CN1587106A - Polyurethane base biological fixing carrier and sewage treating method - Google Patents
Polyurethane base biological fixing carrier and sewage treating method Download PDFInfo
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- CN1587106A CN1587106A CNA2004100625786A CN200410062578A CN1587106A CN 1587106 A CN1587106 A CN 1587106A CN A2004100625786 A CNA2004100625786 A CN A2004100625786A CN 200410062578 A CN200410062578 A CN 200410062578A CN 1587106 A CN1587106 A CN 1587106A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The present invention discloses one kind of polyurethane base biological immobile carrier. The carrier has three kinds of structures: macroporous polyurethane network; polyurethane cross-linked chitosan and coated active carbon; and microporous network formed with chitosan and cross-linked glutaraldehyde, chloropropylene oxide or chloroacetic acid. These three kinds of network interpenetrate to form the polymer capable of fixing bioactive molecule. The carrier of the present invention has the features of coexisting macropores and micropores, coexisting hydrophilicity and reaction property, coexisting powerful adsorption and strong polarity, high biological bearing capacity, good compatibility, high physical, chemical and mechanical performance, etc., and is suitable for various bioreactors for treating sewage.
Description
Technical field
The present invention relates to a kind of biological fixing carrier, more specifically, the present invention relates to a kind of polyurethane base biological fixing carrier that combines chemisorption and crosslinking reaction.
Background technology
At present, along with improving constantly in the requirement aspect environmental protection and the Sustainable development, the multiple mode that waste water is recycled of being used for occurred, a kind of approach wherein is the water-treatment biological reaction, and the water-treatment biological reaction just need be used the biological respinse carrier.
The carrying microorganism carrier is the key material that influences wastewater treatment efficiency in the biological respinse, and the technician once adopted slag, bamboo chip, batten, paper, glass, plastics, pottery etc. as bio-carrier.That the structure of carrier has is solid, hollow, ripple, honeycomb, ring-type, tree-shaped, layering etc., but in the prior art research of carrier still being concentrated on mostly increases specific surface area, prevents to stop up and mounting means, for example in Chinese patent CN 2528765Y, just disclosed the technology of the bigger fibrous reticulum of specific surface area of utilizing as microbe carrier, but the carrier that obtains with these technology is still inert, not biologically active.
The bio-immobilized technology that developed recently gets up is to make the technology of attached growth of microorganisms in carrier by certain immobilization means, and the biological fixnig method mainly contains surface adsorption fixation method, crosslinked fixation method and embedding fixation method etc.The surface adsorption fixation method is meant that microorganism is adsorbed on the fixing means of carrier surface, and biomembrance process is the representative example of this type of fixation method.This method is less to the microorganism active influence, but its fixed microbial biomass is limited.Crosslinked fixation method is to utilize two or more functional group preparations, direct and some amino-acid residue of microorganism peptide chain carries out crosslinking reaction, makes microbial immobilized method (for example referring to Chinese patent open file CN 1478734A) thereby form covalent linkage with microorganism.But this method chemical reaction fierceness is bigger to microorganism active influence, and the linking agent of use is poisonous mostly and cost an arm and a leg, thereby has limited the application of this method.The embedding fixation method is to form with microbial immobilized network, micro-capsule etc. with the macromolecule hydrogel material, or when utilizing water-soluble monomer polymerization formation gel with microorganism embedding (for example referring to Chinese patent open file CN 1277942 A) within it.This method is less to the microorganism active influence, but because of the obstruction of its carrier network structure is unfavorable for mass transfer, and the hydrogel shock-resistance is not good, the life-span short.
The lightweight polyurethane foam plastic is a kind of comparatively ideal carrier, has obtained certain application in recent years, has just adopted Polyurethane reticulated foam carrier in the LINPOR technology as Germany; In the prior art, in order to improve the adsorptive power of carrier, people attempt adding gac in polyurethane foam plastic, United States Patent (USP) 4983299 and Chinese patent open file CN 1105649 disclose such scheme, but these carriers still non-activity, do not have fine aperture, specific surface is little, gac and other additives combine insecure with the Polyurethane body, intensity difference, and poor chemical stability, facile hydrolysis.
