CN104261625B - Cyaniding waste residue leaching liquor processing method - Google Patents

Cyaniding waste residue leaching liquor processing method Download PDF

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Publication number
CN104261625B
CN104261625B CN201410514669.2A CN201410514669A CN104261625B CN 104261625 B CN104261625 B CN 104261625B CN 201410514669 A CN201410514669 A CN 201410514669A CN 104261625 B CN104261625 B CN 104261625B
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leaching liquor
waste water
waste residue
cyaniding
processing method
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CN104261625A (en
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刘强
李哲浩
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Changchun Gold Research Institute
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • C02F1/32Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • C02F2101/18Cyanides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/30Aerobic and anaerobic processes
    • C02F3/302Nitrification and denitrification treatment

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  • 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)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Physical Water Treatments (AREA)

Abstract

The invention discloses a kind of cyaniding waste residue leaching liquor processing method, the method is by Yin Kefa process, ozone Oxidation Treatment, coagulating kinetics, UV/ozone oxidation processes and biofilter processes five step compositions, cyaniding waste residue leaching liquor is when processing, first select Yin Kefa and Ozonation by tractable pollutant removal, waste water after process carries out coagulating sedimentation by dosing coagulant, remove the heavy metal contaminants in waste water, then under the synergism of ultraviolet and ozone, the difficult pollutant removal remaining by waste water, finally by biofilter, the ammonia nitrogen in waste water and some other residual contaminants are removed. the present invention is according to feature complicated containing pollutant, intractable in gold mine cyaniding waste residue leaching liquor, five steps are combined, work in coordination with and cyaniding waste residue leaching liquor is carried out advanced treating, there is high treating effect, treatment effeciency height, system run all right, technological process is simple, it is simple to the advantage realizing commercial Application, and the waste water after process can return to the technological process of production and uses or qualified discharge as recycled water.

