CN110306063A - A method of organic matter in the heavy germanium solution of removing wet zinc-making system tannic acid - Google Patents

A method of organic matter in the heavy germanium solution of removing wet zinc-making system tannic acid Download PDF

Info

Publication number
CN110306063A
CN110306063A CN201910637307.5A CN201910637307A CN110306063A CN 110306063 A CN110306063 A CN 110306063A CN 201910637307 A CN201910637307 A CN 201910637307A CN 110306063 A CN110306063 A CN 110306063A
Authority
CN
China
Prior art keywords
solution
organic matter
tannic acid
added
zinc
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.)
Pending
Application number
CN201910637307.5A
Other languages
Chinese (zh)
Inventor
张威
陆占清
邹利明
焦志良
范茂盛
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.)
Yunnan Hongchi Resource Integration Utilization Co Ltd
Original Assignee
Yunnan Hongchi Resource Integration Utilization Co Ltd
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 Yunnan Hongchi Resource Integration Utilization Co Ltd filed Critical Yunnan Hongchi Resource Integration Utilization Co Ltd
Priority to CN201910637307.5A priority Critical patent/CN110306063A/en
Publication of CN110306063A publication Critical patent/CN110306063A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C22B41/00—Obtaining germanium
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The present invention relates to a kind of methods of organic matter in heavy germanium solution of removing wet zinc-making system tannic acid, belong to Zinc Hydrometallurgy Technology field, the present invention includes an organic matter decomposition, pulp, oxidation, the decomposition of Secondary Organic object, purifies and adsorb several important process steps, according to tannin sink solution after germanium the characteristics of, by the way that decomposing hydrogen dioxide solution organic matter is added, while utilizing the Fe itself contained in solution2+, catalysis acceleration is played to the decomposition of organic matter；The liquid after the tannin of technical solution of the present invention processing sinks germanium will not introduce new impurity, and organic removal rate is up to 75% or more, and purified sulfuric acid zinc electrolysis electricity effect is up to 92.3%, much higher than the 90.97% of currently used potassium permanganate organic matter removal method.

Description

A method of organic matter in the heavy germanium solution of removing wet zinc-making system tannic acid
Technical field
The invention belongs to zinc hydrometallurgy fields, specifically, it is molten to be related to a kind of heavy germanium of removing wet zinc-making system tannic acid The method of organic matter in liquid.
Background technique
In the Zinc hydrometallurgy process using zinc oxide fumes as raw material, due to being rich in rare precious metal germanium in flue dust, at present The recycling of germanium is to be settled out germanium by the way that excessive tannic acid is added in germanium-containing solution.If the additional amount of tannic acid is insufficient, It can make after heavy germanium that Ge content increases in liquid, not only cause germanium metal loss, be also easy that harmful substance is made to be brought into electrolysis system, shadow Zinc metal sheet quality is rung, the additional amount of usual tannic acid is 23-28 times of Ge content in solution.Although the addition of excessive tannic acid guarantees The recycling of germanium, but the drawbacks of postorder solution organic matter increases also is brought simultaneously.Organic matter increases electrolyte in electrolyte Viscosity and resistance carry out difficulty so as to cause process in zinc electrolyzing, and being electrolysed electricity effect reduces.Therefore it needs to have tannin in liquid after heavy germanium The removal of machine object.
Currently, the measure of control organic matter is to add potassium permanganate in liquid after heavy germanium, decompose oxidation operation, and lead to Cross filter press filtering removal.The effect of this controlling measurement content of organics is not significant, the removal rate of organic matter less than 20%, Still it can't resolve influence of the organic matter to process in zinc electrolyzing.
And in the research and practice process to the method, although present inventor have discovered that above-mentioned technique can be to a certain degree The upper raising for inhibiting organic matter, but additive potassium permanganate can bring unnecessary metal ion in wet process into, reduce sulfuric acid The electrolysis electricity of zinc solution is imitated.
Summary of the invention
In order to solve the problems, such as background technique, it is heavy that the present invention provides a kind of removing wet zinc-making system tannic acid The method of organic matter in germanium solution, liquid organic removal rate is up to 75% or more after can making heavy germanium, and will not introduce new impurity, clearly It is clean efficient, it is suitble to industrialized production.
