CN107176711A - The technique of copper in a kind of high efficiente callback high concentration berberine waste water - Google Patents

The technique of copper in a kind of high efficiente callback high concentration berberine waste water Download PDF

Info

Publication number
CN107176711A
CN107176711A CN201710261161.XA CN201710261161A CN107176711A CN 107176711 A CN107176711 A CN 107176711A CN 201710261161 A CN201710261161 A CN 201710261161A CN 107176711 A CN107176711 A CN 107176711A
Authority
CN
China
Prior art keywords
waste water
copper
reaction
iron
berberine
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.)
Granted
Application number
CN201710261161.XA
Other languages
Chinese (zh)
Other versions
CN107176711B (en
Inventor
王敏
谢元华
朱彤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeastern University China
Original Assignee
Northeastern University China
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Northeastern University China filed Critical Northeastern University China
Priority to CN201710261161.XA priority Critical patent/CN107176711B/en
Publication of CN107176711A publication Critical patent/CN107176711A/en
Application granted granted Critical
Publication of CN107176711B publication Critical patent/CN107176711B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0091—Treating solutions by chemical methods by cementation
    • 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
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • 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
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention belongs to water treatment applications and recycling field, the technique for being related to copper in a kind of high efficiente callback high concentration berberine waste water.Berberine copper-containing wastewater is added 1000 5000r/min strong agitations under water treatment flocculant and polyacrylamide (PAM) confection, different rotating speeds by the technique makes medicament be sufficiently mixed with waste water；NaOH is added, by pH value of waste water regulation to 2~3.5；Then filter centrifugation removes precipitation and suspension.After obtained waste water heating, iron powder is slow added into.After the completion of reaction, copper simple substance precipitation is filtrated to get, water outlet enters second order reaction；20 30min are reacted, supernatants after precipitation qualified discharge is filtered.The technological operation is simple, stable, with low cost, it is high to reclaim copper simple substance purity, with good economic benefit and good application prospect.