Description

Cyaniding waste residue leaching liquor processing method
Technical field
The present invention relates to field of Environment Protection Pollutant Treatment method, particularly to the processing method of a kind of gold mine cyaniding waste residue leaching liquor.
Background technology
Gold mine in recovery process due to use Cyanide Process, substantial amounts of cyaniding waste residue can be produced, these cyaniding waste residues can produce substantial amounts of leaching liquor in the process of drenching with rain, these leaching liquors do not contain only a certain amount of severe toxicity cyanide, but also the heavy metal ion containing rhodanate and copper, zinc, lead etc, if can not get effective process, it will produce great environmental protection hidden danger. At present, the method of conventional Treatment of Cyanide-containing Wastewater has acidifying absorption method, Pomolio-Celdecor process, Yin Kefa, sulfur dioxide method etc. both at home and abroad, although adopting acidifying absorption method can reclaim a certain amount of cyanide, but owing to recovery of cyanide is not thorough, the remaining a certain amount of cyanide of meeting in waste water, thiocyanate radical and some heavy metal ion are all without effectively being removed simultaneously. Pomolio-Celdecor process process after can remaining substantial amounts of chlorine residue, produce ClCN product, cause secondary pollution problem, the heavy metal ion such as the copper in waste water, zinc, lead fails effectively to be administered simultaneously. Although Yin Kefa and sulfur dioxide method can make cyanid up to standard, but the rhodanate in waste water fails to be effectively addressed, additionally, it is also more to process the waste residue produced in heavy metal process, it is easy to cause secondary pollution. Therefore, in cyanide wastewater process, also still lacking more satisfactory method, if resolving this problem, the sustainable development of China's gold industry and the environmental conservation of gold mine will be had important meaning.
Summary of the invention
The purpose of the present invention is aiming at the problems referred to above that existing processing method exists, and provides the cyaniding waste residue leaching liquor processing method that a kind of technological process is simple, high treating effect, treatment effeciency are high, stable. The present invention is according to the feature containing the multiple pollutants such as cyanide, rhodanate and heavy metal in gold mine cyaniding waste residue leaching liquor, first select Yin Kefa and Ozonation by tractable pollutant removal, waste water after process carries out coagulating sedimentation by dosing coagulant, remove the heavy metal contaminants in waste water, then under the synergism of ultraviolet and ozone, the difficult pollutant removal remaining by waste water, removes the ammonia nitrogen in waste water and some other residual contaminants finally by biofilter. Concrete technology step is as follows:
(1) under stirring and aeration state, adding acid-base reagent, pyrosulfurous acid sodium reagent and catalyst, it is ensured that the pH value of course of reaction controls between 8��10 in waste water, the response time is 30min��120min;
(2) reacted waste water enters ozone treating system, passes into ozone and carries out oxidation processes, and the process time is 15min��120min;
(3) waste water after processing adds flocculating agent under stirring successively and flocculant carries out coagulating sedimentation, and after coagulation, waste water enters sedimentation tank and staticly settles 15min��120min;
(4) wastewater supernatant fluid after precipitation enters into UV/ozone and processes system, and waste water, when ultra violet lamp, passes into ozone and carries out ultraviolet and the reaction of ozone cooperative advanced oxidation, and the response time is 15min��120min;
(5) after reaction, waste water enters biological filter chamber treatment system, when biologic packing material, biofilm strain and air aeration, carries out a biological disposal upon;
(6) waste water after having processed returns in the technological process of production or qualified discharge.
In described step (1), stirring linear velocity is 0.01m/s��10m/s; The gas liquid ratio that during aeration, air passes into is 3��50:1; Acid reagent is sulphuric acid or hydrochloric acid, and base reagent is sodium hydroxide solution or lime cream; Pyrosulfurous acid sodium reagent is the sodium metabisulfite solution of mass fraction 5%��30%, catalyst is the copper-bath of mass fraction 5%��30%, the dosage of pyrosulfurous acid sodium reagent is how many according to the cyanide content in waste water quality and processes index request and determines, cyanide content is high, it is tight to process index request, the dosage of pyrosulfurous acid sodium reagent increases accordingly, otherwise, cyanide content is low, process index request pine, and the dosage of pyrosulfurous acid sodium reagent reduces accordingly; The dosage of catalyst is determined according to the content of bivalent cupric ion in the dosage of pyrosulfurous acid sodium reagent and cyanide wastewater, the dosage of catalyst becomes positive line sexual relationship with the dosage of pyrosulfurous acid sodium reagent, and the bivalent cupric ion content in cyanide wastewater can partly or entirely replace the dosage of catalyst.