To achieve the above object, the present invention is achieved through the following technical solutions:
The method of organic matter includes the following steps: in the heavy germanium solution of the removing wet zinc-making system tannic acid
(1) primary to decompose: to sink in tannic acid and hydrogen peroxide is added in germanium filtrate, carry out an organic matter and decompose；
(2) paddle: basic solvent adjusting pH value is added in heavy germanium filtrate after once oxidation, obtains dense after pulp liquid；
(3) it aoxidizes: being passed through compressed air in the supernatant of pulp liquid and carry out oxidation reaction, by part Fe2+It is oxidized to Fe3 +, filter after reaction, obtain filtrate and filter residue；
(4) second decomposition: hydrogen peroxide is added in step (3) filtrate, carries out the second decomposition of organic matter；
(5) it purifies: step (4) filtrate is purified；
(6) it adsorbs: active carbon is added, purified filtrate is adsorbed；
(7) filter: the filtrate filtering after being cleaned with activated carbon adsorption, filtrate are sent to zinc sulfate electrowinning process.
Further, the primary decomposition of step (1) organic matter, the heavy germanium solution temperature of tannic acid is 50-60 DEG C, with hydrogen peroxide Volume ratio be 90-110:1, the reaction time be 15-30 minutes.
Further, step (2) paddle process is added basic solvent and adjusts solution PH between 3.0-3.5, in the pH value Range can remain with part Fe in guarantee section iron Precipitation and solution2+, accelerate for subsequent Secondary Organic object Offer condition is provided；The control of paddle solution temperature is 55-60 DEG C.
Further, oxidation described in step (3) is by being passed through compressed air in the supernatant of pulp liquid, and compression is empty Gas is at the uniform velocity added by air sparger, and supernatant is in stirring under the promotion of compressed air, completes the part Fe in solution2+ It is oxidized to Fe3+。
Further, after step (3) oxidation, it is 4.8-5.0 that milk of lime is added again and adjusts terminal PH, makes partial molten iron solution And Precipitation is formed, Fe in solution at this time2+Content is about 30mg/l.
Further, the volume ratio of step (4) filtrate and hydrogen peroxide is 180-220:1.
Further, purification described in step (5) be can be replaced using the metal compared with elecrtonegativity (relatively active) in solution compared with The principle of electropositive metal ion, it is molten out by the way that zinc dust precipitation is added in the solution of zinc sulfate containing impurity such as copper, cadmium, cobalts The foreign ions such as copper, cadmium, cobalt and the process removed by way of filtering in liquid.
Further, the active carbon that step (6) is added is cocoanut active charcoal, and partial size is not more than 0.6mm, additional amount 2- 4kg/m3.Adsorption time is 30-60 minutes.
Further, the basic solvent is milk of lime.
Beneficial effects of the present invention:
1, the present invention utilizes the mechanism of action of Fendon reagent, sinks after germanium liquid containing Fe in conjunction with tannin2+The characteristics of, by list Hydrogen peroxide rather is added in liquid after heavy germanium, makes organic matter in decomposing hydrogen dioxide solution solution, the iron in solution plays the decomposition of organic matter The effect that catalysis accelerates, does not introduce additional impurities, even if tannin sinks after germanium, there is up to 75% or more the removal rate of organic matter in liquid Imitate influence of the organic matter to subsequent process in zinc electrolyzing in solution after reducing the heavy germanium of tannin.
2, the present invention is by being the solution temperature because in a decomposable process twice plus hydrogen peroxide carries out organic decomposition It is 50-60 DEG C, in the high temperature environment, a part of hydrogen peroxide meeting natural decomposition is water and oxygen, weakens the decomposition to organic matter Effect.It, can will be big in solution due to the strong oxidizing property of hydrogen peroxide if the hydrogen peroxide of (or excessive) enough is added in primary decompose The Fe of amount2+Rapid oxidation is Fe3+, and hydrolyzed during subsequent adjustment PH and form precipitating, it is suppressed that Fe2+Accelerate hydrogen peroxide The effect of decomposing organic matter.Therefore, using the hydrogen peroxide method that just organic matter decomposes is added twice, pass through control hydrogen peroxide Fe in additional amount and solution2+Content, can ensure that hydrogen peroxide to the decomposition efficiency of organic matter, also ensures that zinc sulphate electrolyte Residual requirement to iron content.