Chitosan be slough in the chitin molecule ethanoyl and a kind of natural radioactivity macromolecular compound.Contain active hydroxyl and amino isopolarity group in the chitosan molecule; therefore; on the main chain hydrolysis reaction can take place, chemically modifieds such as acetylize, glycolyl, carboxymethylation, cyanoethylation, sulphating, oxidation, xanthation can take place in the hydroxyl on amino on the C-2 position and the C-6 position.Under linking agent effects such as the aldehyde of bifunctional or acid anhydrides, chitosan can carry out crosslinking reaction.Under gamma-radiation or catalyst action, vinyl monomer and acrylic monomer can carry out graft copolymerization with chitosan.Because chitosan not only has good biocompatibility, and nontoxic, readily biodegradable, makes it be with a wide range of applications in fields such as medicine, agricultural, environmental protection, weaving, printing and dyeing, papermaking, catalysis, food, daily cosmetics.For example in the disclosed technical scheme of Chinese patent open file CN 1280104A, it is used in the sewage disposal as flocculation agent.
But do not occur as yet in the prior art up to now, urethane, gac and chitosan biological fixing carrier that be combined as a whole, that have composite efficacy.
Summary of the invention
Based on above-mentioned consideration, the purpose of this invention is to provide a kind of bio-carrier with composite efficacy, the advantage that this carrier can keep lightweight polyurethane foam plastic, gac and chitosan to combine and dispose of sewage and had with microorganism separately, make simultaneously the three collaborative mutually again, become the ideal organic whole.
The raw material of the present invention by selecting carrier, utilize chemisorption to form a kind of carrier, thereby realized above-mentioned purpose with biomolecule activity with the crosslinked bio-immobilized technology that combines.
According to an aspect of the present invention, the application provides a kind of biological fixing carrier that is used for water treatment, and this carrier comprises: a kind of matrix that is made of porous plastics; A kind of sorbent material, it is added in the matrix when the porous plastics matrix is synthetic; And a kind of linking agent, it is added in the matrix when the porous plastics matrix is synthetic, and with matrix generation crosslinking reaction the sorbent material bag is knitted therein.
According to a feature of the present invention, described porous plastics is a polyurethane material.
According to a feature of the present invention, described sorbent material is a gac.
According to a feature of the present invention, described flocculation agent is a chitosan.
According to a further aspect in the invention, the application provides a kind of chitosan crosslinked gac Polyurethane biological fixing carrier, by when polyurethane foam plastic is synthetic, adding chitosan and powdered carbon, and make described biological fixing carrier through foaming, perforate, crosslinking Treatment.
According to a feature of the present invention, the amino of the chitosan that when the polyurethane foam plastic open-cell foaming, adds and Polyurethane generation crosslinking reaction, simultaneously, the amino of chitosan of not participating in crosslinking reaction also with Polyurethane in other key such as acid amides form hydrogen bond, and the gac bag is knitted therein.
According to another feature of the present invention, also use glutaraldehyde, epoxy chloropropane or Mono Chloro Acetic Acid and chitosan to carry out secondary crosslinking, generate trickle aperture reticulated structure.
According to another feature of the present invention, carrier surface contains groups such as primary amino, secondary amino group, amide group, carbonyl, ehter bond, can crosslinked fixation of microbe; Carrier contains N, O atom, thereby can form coordinate bond with metal ion.
According to a feature of the present invention, adding chitosan and powdered carbon have generated the especially big pore network polymkeric substance of Polyurethane when the polyurethane foam plastic open-cell foaming, and the microporous network structure IPN that itself and secondary crosslinking generated has formed complicated reticulated structure.
According to a further aspect in the invention, the application provides a kind of sewage water treatment method, and the method comprising the steps of:
Above-mentioned carrier is joined in the aeration tank, inoculation of activated-sludge or add high-effective microorganism, and filling sewage, vexed exposing to the sun 2-4 days is so that microorganism and carrier generation immobilized reactant; And
Feed sewage, the discharge of sewage is ascending to gradually change, and disposes of sewage continuously behind the certain hour.