Description

The technique of copper in a kind of high efficiente callback high concentration berberine waste water
Technical field
The invention belongs to water treatment applications and recycling field, it is related to a kind of simple but efficient flocculation+iron-deoxidize and returns The technique for receiving copper in high-concentration copper-containing berberine waste water.
Background technology
Berberine copper-containing wastewater be mainly derived from generation berberine in decopper(ing) process procedure, be decopper(ing) reaction waste liquid and The mixture of berberine crude product cleaning fluid, composition is mainly berberine, copper ion and the intermediate product of reaction.Berberine cupric Waste water is a kind of typical chemical synthesis class pharmacy waste water, because the waste water is black dull green solution, is stimulated with sharp sourness Taste, pH value be 1 or so, organic concentration be up to it is tens of thousands of to ten tens of thousands of mg/L, and in waste water copper chloride content also average value 1.5~ 20000 mg/L.It is not preprocessed to be discharged into sewage treatment plant because Cu in waste water ion concentration is higher, to follow-up sewage treatment plant Biological treatment brings enormous impact.Simultaneously as the Cu in waste water ion concentration is higher, with higher recycling valency Value.
Therefore, the copper reclaimed in berberine copper-containing wastewater is reclaimed, on the one hand can plays recycling, the opposing party Face can mitigate subsequent wastewater treatment difficulty.At present to reclaim the copper ion in berberine production waste water, patent of invention (once duckweed etc., ZL201310042379.8 the technique that a kind of utilization berberine copper-containing wastewater prepares basic copper chloride, recoverable wastewater) are disclosed In 99.9% copper.But, the basic copper chloride that this method is reclaimed also needs further processing, and berberine and acids in water Also need further processing so that technique is more complicated；Xiao book tiger et al. is using the electrochemical bipolar method processing high-concentration copper-containing coptis Plain pharmacy waste water (environment project journal, 2011,1 (4)：295-299), the clearance of berberine and copper is respectively reached 93.3% and more than 99.9%, the average recovery rate of copper is up to recyclable copper about 21.4kg in 97.1%, copper-containing wastewater per ton.But Be this method in practical application, the easy fouling of electrode, influence reaction further progress so that production can not carry out.Cui Xiaoyu Copper recovery, copper ion clearance are carried out to berberine pharmaceutical wastewater Deng using iron-carbon micro-electrolysis pond-ion exchange column group technology 97% or so is reached, organic concentration clearance is up to more than 44%, the recyclable copper 13kg (environment projects of waste water per ton Report, 2012,2 (4)：319-324).But these methods processing berberine copper-containing wastewater can not be effectively long-term in Practical Project Operation, reason be in waste water contain a class colloid substance, when in waste water pH value regulation to more than 3 when, such colloid substance by Dissolved state is changed into solid-state, and on the one hand influence copper ion is reduced into the course of reaction of elemental copper so that its reaction is insufficient；It is another Aspect, the jelly of precipitation adheres to reactor wall, and is easy to cause waste water transfer canal to block, and influence waste water is subsequently located Reason.
Course of reaction and reaction efficiency problem are influenceed based on jelly present in actual recovery process in copper-containing wastewater, I Propose to remove gluey organic matter using flocculation first, then carry out berberine cupric with the technique of two grades of iron simple substance displacement copper ions The copper of waste water is reclaimed.In existing report, there is not yet combining to enter berberine copper-containing wastewater using flocculation+iron second-stage reduction The technique that row is reclaimed.
The content of the invention
The present invention provides a kind of technique of copper in high efficiente callback high concentration berberine waste water, and the technological operation is simple, operation Stable, with low cost, recovery copper simple substance purity is high, with good economic benefit and good application prospect.
The technique of copper, is adopted the following technical scheme that in a kind of high efficiente callback high concentration berberine waste water of the present invention：
(1) be well mixed a production cycle berberine copper-containing wastewater, according to COD concentration add water treatment flocculant and Polyacrylamide (PAM) confection, described water treatment flocculant includes aluminum sulfate, aluminium chloride, ferric sulfate, iron chloride, poly- Close the flocculants such as ferric sulfate, aluminium polychloride, PAFC；1000-5000r/min strong agitations make medicine under different rotating speeds Agent is sufficiently mixed with waste water；
(2) NaOH is added, is thoroughly mixed uniformly, by pH value of waste water regulation to 2~3.5, stands 30min；
(3) above-mentioned waste water is centrifuged using perforated wall centrifuge, rotating speed is 3000-5000r/min, during centrifugation Between be 10-25min, remove precipitation and suspension.The supernatant of centrifugation enters one-level iron reduction reaction；