3, the present invention can make iron precipitating analysis in solution by liquid pH value after the heavy germanium of addition milk of lime adjustment tannin twice Out, Fe is in turn ensured2+The catalysis that organic matter decomposes is accelerated, and then it is effectively net to ensure that purified solution of zinc sulfate has obtained Change.
4, the present invention makes Fe in solution by blasting compressed air2+It is oxidized to Fe3+, ensure that the effective of iron sinks in solution It forms sediment, ensure that the clean-up effect of solution of zinc sulfate.
5, the present invention enhances the purification effect of solution of zinc sulfate by the way that the further adsorbing contaminant of active carbon and organic matter is added Fruit.
6, the present invention is by the implementation of overall technical architecture, efficiently solves tannin and sinks in germanium solution organic matter and other miscellaneous The removal of matter is imitated the electrolysis electricity of solution of zinc sulfate and is improved to 92.3% or more, provides qualified zinc sulfate for the electrolysis of zinc Solution.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention；
Fig. 2 is sour heavy germanium solution organic matter removal process flow diagram peaceful at present.
Specific embodiment
It, below will be to preferred reality of the invention in order to keep the purpose of the present invention, technical scheme and beneficial effects clearer It applies example to be described in detail, to facilitate the technical staff to understand.
Embodiment 1
By 27.5% industrial hydrogen peroxide solution according to 0.6m3The flow velocity of/h is even added to the filter after the heavy germanium of tannic acid In liquid (TOC content is 194mg/l), carries out an organic matter and decompose.According to the mechanism of action of Fendon reagent, Fe in solution2+ Presence, catalytic action is played to hydrogen peroxide decomposing organic matter, accelerates the decomposition of organic matter.The volume ratio of filtrate and hydrogen peroxide For 100:1, it is stirred to react 15 minutes；Milk of lime and constantly agitating paddle are added in the solution, measurement solution terminal PH is 3.2, It persistently stirs 1 hour, real-time monitoring solution temperature in whipping process, is 55-60 using steam computer heating control paddle reaction temperature ℃.By increasing pH value, part iron Precipitation can be made, at this time the Fe in solution2+Content 6.3g/L.By measuring paddle solution In TOC content be 96mg/l, the TOC removal rate in this stage reaches 50.51%；
After dense, supernatant is passed through compressed air and carries out removing iron by oxidation paddle solution, makes Fe2+It is oxidized to Fe3+, compression Air pressure is 0.4Mpa, flow velocity 450m3/ h, is added by air sparger, and the compressed air being passed through plays sky to solution Gas agitating effect, and then accelerated oxidation.It is 5.0 that milk of lime is added after removing iron by oxidation and adjusts solution terminal PH, makes the Fe in solution Precipitation, while keeping Fe in solution2+Content is between 0.02-0.05g/L.So that Fe2+Secondary Organic object is decomposed and is continued Play catalytic action.Through testing and analyzing, Fe in solution at this time2+Content is 0.03g/L.
According to 0.3m in solution in and after heavy iron3The flow of/h is added hydrogen peroxide and carries out the decomposition of Secondary Organic object, filter The volume ratio of liquid and hydrogen peroxide is 200:1, Fe in solution2+Still the catalyst decomposed as organic matter, Secondary Organic object decompose After filter, through detecting, content of organics drops to 64mg/l in filtrate, at this time the removal rate of TOC be 67.01%.