Embodiment
Hereinafter will the present invention will be described in detail in conjunction with concrete embodiment, but these descriptions only are exemplary, those skilled in the art can figure out: in claims institute restricted portion, multiple other embodiment can also be arranged, and all based on the embodiment of design philosophy of the present invention all within the scope of the invention.
By adding gac and chitosan when the synthesizing polyurethane porous plastics, and made a kind of chitosan crosslinked gac Polyurethane biological fixing carrier through foaming, perforate, processings such as crosslinked, it shows especially big hole and micro-holes, wetting ability and reactivity, adsorptive type and the characteristic that coexists of polarity by force by force; And mass transfer, heat transfer and momentum transfer speed are fast; Biological bearing capacity is high and consistency is good; Physical and chemical performance is stable, have in acid/alkali aqueous solution do not dissolve, characteristics that anti-hydrolysis ability is strong.The dry density of this carrier is 12-35g/m
3, wet density is 950-1100kg/m
3, porosity 98%, specific surface is 150m
2/ g, water holding capacity 3000%.
When implementing sewage disposal, carrier is added in the aeration tank inoculation of activated-sludge or add high-effective microorganism, vexed exposing to the sun 2-4 days behind the adding sewage carried out the immobilized reactant of microorganism and carrier, then water inlet, flow can be used for disposing of sewage continuously after 15-20 days from small to large.
Carrier of the present invention is applicable to Treating Municipal Sewage, industrial sewage, percolate and fowl poultry waste liquid, and can be used for the environment water of rivers and lakes is repaired.Introduce some below and use the example that this carrier is carried out water treatment
Example 1
Utilize with chitosan crosslinked gac Polyurethane biological fixing carrier and handle coked waste water
The above-mentioned carrier of filling 2/3 volumetrical in BAF, (B350 contains 28 kinds of special microorganisms and cellulase, amylase, lipase and lytic enzyme to add high effective microbial community B350, bulk density is 0.6-0.8g/cm3, and microbe population is hundred million of 30-50/g).Lay micropore aeration pipe at the bottom of the pond to system's aeration.Table 1 is 90 days result of operation.
Table 1 coked waste water result (unit: mg/L, pH value, colourity except)
| Project | Import | Outlet | |||
| Concentration | Mean value | Concentration | Mean value | Clearance | |
| The pH value | ??9.07-9.29 | ??9.13 | ????7.63-8.91 | ????8.29 | |
| ??COD | ??3250-3590 | ??3450 | ????36.3-90.5 | ????67.7 | ????98％ |
| Ammonia nitrogen | ??423-498 | ??451 | ????0.120-0.469 | ????0.295 | ????99％ |
| Volatile phenol | ??132-281 | ??177 | ????0.056-1.520 | ????0.398 | ????99％ |
| ??SS | ??62-135 | ??94 | ????12-74 | ????42 | ????56％ |
| Colourity | ??120 | ????12 | ????90％ | ||
Water outlet result as seen from Table 1 is better than the first discharge standard of CNS " waste water comprehensive discharge " in (GB8978-1996) (volatile phenol≤0.5mg/L, SS≤70mg/L, colourity≤50 times, the pH value is 6-9 for COD≤100mg/L, ammonia nitrogen≤15mg/L).
Example 2
Utilize chitosan crosslinked gac Polyurethane biological fixing carrier to handle Organic Chemical Plant's waste water
One is mainly to contain oil of mirbane, nitrophenol, aniline, phenylpropyl alcohol than 16 kinds of antibionts degradeds such as azoles, morpholine and to the virose pollutent of biology in institute of the Organic Chemical Plant effluent of main products with rubber ingredients, COD is 14400mg/L to the maximum, ammonia nitrogen is 70-110mg/L, oil of mirbane is 120mg/L, and aniline is 700mg/L.Adopt carrier of the present invention, add microorganism species B350, waste water is carried out aeration handle, water outlet is up to standard comprehensively, and principal pollutant COD clearance reaches 94.7%, ammonia nitrogen removal frank 99.5%.Table 2 is 30 days a detected result of environmental monitoring station.
