carried out ammonium hydrogen carbonate recovery, stripper overhead temperature 80 DEG C (overhead condenser leaving water temperature 80 DEG C is controlled by overhead condenser (9), backflow temperature 80 DEG C, tower top leaving water temperature 80 DEG C；Stripper column bottom temperature 120 DEG C, leaving water temperature 120 DEG C at the bottom of tower), overhead fraction cooled device (10) crystallisation by cooling, plate filter (11) are filtrated to get ammonium hydrogen carbonate solid (purity 97.2%)。
Embodiment 2:
Waste water described in embodiment 1, other conditions are constant, regulate high-pressure cylinder oxygen pressure 6MPa, are heated to 260 DEG C and carry out oxidation reaction 2h, obtain ammonium hydrogen carbonate solid (purity 99.3%)。
Embodiment 3:
Adding 0.2 ‰ manganese sulfates and 0.1 ‰ nickel sulfate in waste water described in embodiment 1, other conditions are constant, finally obtain ammonium hydrogen carbonate solid (purity 96.5%)。
Embodiment 4:
Waste water described in embodiment 1 adds 0.2 ‰ copper sulfate and 0.2 ‰ zinc sulfate, other conditions
Constant, finally obtain ammonium hydrogen carbonate solid (purity 97.4%)。
Embodiment 5 (comparative example):
Waste water described in embodiment 1, other conditions are constant, carry out wastewater treatment when catalyst-free, finally obtain ammonium hydrogen carbonate solid (purity 89.5%)。
Embodiment 6:
The COD recording glutamic acid wastewater is about 36900mg/L, total nitrogen is about 27322mg/L, ammonia nitrogen is about 17760mg/L, organic nitrogen is about 9562mg/L, and step described in embodiment 1 processes, and finally obtains ammonium hydrogen carbonate solid (purity 97.9%)。
The treatment effect of embodiment 1～6 method of wastewater treatment is as shown in table 1。
Table 1: water treatment effect contrast table in embodiment 1～6
Claims (5)
1. a recycling processing method for amino acid wastewater, described method includes:
(1) CWO: waste water 200～280 DEG C, 2～8Mpa when, with air or oxygen for oxidant, add multicomponent soluble transition metal salt-mixture carry out wet oxidation reaction as catalyst, the treatment fluid 1 obtained；The described low transition metal salt-mixture two or more mixture in bivalence or trivalent iron salt, cupric salt, divalent nickel salt, manganous salt, divalent zinc salt, divalent cobalt, dosage is 0.1 ‰～5 ‰；
(2) stripping: the treatment fluid 1 after oxidation processes is obtained ammonium bicarbonate aqueous solution through stripping, obtains ammonium hydrogen carbonate solid then through cold analysis。
2. the method for claim 1, it is characterized in that described step (1) and (2) reaction are successive reaction, first flow through heat exchanger after waste water and compression air or oxygen mixing to heat up, enter back into reactor and carry out CWO reaction, the treatment fluid flowed out enters gas-liquid separator separates after heat exchanger is lowered the temperature, treatment fluid after separation enters back into stripping knockout tower device continuously, and described continuous stripping knockout tower device is made up of discharging pump, overhead condenser, tower top cooler at the bottom of feed pump, stripper, reboiler, tower。
3. method as claimed in claim 1 or 2, it is characterised in that step (2) stripping parameter is as follows: control tower top temperature 70～100 DEG C, overhead condenser leaving water temperature 70～100 DEG C, backflow temperature 70～100 DEG C, tower top leaving water temperature 70～100 DEG C；Stripper column bottom temperature 100～130 DEG C, leaving water temperature 100～130 DEG C at the bottom of tower。
4. method as claimed in claim 3, it is characterised in that described reboiler adopts step (1) treatment fluid to do thermal source at the used heat obtained when heat exchange is lowered the temperature。
5. method as claimed in claim 1 or 2, it is characterised in that described catalyst is two or more mixture following: copper sulfate, nickel sulfate, manganese sulfate, zinc sulfate。
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| CN201610093769.1A CN105692995A (en) | 2016-02-19 | 2016-02-19 | Recycling treatment method of amino acid wastewater |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610093769.1A CN105692995A (en) | 2016-02-19 | 2016-02-19 | Recycling treatment method of amino acid wastewater |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380021A (en) * | 2016-11-23 | 2017-02-08 | 江苏省环境科学研究院 | High-concentration organic wastewater wet oxidation treatment system and method |
| CN106966483A (en) * | 2017-03-29 | 2017-07-21 | 濮阳市盛源能源科技股份有限公司 | A kind of maleic anhydride method of wastewater treatment |
| CN110683695A (en) * | 2019-09-20 | 2020-01-14 | 浙江奇彩环境科技股份有限公司 | Glycine wastewater recycling treatment process |
| CN112495982A (en) * | 2020-10-22 | 2021-03-16 | 湖北君集水处理有限公司 | Method for converting kitchen waste into wastewater denitrification carbon source through catalytic wet oxidation |
| CN117550992A (en) * | 2023-04-19 | 2024-02-13 | 贵州茅台酒厂(集团)循环经济产业投资开发有限公司 | Resource utilization method of pit bottom liquid in Maotai-flavor liquor production |
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| CN106966483A (en) * | 2017-03-29 | 2017-07-21 | 濮阳市盛源能源科技股份有限公司 | A kind of maleic anhydride method of wastewater treatment |
| CN110683695A (en) * | 2019-09-20 | 2020-01-14 | 浙江奇彩环境科技股份有限公司 | Glycine wastewater recycling treatment process |
| CN112495982A (en) * | 2020-10-22 | 2021-03-16 | 湖北君集水处理有限公司 | Method for converting kitchen waste into wastewater denitrification carbon source through catalytic wet oxidation |
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