Filtrate carry out one, two, three section of purification and impurity removal (utilize the metal compared with elecrtonegativity (relatively active) can replace in solution compared with The principle of electropositive metal ion, it is molten out by the way that zinc dust precipitation is added in the solution of zinc sulfate containing impurity such as copper, cadmium, cobalts The foreign ions such as copper, cadmium, cobalt and the process removed by way of filtering in liquid)；180kg is added in solution after three sections of purifications Active carbon, stirring is filtered after 30 minutes, and through detecting, the TOC of filtrate drops to 47mg/l, and the removal rate of organic matter is up to 75.77%. Gained filtrate is purified solution of zinc sulfate, is sent directly into zinc electrolysis system.The electrolysis of solution of zinc sulfate after detection purification Electricity effect is 92.3%.
Purified solution of zinc sulfate situation is shown in Table 1:
The purified solution of zinc sulfate main matter content of table 1 and electricity effect situation table
Embodiment 2
By 27.5% industrial hydrogen peroxide solution according to 0.6m3The flow velocity of/h is even added to the filter after the heavy germanium of tannic acid In liquid (TOC content is 194mg/l), carries out an organic matter and decompose.According to the mechanism of action of Fendon reagent, Fe in solution2+ Presence, catalytic action is played to hydrogen peroxide decomposing organic matter, accelerates the decomposition of organic matter.The volume ratio of filtrate and hydrogen peroxide For 120:1, it is stirred to react 25 minutes；Milk of lime and constantly agitating paddle are added in the solution, measurement solution terminal PH is 3.4, It persistently stirs 1 hour, real-time monitoring solution temperature in whipping process, is 55-60 using steam computer heating control paddle reaction temperature ℃.By increasing pH value, part iron Precipitation can be made, at this time the Fe in solution2+Content 5.1g/L.By measuring paddle solution In TOC content be 95mg/l, the TOC removal rate in this stage reaches 51.04%；
After dense, supernatant is passed through compressed air and carries out removing iron by oxidation paddle solution, makes Fe2+It is oxidized to Fe3+, compression Air pressure is 0.45Mpa, flow velocity 450m3/ h, is added by air sparger, and the compressed air being passed through plays sky to solution Gas agitating effect, and then accelerated oxidation.It is 4.8 that milk of lime is added after removing iron by oxidation and adjusts solution terminal PH, makes the Fe in solution Precipitation, while keeping Fe in solution2+Content is between 0.02-0.05g/L.So that Fe2+Secondary Organic object is decomposed and is continued Play catalytic action.Through testing and analyzing, Fe in solution at this time2+Content is 0.03g/L.
According to 0.3m in solution in and after heavy iron3The flow of/h is added hydrogen peroxide and carries out the decomposition of Secondary Organic object, filter The volume ratio of liquid and hydrogen peroxide is 220:1, Fe in solution2+Still the catalyst decomposed as organic matter, Secondary Organic object decompose After filter, through detecting, content of organics drops to 60mg/l in filtrate, at this time the removal rate of TOC be 71.48%.
Filtrate carry out one, two, three section of purification and impurity removal (utilize the metal compared with elecrtonegativity (relatively active) can replace in solution compared with The principle of electropositive metal ion, it is molten out by the way that zinc dust precipitation is added in the solution of zinc sulfate containing impurity such as copper, cadmium, cobalts The foreign ions such as copper, cadmium, cobalt and the process removed by way of filtering in liquid)；180kg is added in solution after three sections of purifications Active carbon, stirring is filtered after 30 minutes, and through detecting, the TOC of filtrate drops to 46mg/l, and the removal rate of organic matter is up to 77.42%. Gained filtrate is purified solution of zinc sulfate, is sent directly into zinc electrolysis system.The electrolysis of solution of zinc sulfate after detection purification Electricity effect is 92.8%.
Purified solution of zinc sulfate situation is shown in Table 1:
The purified solution of zinc sulfate main matter content of table 2 and electricity effect situation table
Embodiment 3
By 27.5% industrial hydrogen peroxide solution according to 0.6m3The flow velocity of/h is even added to filtrate after the heavy germanium of tannic acid In (TOC content is 192mg/l), carries out an organic matter and decompose.According to the mechanism of action of Fendon reagent, Fe in solution2+'s In the presence of playing catalytic action to hydrogen peroxide decomposing organic matter, accelerate the decomposition of organic matter.The volume ratio of filtrate and hydrogen peroxide is 100:1 is stirred to react 15 minutes；Milk of lime and constantly agitating paddle are added in the solution, until solution terminal PH to 5.0, holds Continuous stirring 1 hour, real-time monitoring solution temperature in whipping process are 55-60 DEG C using steam computer heating control paddle reaction temperature. By increasing pH value, make part iron Precipitation, at this time the Fe in solution2+Content is 0.5g/L.By in measurement paddle solution TOC content be 104mg/l, the TOC removal rate in this stage reaches 45.83%.