In described step (2), ozone intake according to the cyanide in waste liquid and COD content number and process require and determine, cyanide and COD content are high, it is tight to process index request, the intake of ozone increases accordingly, otherwise, cyanide and COD content is low, process index request pine, the intake of ozone reduces accordingly.
In described step (3), stirring linear velocity is 0.01m/s��10m/s, and flocculating agent is polymer-inorganic salt flocculating agent, and flocculant is that polyacrylamide, flocculating agent and flocculant are all configured to solution state and add.
In described step (4), uviol lamp wavelength is 200nm��400nm, the power of uviol lamp and the intake of ozone are how many according to cyanide content remaining in waste water and process index request and determine, cyanide content is high, it is tight to process index request, and the power of uviol lamp increases accordingly, and the intake of ozone increases accordingly, otherwise, cyanide content is low, process index request pine, and the power of uviol lamp reduces accordingly, and the intake of ozone reduces accordingly.
In described step (5), biofilter is up flow type or downflow system reaction tank, water-distributing device and aerator it is provided with at the bottom of pond, aerator is arranged above activated carbon, zeolite or biological potsherd filling layer, loadings accounts for the 1/5��4/5 of reactor volume, biofilm strain is nitrite bacteria and nitrobacteria, and strain biofilm mode is taked manually to add strain biofilm or Biofilmculturing, and gas liquid ratio is set as 1��15:1.
Beneficial effects of the present invention:
The present invention is according to feature complicated containing pollutant, intractable in gold mine cyaniding waste residue leaching liquor, Yin Kefa, Ozonation, coagulant sedimentation, UV/ozone high-level oxidation technology and biofilter treatment technology are combined, work in coordination with and cyaniding waste residue leaching liquor is carried out advanced treating, there is high treating effect, treatment effeciency height, system run all right, technological process is simple, the advantage facilitating implementation commercial Application, the waste water after process can return to the technological process of production and uses or qualified discharge as recycled water.
Detailed description of the invention
The present invention comprises the following steps:
(1) under stirring and aeration state, adding acid-base reagent, pyrosulfurous acid sodium reagent and catalyst, it is ensured that the pH value of course of reaction controls between 8��10 in waste water, the response time is 30min��120min;
(2) reacted waste water enters ozone treating system, passes into ozone and carries out oxidation processes, and the process time is 15min��120min;
(3) waste water after processing adds flocculating agent under stirring successively and flocculant carries out coagulating sedimentation, and after coagulation, waste water enters sedimentation tank and staticly settles 15min��120min;
(4) wastewater supernatant fluid after precipitation enters into UV/ozone and processes system, and waste water, when ultra violet lamp, passes into ozone and carries out ultraviolet and the reaction of ozone cooperative advanced oxidation, and the response time is 15min��120min;
(5) after reaction, waste water enters biological filter chamber treatment system, when biologic packing material, biofilm strain and air aeration, carries out a biological disposal upon;
(6) waste water after having processed returns in the technological process of production or qualified discharge.
In described step (1), stirring linear velocity is 0.01m/s��10m/s; The gas liquid ratio that during aeration, air passes into is 3��50:1; Acid reagent is sulphuric acid or hydrochloric acid, and base reagent is sodium hydroxide solution or lime cream; Pyrosulfurous acid sodium reagent is the sodium metabisulfite solution of mass fraction 5%��30%, catalyst is the copper-bath of mass fraction 5%��30%, the dosage of pyrosulfurous acid sodium reagent is how many according to the cyanide content in waste water quality and processes index request and determines, cyanide content is high, it is tight to process index request, the dosage of pyrosulfurous acid sodium reagent increases accordingly, otherwise, cyanide content is low, process index request pine, and the dosage of pyrosulfurous acid sodium reagent reduces accordingly; The dosage of catalyst is determined according to the content of bivalent cupric ion in the dosage of pyrosulfurous acid sodium reagent and cyanide wastewater, the dosage of catalyst becomes positive line sexual relationship with the dosage of pyrosulfurous acid sodium reagent, and the bivalent cupric ion content in cyanide wastewater can partly or entirely replace the dosage of catalyst.
In described step (2), ozone intake according to the cyanide in waste liquid and COD content number and process require and determine, cyanide and COD content are high, it is tight to process index request, the intake of ozone increases accordingly, otherwise, cyanide and COD content is low, process index request pine, the intake of ozone reduces accordingly.
In described step (3), stirring linear velocity is 0.01m/s��10m/s, and flocculating agent is polymer-inorganic salt flocculating agent, and flocculant is that polyacrylamide, flocculating agent and flocculant are all configured to solution state and add.
In described step (4), uviol lamp wavelength is 200nm��400nm, the power of uviol lamp and the intake of ozone are how many according to cyanide content remaining in waste water and process index request and determine, cyanide content is high, it is tight to process index request, and the power of uviol lamp increases accordingly, and the intake of ozone increases accordingly, otherwise, cyanide content is low, process index request pine, and the power of uviol lamp reduces accordingly, and the intake of ozone reduces accordingly.