Table 2 rubber ingredients organic chemical waste water result (unit: mg/L)
Project COD ammonia nitrogen oil of mirbane aniline sulfide
Water inlet maximum 2,166 142 106 523 65.7
Minimum 822 42.8 23 89.6 2.60
Average 1,680 86.3 88.4 226.5 28.3
Water outlet maximum 168 1.60 3.2 1.53 0.42
Minimum 32.3 0 0.23 0.22 0
Average 89.4 0.43 0.65 0.72 0.062
Clearance 94.7% 99.5% 99.3% 99.7% 99.8%
Example 3
Utilize chitosan crosslinked gac Polyurethane biological fixing carrier to handle paper mill effluent
Main COD material is Mierocrystalline cellulose, hemicellulose and poisonous biorefractory xylogen is arranged in the paper mill effluent.Paper mill effluent is typical high density, organic wastewater with difficult degradation thereby, adopts chitosan crosslinked gac Polyurethane biological fixing carrier system that paper mill effluent is handled, and water outlet reaches paper waste first discharge standard (COD≤420mg/L).Table 3 is examining reports of 60 days of environmental monitoring station.
Table 3 paper mill effluent result (unit: mg/L)
The project water removal rate of intaking out
COD maximum 6,900 430 93.8%
(mg/L) minimum 2,020 189 91%
Average 4,300 280 93.4%
Example 4
Utilize chitosan crosslinked gac Polyurethane biological fixing carrier to handle tannery's waste water
Adopt chitosan crosslinked gac Polyurethane biological fixing carrier system that tannery's waste water is handled, table 4 is detected results of 40 days of environmental monitoring station.
Table 4 leather waste water result (unit: mg/L)
Import export
Project
Concentration mean value concentration mean value clearance
COD?????????3200-2590??????2850????????55.0-120????????70.3???????97.5％
Ammonia nitrogen 123-198 151 0.30-1.69 0.495 99.8%
Sulfide 20-138 64 0-0.005 0.002 99.9%
Total chromium 20-50 28 0.002-0.009 0.004 99.9%
Conclusion: from above-mentioned example as seen, vehicle treated waste water effect of the present invention is obvious, stable, has good universality, and has special advantages aspect processing high density, hardly degraded organic substance and the high ammonia nitrogen.
Claims (10)
1, a kind of biological fixing carrier that is used for water treatment, this carrier comprises: a kind of matrix that is made of porous plastics; A kind of sorbent material, it is added in the matrix when the porous plastics matrix is synthetic; And a kind of linking agent, it is added in the matrix when the porous plastics matrix is synthetic, and with matrix generation crosslinking reaction the sorbent material bag is knitted therein.
2, biological fixing carrier according to claim 1 is characterized in that: described porous plastics is a polyurethane material.
3, biological fixing carrier according to claim 2 is characterized in that: described sorbent material is a gac.
4, biological fixing carrier according to claim 3 is characterized in that: described flocculation agent is a chitosan.
5, a kind of chitosan crosslinked gac Polyurethane biological fixing carrier, this carrier is by adding chitosan and powdered carbon and making through foaming-perforate-crosslinking Treatment when polyurethane foam plastic is synthetic.
6, biological fixing carrier according to claim 5, it is characterized in that: the amino of the chitosan that when the polyurethane foam plastic open-cell foaming, adds and Polyurethane generation crosslinking reaction, simultaneously, the amino of chitosan of not participating in crosslinking reaction also with Polyurethane in other key such as acid amides form hydrogen bond, and the gac bag is knitted therein.
7, biological fixing carrier according to claim 5 is characterized in that: also use glutaraldehyde, epoxy chloropropane or Mono Chloro Acetic Acid and chitosan to carry out secondary crosslinking, generate trickle aperture reticulated structure.
8, biological fixing carrier according to claim 7 is characterized in that: carrier surface contains groups such as primary amino, secondary amino group, amide group, carbonyl, ehter bond, can crosslinked fixation of microbe; Carrier contains N, O atom, thereby can form coordinate bond with metal ion; Adding chitosan and powdered carbon have generated the especially big pore network polymkeric substance of Polyurethane when the polyurethane foam plastic open-cell foaming, and the microporous network structure IPN that itself and secondary crosslinking generated has formed complicated reticulated structure.