After dense, supernatant is passed through compressed air and carries out removing iron by oxidation paddle solution, makes Fe2+It is oxidized to Fe3+, compression Air pressure is 0.4Mpa, flow velocity 450m3/ h, is added by air sparger, and the compressed air being passed through plays sky to solution Gas agitating effect, and then accelerated oxidation.It is filtered after oxidation, through testing and analyzing, Fe in filtrate at this time2+Content is only 0.004g/l.
According to 0.3m in solution in and after heavy iron3The flow of/h is added hydrogen peroxide and carries out the decomposition of Secondary Organic object, filter The volume ratio of liquid and hydrogen peroxide is 200:1, Fe in solution2+Still the catalyst decomposed as organic matter, Secondary Organic object decompose After filter, through detecting, content of organics drops to 86mg/l in filtrate, at this time the removal rate of TOC be 55.2%.
Filtrate carry out one, two, three section of purification and impurity removal (utilize the metal compared with elecrtonegativity (relatively active) can replace in solution compared with The principle of electropositive metal ion, it is molten out by the way that zinc dust precipitation is added in the solution of zinc sulfate containing impurity such as copper, cadmium, cobalts The foreign ions such as copper, cadmium, cobalt and the process removed by way of filtering in liquid)；180kg is added in solution after three sections of purifications Active carbon, stirring is filtered after 30 minutes, and through detecting, the TOC of filtrate drops to 68mg/l, and the removal rate of organic matter is up to 64.58%. Gained filtrate is purified solution of zinc sulfate, is sent directly into zinc electrolysis system.The electrolysis of solution of zinc sulfate after detection purification Electricity effect are as follows: 91.2%.
Purified solution of zinc sulfate situation is shown in Table 2:
The purified solution of zinc sulfate main matter content of table 3 and electricity effect situation table
Embodiment 4
By 27.5% industrial hydrogen peroxide solution according to 0.9m3The flow velocity of/h is even added to filtrate after the heavy germanium of tannic acid In (TOC content is 196mg/l), organic matter decomposition is carried out.The volume ratio of filtrate and hydrogen peroxide is 150:1, and decomposition temperature is lasting Control is 50-60 DEG C, is stirred to react 15 minutes；Milk of lime and constantly agitating paddle are added in solution tank, measures solution pH value It is 3.4, and continues stirring 1 hour, real-time monitoring solution temperature in whipping process utilizes steam computer heating control paddle solution temperature At 55-60 DEG C；After dense, supernatant is passed through compressed air and carries out removing iron by oxidation paddle solution, makes Fe2+It is oxidized to Fe3+, pressure Contracting air pressure is 0.4mpa, flow velocity 450m3/h.It is 5.0 that milk of lime is added after removing iron by oxidation and adjusts solution terminal PH, is made molten Fe Precipitation in liquid filters after heavy iron, will neutralize filtrate after heavy iron carry out one, two, three section of purification and impurity removal matter (utilize compared with The metal of elecrtonegativity (relatively active) can replace in solution compared with the principle of electropositive metal ion, contain the impurity such as copper, cadmium, cobalt In solution of zinc sulfate, go out the foreign ions such as copper in solution, cadmium, cobalt by the way that zinc dust precipitation is added and by filtering by way of remove Process)；180kg active carbon is added in solution after three sections of purifications, stirring is filtered after 30 minutes, and filtrate is that finished product sulfuric acid zinc is molten Liquid is sent to zinc electrolysis system.The content of organics of solution of zinc sulfate is 71mg/l, organic removal rate after detection purification are as follows: 63.77%, it is electrolysed electricity effect are as follows: 91.16%