In described step (5), biofilter is up flow type or downflow system reaction tank, water-distributing device and aerator it is provided with at the bottom of pond, aerator is arranged above activated carbon, zeolite or biological potsherd filling layer, loadings accounts for the 1/5��4/5 of reactor volume, biofilm strain is nitrite bacteria and nitrobacteria, and strain biofilm mode is taked manually to add strain biofilm or Biofilmculturing, and gas liquid ratio is set as 1��15:1.
Instantiation 1:
Certain gold mine cyaniding waste residue leaching liquor, pH is 9.6, CNTFor 236.65mg/L, SCN��For 78.48mg/L, Cu2+It is 217.45mg/L, NH for 82.56mg/L, COD3-N is 34.26mg/L, additionally contains other heavy metal ion of trace. take 3L waste water and be placed in equipped with in the oxidation reaction groove of stirring system and aerating system, open stirring system, regulating stirring linear velocity is 0.8m/s, open aerating system, aeration rate is adjusted to 1L/min, slowly add the sodium metabisulfite solution 15mL of mass fraction 10%, reaction 30min, stop aeration, reacted waste liquid is placed in ozone-oxidizing device, ozone-oxidizing device interior bottom portion is provided with ceramic micropore aerator, reaction opens ozonation aerated system after starting, pass into ozone reaction 30min, ozone intake is 320mg, reaction stops passing into ozone after terminating, waste water is moved in agitator tank, open stirring, 5min is stirred stirring the polymeric aluminum chlorides solution 15mL adding 10g/L when linear velocity is 0.8m/s, then mass fraction 0.5 �� PAMA solution 4mL is added, regulate stirring linear velocity 0.1m/s after continuing stirring 2min and stir 5min, stop stirring, stand 30min, with peristaltic pump, supernatant is pumped in the reactor equipped with ultraviolet lamp device and ozonation aerated device, uviol lamp power is 4W, wavelength is 254nm, erect the center being placed on inside reactor, ozonation aerated device adopts ceramic micropore aerator, it is placed in the bottom in reactor, reaction opens uviol lamp after starting, pass into ozone reaction 30min, ozone intake is 210mg, reaction stops passing into ozone after terminating, waste water is moved in biofilter and processes, biofilter is up flow type bioreactor, biofilter filling filler is particulate coal activated carbon, amount of fill is 5kg, air aeration device adopts Ti-alloyed filter element, it is placed in reactor bottom, gas liquid ratio is set as 3:1, reactor carries out biofilm by manually adding strain, the waste water reaction time of staying is 60min. waste water through system process after water outlet through assay pH between 8��9, CNT< 0.1mg/L, SCN��< 0.5mg/L, Cu2+< 0.5mg/L, COD < 20mg/L, NH3-N < 1.0mg/L, first kind pollutant are all within the highest permission concentration of emission limit value, and after process, water quality can reach reuse or discharge standard.
Instantiation 2:
Certain gold mine cyaniding waste residue leaching liquor, pH is 8.5, CNTFor 123.26mg/L, SCN��For 45.62mg/L, Cu2+For 7.83mg/L, Fe3+For 24.69mg/L, Pb2+It is 142.55mg/L, NH for 5.42mg/L, COD3-N is 22.73mg/L, additionally contains other heavy metal ion of trace.Take 3L waste water and be placed in equipped with in the oxidation reaction groove of stirring system and aerating system, open stirring system, regulating stirring linear velocity is 0.8m/s, open aerating system, aeration rate is adjusted to 1L/min, slowly add the sodium metabisulfite solution 10mL of the mass fraction 10% and copper-bath 1mL of mass fraction 5%, reaction 30min, stop aeration, reacted waste liquid is placed in ozone-oxidizing device, ozone-oxidizing device interior bottom portion is provided with ceramic micropore aerator, reaction opens ozonation aerated system after starting, pass into ozone reaction 30min, ozone intake is 180mg, reaction stops passing into ozone after terminating, waste water is moved in agitator tank, open stirring, 5min is stirred stirring the polymeric aluminum chlorides solution 10mL adding 10g/L when linear velocity is 0.8m/s, then mass fraction 0.5 �� PAMA solution 2mL is added, regulate stirring linear velocity 0.1m/s after continuing stirring 2min and stir 5min, stop stirring, stand 30min, with peristaltic pump, supernatant is pumped in the reactor equipped with ultraviolet lamp device and ozonation aerated device, uviol lamp power is 4W, wavelength is 254nm, erect the center being placed on inside reactor, ozonation aerated device adopts ceramic micropore aerator, it is placed in the bottom in reactor, reaction opens uviol lamp after starting, pass into ozone reaction 30min, ozone intake is 150mg, reaction stops passing into ozone after terminating, waste water is moved in biofilter and processes, biofilter is up flow type bioreactor, biofilter filling filler is particulate coal activated carbon, amount of fill is 5kg, air aeration device adopts Ti-alloyed filter element, it is placed in reactor bottom, gas liquid ratio is set as 3:1, reactor carries out biofilm by manually adding strain, the waste water reaction time of staying is 60min. waste water through system process after water outlet through assay pH between 8��9, CNT< 0.1mg/L, SCN��< 0.5mg/L, Cu2+< 0.5mg/L, COD < 20mg/L, NH3-N < 1.0mg/L, first kind pollutant are all within the highest permission concentration of emission limit value, and after process, water quality can reach reuse or discharge standard.