(4) waste water is heated to 75~95 DEG C；Then according to Cu in waste water2+Concentration, the iron powder amount according to needed for reduction reaction, The slow distributed iron powder for adding excess 10-40%.When adding iron powder, waste water is persistently stirred, is made between iron powder and waste water fully Contact.Add after whole iron powders, continue to stir in insulation and react 20-50min at 80-95 DEG C, after the completion of reaction, be filtrated to get copper Simple substance is precipitated, and water outlet enters second order reaction；(2) water outlet after one-level reduction reaction, in the case where 80-95 DEG C is incubated, adds one-level anti- The 10~20% of added iron total amount, carry out second order reaction in answering, and react 20-30min, filter supernatants after precipitation qualified discharge.
This method produces waste water as process object using high-concentration copper-containing berberine, is mainly first removed using flocculant in waste water Gluey organic matter, then uses cheap iron powder for raw material, passes through the Cu in the reduction reducing waste water of simple iron2+For copper list Matter, plays the resource reclaim of metallic copper and recycles, while COD in gluey organic matter in waste water, reduction waste water can also be removed While, reduce blocking of the gluey organic matter to pipeline in waste water in factory's actual motion.This method can be reclaimed in waste water Cu in more than 99% copper, water outlet2+Concentration is less than 50mg/L, effectively increases the biodegradability of waste water.
Brief description of the drawings
Accompanying drawing 1 is the process chart of copper in high efficiente callback high concentration berberine waste water of the invention.
Embodiment
Example 1 takes 400mL cuprics berberine to generate waste water, wherein Cu2+Concentration is 18 000mg/L, CODCrConcentration is 87000mg/L, initial pH value is 0.1.Plus 10g aluminium chlorides, rotating speed is stirring 20 minutes under 2000r/min, is then added 0.4g PAM flocculation aids, rotating speed is to stir 10 minutes under 1000r/min, then adds 5g NaOH and wastewater pH is adjusted into 3.0, quiet Put reaction 30min.Rotating speed is centrifuges 20min under 4000r/min, collecting 320mL supernatants waste liquid is used for one-level reduction reaction.Will be useless Water is heated to 90 DEG C, is slowly added to 6.6g purity for more than 95% iron powder, and continue the stirring reaction under 500r/min 30min.Then water outlet, is filtrated to get the elemental copper after first order reaction, and waste water to second-stage reduction reacts.First order reaction water outlet Cu2+ Concentration is 53mg/L.Before second order reaction, waste water is first heated to 90 DEG C, it is more than 95% to be slowly added to 0.66g purity Iron powder, continues stirring reaction 30min, then water outlet under 500r/min, is filtrated to get the mixed of the copper after second order reaction and iron etc. Cu in compound, water outlet2+Concentration is 8.9mg/L, and CODCr concentration is 53000mg/L.
The 400mL cuprics berberine of example 2 generates waste water, Cu2+Concentration is 18 000mg/L, CODCrConcentration is 87000mg/ L, initial pH value is 0.1.Plus 8g aluminium chlorides, rotating speed is stirring 30 minutes under 3000r/min, then adds 0.2g PAM and helps Then solidifying agent, rotating speed adds 5.2g NaOH and wastewater pH is adjusted into 3.5, stand reaction to be stirred under 500r/min 10 minutes 40min.Rotating speed is centrifuges 20min under 5000r/min, collecting 320mL supernatants waste liquid is used for one-level reduction reaction.Waste water is heated 75 DEG C are warming up to, 5.1g purity is slowly added to for more than 95% iron powder, and continue the stirring reaction 30min under 1000r/min.So Water outlet afterwards, is filtrated to get the elemental copper after first order reaction, waste water to second-stage reduction retort.Cu in primary effluent2+Concentration is 131mg/L.Second order reaction keeping temperature is slowly added to 0.51g purity for more than 95% iron powder, continued in 500r/min in 90 DEG C Lower stirring reaction 30min, then water outlet is filtrated to get Cu in the mixture of the copper after second order reaction and iron etc., secondary effluent2+It is dense Spend for 29mg/L, CODCr concentration is 67000mg/L.
The 400mL cuprics berberine of example 3 generates waste water, Cu2+Concentration is 18 000mg/L, CODCrConcentration is 87000mg/ L, initial pH value is 0.1.Plus 10g aluminium chlorides, rotating speed is stirring 30 minutes under 3000r/min, then adds 0.4g PAM Then flocculation aid, rotating speed adds 4.6g NaOH and wastewater pH is adjusted into 2.5, stand reaction to be stirred under 500r/min 10 minutes 30min.Rotating speed is centrifuges 30min under 5000r/min, collecting 320mL supernatants waste liquid is used for one-level reduction reaction.Waste water is heated 90 DEG C are warming up to, 6.6g purity is slowly added to for more than 95% iron powder, and continue the stirring reaction 40min under 1000r/min.So Water outlet afterwards, is filtrated to get the elemental copper after first order reaction, waste water to second-stage reduction retort.Cu in primary effluent2+Concentration is 461mg/L.Second order reaction keeping temperature is slowly added to 1.11g purity for more than 95% iron powder, continued in 500r/min in 90 DEG C Lower stirring reaction 40min, then water outlet is filtrated to get Cu in the mixture of the copper after second order reaction and iron etc., secondary effluent2+It is dense Spend for 46mg/L, CODCr concentration is 67000mg/L.