9, a kind of sewage water treatment method, the method comprising the steps of:
To join in the aeration tank according to the described carrier of one of claim 1-8, inoculation of activated-sludge or add high-effective microorganism, and filling sewage, vexed exposing to the sun 2-4 days is so that microorganism and carrier generation immobilized reactant; And
Feed sewage, the discharge of sewage is ascending to gradually change, and disposes of sewage continuously behind the certain hour.
10, sewage water treatment method according to claim 9 is characterized in that: this method is applicable to Treating Municipal Sewage, industrial sewage, percolate and fowl poultry waste liquid, and can be used for the environment water of rivers and lakes is repaired.
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| CNA2004100625786A CN1587106A (en) | 2004-07-02 | 2004-07-02 | Polyurethane base biological fixing carrier and sewage treating method |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100537450C (en) * | 2006-07-03 | 2009-09-09 | 浙江工业大学 | Bio-affinity water treatment filling |
| CN101885562A (en) * | 2010-07-01 | 2010-11-17 | 杨国录 | Remediation method of polluted water body of rivers and lakes |
| CN102134143A (en) * | 2011-01-28 | 2011-07-27 | 北京市水利科学研究所 | Method and device for treating sewage in anaerobic bio-filter and solar aeration bio-filter |
| CN102531149A (en) * | 2010-12-10 | 2012-07-04 | 新奥科技发展有限公司 | Packing for bearing microorganism |
| CN102702567A (en) * | 2012-05-18 | 2012-10-03 | 苏州科技学院 | Method for preparing surface function modified polyurethane foaming plastic carriers |
| CN102935354A (en) * | 2012-05-25 | 2013-02-20 | 高巍 | Novel open micropore molecule carrier and preparation method thereof |
| CN103418236A (en) * | 2013-08-28 | 2013-12-04 | 上海交通大学 | Biological deodorizing packing and device |
| CN103627015A (en) * | 2012-08-27 | 2014-03-12 | 苏州科技学院 | Preparation method of hydrophilic polymer-modified polyurethane foaming plastic carrier |
| CN105236568A (en) * | 2015-08-07 | 2016-01-13 | 北京大学 | Method for running anammox by utilizing microbial immobilization membrane bioreactor |
| CN106268691A (en) * | 2016-09-07 | 2017-01-04 | 中国海洋大学 | A kind of polysaccharide polyurethane heavy metal absorbent and preparation method thereof |
| CN106746378A (en) * | 2017-03-15 | 2017-05-31 | 青岛思普润水处理股份有限公司 | One kind solidification high-effective microorganism film sewage water treatment method and equipment |
| CN107879551A (en) * | 2017-11-17 | 2018-04-06 | 大理大学 | A kind of method that sewage is handled using bio-denitrification technology |
| CN108467113A (en) * | 2018-05-22 | 2018-08-31 | 北京华明广远环境科技有限公司 | Efficient denitrification filter pool |
| CN108483644A (en) * | 2018-04-28 | 2018-09-04 | 南京大学 | It is a kind of that Anammox is promoted quickly to start the composite biological packing and its preparation method and application with stable operation |
| CN108516614A (en) * | 2018-05-25 | 2018-09-11 | 北京华明广远环境科技有限公司 | Skid-mounted type bio-packing apparatus and its application |
| CN109970182A (en) * | 2019-03-21 | 2019-07-05 | 华北电力大学 | A kind of composite filling for immobilized microorganism technique |
| CN111549719A (en) * | 2020-05-15 | 2020-08-18 | 南京市生态环境保护科学研究院 | Ecological restoration system for hard river channel and treatment method thereof |
| CN115215502A (en) * | 2021-04-14 | 2022-10-21 | 中国石油天然气集团有限公司 | Method for purifying coal bed gas produced water |
-
2004
- 2004-07-02 CN CNA2004100625786A patent/CN1587106A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100537450C (en) * | 2006-07-03 | 2009-09-09 | 浙江工业大学 | Bio-affinity water treatment filling |