Claims (10)

1. a cyaniding waste residue leaching liquor processing method, the step of the method is as follows:
(1) under stirring and aeration state, adding acid-base reagent, pyrosulfurous acid sodium reagent and catalyst, it is ensured that the pH value of course of reaction controls between 8��10 in waste water, the response time is 30min��120min;
(2) reacted waste water enters ozone treating system, passes into ozone and carries out oxidation processes, and the process time is 15min��120min;
(3) waste water after processing adds flocculating agent under stirring successively and flocculant carries out coagulating sedimentation, and after coagulation, waste water enters sedimentation tank and staticly settles 15min��120min;
(4) wastewater supernatant fluid after precipitation enters into UV/ozone and processes system, and waste water, when ultra violet lamp, passes into ozone and carries out ultraviolet and the reaction of ozone cooperative advanced oxidation, and the response time is 15min��120min;
(5) after reaction, waste water enters biological filter chamber treatment system, when biologic packing material, biofilm strain and air aeration, carries out a biological disposal upon;
(6) waste water after having processed returns in the technological process of production or qualified discharge.
2. a kind of cyaniding waste residue leaching liquor processing method according to claim 1, it is characterised in that: in described step (1), stirring linear velocity is 0.01m/s��10m/s.
3. a kind of cyaniding waste residue leaching liquor processing method according to claim 1, it is characterised in that: in described step (1), the gas liquid ratio that during aeration, air passes into is 3��50:1.
4. a kind of cyaniding waste residue leaching liquor processing method according to claim 1, it is characterised in that: in described step (1), acid reagent is sulphuric acid or hydrochloric acid, and base reagent is sodium hydroxide solution or lime cream.
5. cyaniding waste residue leaching liquor processing method according to claim 1, it is characterised in that: in described step (1), pyrosulfurous acid sodium reagent is the sodium metabisulfite solution of mass fraction 5%��30%; Described catalyst is the copper-bath of mass fraction 5%��30%.
6. a kind of cyaniding waste residue leaching liquor processing method according to claim 1, it is characterised in that: in described step (3), stirring linear velocity is 0.01m/s��10m/s.
7. a kind of cyaniding waste residue leaching liquor processing method according to claim 1, it is characterized in that: in described step (3), flocculating agent is polymer-inorganic salt flocculating agent, and flocculant is that polyacrylamide, flocculating agent and flocculant are all configured to solution state and add.
8. a kind of cyaniding waste residue leaching liquor processing method according to claim 1, it is characterised in that: in described step (4), uviol lamp wavelength is 200nm��400nm.
9. a kind of cyaniding waste residue leaching liquor processing method according to claim 1, it is characterized in that: in described step (5), biofilter is up flow type or downflow system reaction tank, water-distributing device and aerator it is provided with at the bottom of pond, aerator is arranged above activated carbon, zeolite or biological potsherd filling layer, and loadings accounts for the 1/5��4/5 of reactor volume.
10. a kind of cyaniding waste residue leaching liquor processing method according to claim 1, it is characterized in that: in described step (5), biofilter biofilm strain is nitrite bacteria and nitrobacteria, strain biofilm mode is taked manually to add strain biofilm or Biofilmculturing, and gas liquid ratio is set as 1��15:1.
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CN104944645A (en) * 2015-07-17 2015-09-30 北京矿冶研究总院 Cyanide-containing tailing slurry treatment method
CN105127181B (en) * 2015-08-23 2018-08-28 长春黄金研究院 A kind of gold tailing ponds in-situ immobilization processing method
CN109824205A (en) * 2019-03-04 2019-05-31 广东益诺欧环保股份有限公司 A kind of method and system handling high toxicity high concentrated organic wastewater

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