Claims (1)

1. a kind of technique of copper in high efficiente callback high concentration berberine waste water, it is characterised in that following steps,
(1) the berberine copper-containing wastewater of a production cycle is well mixed, water treatment flocculant and poly- third is added according to COD concentration Acrylamide (PAM) confection, described water treatment flocculant includes aluminum sulfate, aluminium chloride, ferric sulfate, iron chloride, polymerised sulphur The flocculants such as sour iron, aluminium polychloride, PAFC；Under different rotating speeds 1000-5000r/min strong agitations make medicament with Waste water is sufficiently mixed；
(2) NaOH is added, is thoroughly mixed uniformly, by pH value of waste water regulation to 2~3.5, stands 30min；
(3) above-mentioned waste water is centrifuged using perforated wall centrifuge, rotating speed is 3000-5000r/min, and centrifugation time is 10-25min, removes precipitation and suspension, and the supernatant of centrifugation enters one-level iron reduction reaction；
(4) waste water is heated to 75~95 DEG C；Then according to Cu in waste water2+Concentration, the iron powder amount according to needed for reduction reaction, slowly Distribution adds excess 10-40% iron powder；When adding iron powder, waste water is persistently stirred, makes fully to contact between iron powder and waste water； Add after whole iron powders, continue to stir in insulation and react 20-50min at 80-95 DEG C, after the completion of reaction, be filtrated to get copper simple substance Precipitation, water outlet enters second order reaction；
(5) water outlet after one-level reduction reaction, in the case where 80-95 DEG C is incubated, the 10 of iron total amount added by addition first order reaction~ 20%, second order reaction is carried out, 20-30min is reacted, supernatants after precipitation qualified discharge is filtered.
CN201710261161.XA 2017-04-20 2017-04-20 Process for efficiently recovering copper in high-concentration berberine wastewater Active CN107176711B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710261161.XA CN107176711B (en) 2017-04-20 2017-04-20 Process for efficiently recovering copper in high-concentration berberine wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710261161.XA CN107176711B (en) 2017-04-20 2017-04-20 Process for efficiently recovering copper in high-concentration berberine wastewater

Publications (2)

Publication Number Publication Date
CN107176711A true CN107176711A (en) 2017-09-19
CN107176711B CN107176711B (en) 2020-10-16

Family

ID=59831994

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710261161.XA Active CN107176711B (en) 2017-04-20 2017-04-20 Process for efficiently recovering copper in high-concentration berberine wastewater

Country Status (1)

Country Link
CN (1) CN107176711B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108746602A (en) * 2018-05-26 2018-11-06 烟台大学 A method of preparing copper-clad iron powder using copper-containing wastewater

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515389A (en) * 2011-12-09 2012-06-27 紫金矿业集团股份有限公司 Harmless treatment process for acidic copper-containing wastewater
CN103011360A (en) * 2012-12-07 2013-04-03 常州大学 Treatment method for industrial wastewater generated by copper wet-process smelting
JP2013094694A (en) * 2011-10-28 2013-05-20 Vision Development Co Ltd Processing method for waste liquid containing metal atom, and adsorbent
CN103145227A (en) * 2013-03-25 2013-06-12 西安德奇水处理有限公司 Flocculation treatment method for copper-containing wastewater
CN103214121A (en) * 2013-04-27 2013-07-24 福建格林锘贝尔环保科技有限公司 Method for recycling copper and iron in acid mine wastewater by high-polymer chelating-precipitating agent two-step process
CN105347546A (en) * 2015-11-03 2016-02-24 湖北祥云(集团)化工股份有限公司 Treatment method and system of waste water produced by acid preparation from pyrite
JP5884493B2 (en) * 2012-01-11 2016-03-15 栗田工業株式会社 Treatment method for wastewater containing heavy metals
CN105621744A (en) * 2016-03-07 2016-06-01 山东国信环境系统股份有限公司 Copper ore acid wastewater treatment and recovery device and method
CN105692833A (en) * 2016-03-08 2016-06-22 江苏国松环境科技开发有限公司 Process for treating wastewater in copper industry by using polymeric ferric sulfate