Purified solution of zinc sulfate situation is shown in Table 3:
The purified solution of zinc sulfate main matter content of table 4 and electricity effect situation table
Embodiment 5
By 27.5% industrial hydrogen peroxide solution according to 0.9m3The flow velocity of/h is even added to filtrate after the heavy germanium of tannic acid In (TOC content be 193mg/l), carry out organic matter decomposition.The volume ratio of filtrate and hydrogen peroxide is 150:1, and decomposition temperature is lasting Control is stirred to react 15 minutes between 50-60 DEG C；Milk of lime and constantly agitating paddle are added in solution tank, until solution PH is adjusted to 4.9, and continues stirring 1 hour, and real-time monitoring solution temperature in whipping process is molten using steam computer heating control paddle Liquid temperature is at 55-60 DEG C；After dense, supernatant is passed through compressed air and carries out removing iron by oxidation paddle solution, makes Fe2+It is oxidized to Fe3+, compressed air pressure 0.4mpa, flow velocity 450m3/h.After removing iron by oxidation, filtrate after heavy iron is carried out one, two, three section Purification and impurity removal matter (utilize the metal compared with elecrtonegativity (relatively active) that can replace in solution compared with the principle of electropositive metal ion, In solution of zinc sulfate containing impurity such as copper, cadmium, cobalts, go out the foreign ions such as copper in solution, cadmium, cobalt simultaneously by the way that zinc dust precipitation is added The process removed by way of filtering)；180kg active carbon is added in solution after three sections of purifications, stirring is filtered after 30 minutes, Filtrate is finished product sulfuric acid zinc solution, is sent to zinc electrolysis system.The content of organics of solution of zinc sulfate after detection purification are as follows: 82mg/l, organic removal rate are as follows: 57.51%, it is electrolysed electricity effect are as follows: 91.02%.
Purified solution of zinc sulfate situation is shown in Table 4:
The purified solution of zinc sulfate main matter content of table 5 and electricity effect situation table
Embodiment 6
By pulp of blunging in solid potassium permanganate addition pulp bucket, the mass ratio of potassium permanganate and water is 1:2, is kept Pulp bucket persistently stirs.Potassium permanganate pulp liquid according to 0.4m3The flow velocity of/h is even added to filtrate after the heavy germanium of tannic acid In (TOC content is 195mg/l), organic matter decomposition is carried out.The volume ratio of filtrate and potassium permanganate pulp liquid is 200:1, is decomposed Constant temperature control is 50-60 DEG C, is stirred to react 30 minutes；Milk of lime and constantly agitating paddle, measurement are added in solution tank Solution pH value is 3.3, and continues stirring 1.5 hours, and real-time monitoring solution temperature in whipping process utilizes steam computer heating control paddle Change solution temperature at 55-60 DEG C；It is 5.0 that paddle solution, which enters dense slot and milk of lime is added again to adjust solution terminal PH, is made Fe Precipitation in solution filters after heavy iron, and filtrate carries out one, two, three section of purification and impurity removal matter after neutralizing heavy iron；At three sections 180kg active carbon is added after purification in solution, stirring is filtered after 30 minutes, and filtrate is finished product sulfuric acid zinc solution, is sent to zinc electrolysis System.The content of organics of solution of zinc sulfate is 156.78mg/l, organic removal rate after detection purification are as follows: 19.6%, electricity Solution electricity effect are as follows: 86.97%.