| CN101885562A (en) * | 2010-07-01 | 2010-11-17 | 杨国录 | Remediation method of polluted water body of rivers and lakes |
| CN101885562B (en) * | 2010-07-01 | 2011-10-26 | 杨国录 | Remediation method of polluted water body of rivers and lakes |
| CN102531149B (en) * | 2010-12-10 | 2015-09-02 | 新奥科技发展有限公司 | A kind of filler of bearing microorganism |
| CN102531149A (en) * | 2010-12-10 | 2012-07-04 | 新奥科技发展有限公司 | Packing for bearing microorganism |
| CN102134143A (en) * | 2011-01-28 | 2011-07-27 | 北京市水利科学研究所 | Method and device for treating sewage in anaerobic bio-filter and solar aeration bio-filter |
| CN102134143B (en) * | 2011-01-28 | 2013-07-10 | 北京市水利科学研究所 | Method for treating sewage in anaerobic bio-filter and solar aeration bio-filter |
| CN102702567A (en) * | 2012-05-18 | 2012-10-03 | 苏州科技学院 | Method for preparing surface function modified polyurethane foaming plastic carriers |
| CN102935354A (en) * | 2012-05-25 | 2013-02-20 | 高巍 | Novel open micropore molecule carrier and preparation method thereof |
| CN102935354B (en) * | 2012-05-25 | 2015-05-13 | 高巍 | Novel open micropore molecule carrier and preparation method thereof |
| CN103627015A (en) * | 2012-08-27 | 2014-03-12 | 苏州科技学院 | Preparation method of hydrophilic polymer-modified polyurethane foaming plastic carrier |
| CN103627015B (en) * | 2012-08-27 | 2016-06-08 | 江苏陆博环保科技有限公司 | The preparation method of a kind of hydrophilic polymer modified urethane foam carrier |
| CN103418236A (en) * | 2013-08-28 | 2013-12-04 | 上海交通大学 | Biological deodorizing packing and device |
| CN105236568A (en) * | 2015-08-07 | 2016-01-13 | 北京大学 | Method for running anammox by utilizing microbial immobilization membrane bioreactor |
| CN105236568B (en) * | 2015-08-07 | 2017-06-16 | 北京大学 | A kind of method that Anammox is run using microbial immobilized membrane bioreactor |
| CN106268691A (en) * | 2016-09-07 | 2017-01-04 | 中国海洋大学 | A kind of polysaccharide polyurethane heavy metal absorbent and preparation method thereof |
| CN106746378A (en) * | 2017-03-15 | 2017-05-31 | 青岛思普润水处理股份有限公司 | One kind solidification high-effective microorganism film sewage water treatment method and equipment |
| CN107879551A (en) * | 2017-11-17 | 2018-04-06 | 大理大学 | A kind of method that sewage is handled using bio-denitrification technology |
| CN107879551B (en) * | 2017-11-17 | 2021-03-30 | 大理大学 | Method for treating sewage by using biological denitrification technology |
| CN108483644B (en) * | 2018-04-28 | 2020-06-26 | 南京大学 | Composite biological filler for promoting rapid start and stable operation of anaerobic ammonia oxidation and preparation method and application thereof |
| CN108483644A (en) * | 2018-04-28 | 2018-09-04 | 南京大学 | It is a kind of that Anammox is promoted quickly to start the composite biological packing and its preparation method and application with stable operation |
| CN108467113A (en) * | 2018-05-22 | 2018-08-31 | 北京华明广远环境科技有限公司 | Efficient denitrification filter pool |
| CN108516614A (en) * | 2018-05-25 | 2018-09-11 | 北京华明广远环境科技有限公司 | Skid-mounted type bio-packing apparatus and its application |
| CN109970182A (en) * | 2019-03-21 | 2019-07-05 | 华北电力大学 | A kind of composite filling for immobilized microorganism technique |
| CN111549719A (en) * | 2020-05-15 | 2020-08-18 | 南京市生态环境保护科学研究院 | Ecological restoration system for hard river channel and treatment method thereof |
| CN111549719B (en) * | 2020-05-15 | 2020-11-10 | 南京市生态环境保护科学研究院 | Ecological restoration system for hard river channel |
| CN115215502A (en) * | 2021-04-14 | 2022-10-21 | 中国石油天然气集团有限公司 | Method for purifying coal bed gas produced water |
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