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013094694A (en) * 2011-10-28 2013-05-20 Vision Development Co Ltd Processing method for waste liquid containing metal atom, and adsorbent
CN102515389A (en) * 2011-12-09 2012-06-27 紫金矿业集团股份有限公司 Harmless treatment process for acidic copper-containing wastewater
JP5884493B2 (en) * 2012-01-11 2016-03-15 栗田工業株式会社 Treatment method for wastewater containing heavy metals
CN103011360A (en) * 2012-12-07 2013-04-03 常州大学 Treatment method for industrial wastewater generated by copper wet-process smelting
CN103145227A (en) * 2013-03-25 2013-06-12 西安德奇水处理有限公司 Flocculation treatment method for copper-containing wastewater
CN103214121A (en) * 2013-04-27 2013-07-24 福建格林锘贝尔环保科技有限公司 Method for recycling copper and iron in acid mine wastewater by high-polymer chelating-precipitating agent two-step process
CN105347546A (en) * 2015-11-03 2016-02-24 湖北祥云(集团)化工股份有限公司 Treatment method and system of waste water produced by acid preparation from pyrite
CN105621744A (en) * 2016-03-07 2016-06-01 山东国信环境系统股份有限公司 Copper ore acid wastewater treatment and recovery device and method
CN105692833A (en) * 2016-03-08 2016-06-22 江苏国松环境科技开发有限公司 Process for treating wastewater in copper industry by using polymeric ferric sulfate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘定富等: ""铁粉置换分离电镀废水中的铜和镍"", 《环保科技》 *
曾常华等: ""复合絮凝剂应用于废水重金属去除效率的因素影响及其动力学研究"", 《江西科学》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108746602A (en) * 2018-05-26 2018-11-06 烟台大学 A method of preparing copper-clad iron powder using copper-containing wastewater

Also Published As

Publication number Publication date
CN107176711B (en) 2020-10-16

Similar Documents

Publication Publication Date Title
CN104386874B (en) A kind of wiring board industry high-concentration waste liquor treating process
KR101957548B1 (en) System for treating coal gasification wastewater, and method for treating coal gasification wastewater
CN101734828B (en) Process for treating and recovering dyeing sewage water
CN110002639B (en) Device and method for treating landfill leachate of middle and late-stage domestic garbage landfill
CN106830449A (en) Effectively reduce the method and its processing system of chemical nickle-plating wastewater pollutant
CN113880340B (en) Method for purifying byproduct sodium chloride in organic silicon high-salt wastewater
CN105347542A (en) Guar gum fracturing flow-back fluid water treatment and reuse technology
CN107698098B (en) Organic silicon wastewater treatment system and treatment method thereof
JP2003200199A (en) Sewage treatment method
CN104944692A (en) Water-based ink wastewater treatment method
CN106517588A (en) Efficient treatment method for wastewater of graphene production process
CN108793498A (en) A kind of sulfate radical removal precipitating reagent circulation utilization method
CN110526448A (en) A kind of processing method of high-concentration phosphorus-containing wastewater
CN106348545B (en) A kind of integrated treatment process of Clindamycin Hydrochloride production waste water
CN111253013A (en) Method and device for treating landfill leachate membrane concentrated solution
CN203486994U (en) Treatment system for wastewater containing high-concentration ammonia nitrogen and heavy metal ions
CN102976537A (en) Comprehensive physical and chemical treatment device and method of organic silicon wastewater
CN103755089A (en) Dithiophosphate wastewater pretreatment method
CN107176711A (en) The technique of copper in a kind of high efficiente callback high concentration berberine waste water
CN105084498B (en) A kind of preparation method and application of chitin modified collagen iron and manganese oxides
CN104478159B (en) The method of a kind of sodium formate method sodium hydrosulfite wastewater process
CN102276031B (en) Method for producing high concentration composite water purifying agent with multi-ions of aluminium, zinc and magnesian
CN103112970A (en) Heavy metal recovery and zero emission system and process
CN108249714A (en) A kind of river bottom mud stabilizes and the method for recycling
CN101973659A (en) Device and method for refining waste water by treating vitamin B12 by means of co-use of micro-electrolysis and physicochemical method

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