Purified solution of zinc sulfate situation is shown in Table 5:
The purified solution of zinc sulfate main matter content of table 6 and electricity effect situation table
It should be noted that the present invention adjusts PH using addition milk of lime twice, it, can if the adjustment of first time PH is excessively high Keep iron amount of precipitation excessive, Fe in solution2+Concentration reduces, and does not have catalytic action to the decomposition of organic matter；PH value control is too low, then Fe in solution3+Residual quantity is excessive, will increase the resistance of zinc electrolysis, reduces zinc electrolysis electricity effect.Due to Fe2+It hydrolyzes pH value and is higher than Fe3+ Hydrolyze pH value.To by iron ion removing in solution, more effective method is first to oxidize divalent iron ions into trivalent, then into one Step improves solution ph, removes ferric ion hydrolytic precipitation from solution.PH is adjusted in two times, is because adjusting for the first time PH is by the part Fe in solution3+Hydrolysis removal, while retaining the Fe in solution2+Content accelerates decomposing hydrogen dioxide solution organic matter, Second of adjustment PH, is to be passed through air in the solution for part Fe2+It is oxidized to Fe3+Afterwards, Fe is allowed by improving PH3+Hydrolysis removal. If only using Primary regulation PH, the lime breast amount being added is more, will cause that solution PH is excessively high, and not only iron hydrolyzes, Zn2+Also can It hydrolyzes, causes zinc metal loss.And the present inventor passes through a large amount of practical proofs, discovery is between PH 3.0-3.5 and contains There is Fe2+Solution in, hydrogen peroxide is stronger to the oxidative decomposition capacity of organic matter, lower than the capacity of decomposition of the PH range organic matter Weakened.
Secondly, can introduce potassium ion and manganese ion using the method for potassium permanganate removal organic matter, potassium ion is alkali metal Ion will lead to density of electrolyte increase, increase electrolyte specific resistance, increase slot although not reacting in electrolytic process Voltage increases power consumption；System manganese ion increases, and will lead to the increase of electrolytic process manganese ion amount of precipitation, reduces Faradaic current The efficiency earth of positive pole largely generates, and increases clear slot amount and clear slot frequency.Further, since the earth of positive pole largely generates, it is easy to cause anode Plate Anodic mud is blocked up, increases yin-yang interpolar and touches the probability of electricity, and increases the probability of slot bottom earth of positive pole contact pole plate bottom.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention rather than limits, although logical It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be Various changes are made to it in form and in details, without departing from claims of the present invention limited range.

Claims (9)

1. a kind of method of organic matter in heavy germanium solution of removing wet zinc-making system tannic acid, it is characterised in that: the removing The method of organic matter includes: in the heavy germanium solution of wet zinc-making system tannic acid
(1) primary to decompose: to sink in tannic acid and hydrogen peroxide is added in germanium filtrate, carry out an organic matter and decompose；
(2) paddle: basic solvent adjusting pH value is added in heavy germanium filtrate after once oxidation, obtains dense after pulp liquid；
(3) it aoxidizes: being passed through compressed air in the supernatant of pulp liquid and carry out oxidation reaction, by part Fe2+It is oxidized to Fe3+, instead It is filtered after answering, obtains filtrate and filter residue；
(4) second decomposition: hydrogen peroxide is added in step (3) filtrate, carries out the second decomposition of organic matter；
(5) it purifies: step (4) filtrate is purified；
(6) it adsorbs: active carbon is added, purified filtrate is adsorbed；
(7) filter: the filtrate filtering after being cleaned with activated carbon adsorption, filtrate are sent to zinc sulfate electrowinning process.
2. the method for organic matter in a kind of heavy germanium solution of removing wet zinc-making system tannic acid according to claim 1, Be characterized in that: the primary decomposition of step (1) organic matter, the heavy germanium solution temperature of tannic acid is 50-60 DEG C, the volume ratio with hydrogen peroxide For 90-110:1, the reaction time is 15-30 minutes.
3. the method for organic matter in a kind of heavy germanium solution of removing wet zinc-making system tannic acid according to claim 1, Be characterized in that: step (2) paddle process is added basic solvent and adjusts solution PH between 3.0-3.5, the pH range can Guarantee section iron Precipitation, and can guarantee and remain with part Fe in solution2+, allow Fe2+It is lasting to accelerate the residue after primary decompose Decomposition of the hydrogen peroxide to organic matter in solution, while also providing condition for subsequent Secondary Organic object accelerated decomposition；Paddle temperature Degree control is 55-60 DEG C.
4. the method for organic matter in a kind of heavy germanium solution of removing wet zinc-making system tannic acid according to claim 1, Be characterized in that: oxidation described in step (3) is by being passed through compressed air in the supernatant of pulp liquid, and compressed air is by air Distributor is at the uniform velocity added, and supernatant is in stirring under the promotion of compressed air, completes the part Fe in solution2+It is oxidized to Fe3+。
5. the method for organic matter in a kind of heavy germanium solution of removing wet zinc-making system tannic acid according to claim 1, Be characterized in that: after step (3) oxidation, it is 4.8-5.0 that basic solvent is added again and adjusts terminal PH, makes partial molten iron solution and is formed Precipitation, while guaranteeing still to contain a certain amount of Fe in solution2+, condition is provided for subsequent Secondary Organic object accelerated decomposition.
6. the method for organic matter in a kind of heavy germanium solution of removing wet zinc-making system tannic acid according to claim 1, Be characterized in that: the volume ratio of step (4) filtrate and hydrogen peroxide is 180-220:1.
7. the method for organic matter in a kind of heavy germanium solution of removing wet zinc-making system tannic acid according to claim 1, Be characterized in that: purification described in step (5) is to be replaced in solution using the metal compared with elecrtonegativity (relatively active) compared with electropositive gold Belong to ion principle, in the solution of zinc sulfate containing impurity such as copper, cadmium, cobalts, by be added zinc dust precipitation go out copper in solution, The foreign ions such as cadmium, cobalt and the process removed by way of filtering.
8. the method for organic matter in a kind of heavy germanium solution of removing wet zinc-making system tannic acid according to claim 1, Be characterized in that: the active carbon that step (6) is added is cocoanut active charcoal, and partial size is not more than 0.6mm, additional amount 2-4kg/m3,
Adsorption time 30-60 minutes.
9. according to claim 1, a kind of 3 or 5 described in any item removing wet zinc-making system tannic acid sink organic in germanium solution The method of object, it is characterised in that: the basic solvent is milk of lime.
CN201910637307.5A 2019-07-15 2019-07-15 A method of organic matter in the heavy germanium solution of removing wet zinc-making system tannic acid Pending CN110306063A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910637307.5A CN110306063A (en) 2019-07-15 2019-07-15 A method of organic matter in the heavy germanium solution of removing wet zinc-making system tannic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910637307.5A CN110306063A (en) 2019-07-15 2019-07-15 A method of organic matter in the heavy germanium solution of removing wet zinc-making system tannic acid

Publications (1)

Publication Number Publication Date
CN110306063A true CN110306063A (en) 2019-10-08

Family

ID=68081506

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910637307.5A Pending CN110306063A (en) 2019-07-15 2019-07-15 A method of organic matter in the heavy germanium solution of removing wet zinc-making system tannic acid

Country Status (1)

Country Link
CN (1) CN110306063A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111041227A (en) * 2019-11-27 2020-04-21 曲靖师范学院 Method for removing arsenic, iron and organic matters from zinc sulfate solution obtained after germanium precipitation of zinc oxide smoke leachate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073105A (en) * 2013-02-28 2013-05-01 陈振选 Method for removing hard biodegradable organic matters from sewage
CN206219348U (en) * 2016-11-25 2017-06-06 中冶赛迪工程技术股份有限公司 A kind of coking advanced waste treatment system
CN107555641A (en) * 2016-06-30 2018-01-09 鞍钢股份有限公司 A kind of preprocess method of coking chemical waste water
CN107555701A (en) * 2016-06-30 2018-01-09 鞍钢股份有限公司 A kind of method of low-cost processes coking chemical waste water
CN109626714A (en) * 2018-12-06 2019-04-16 江苏维尔利环保科技股份有限公司 The film filtration concentrated processing method of landfill leachate nanofiltration concentrate second level minimizing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073105A (en) * 2013-02-28 2013-05-01 陈振选 Method for removing hard biodegradable organic matters from sewage
CN107555641A (en) * 2016-06-30 2018-01-09 鞍钢股份有限公司 A kind of preprocess method of coking chemical waste water
CN107555701A (en) * 2016-06-30 2018-01-09 鞍钢股份有限公司 A kind of method of low-cost processes coking chemical waste water
CN206219348U (en) * 2016-11-25 2017-06-06 中冶赛迪工程技术股份有限公司 A kind of coking advanced waste treatment system
CN109626714A (en) * 2018-12-06 2019-04-16 江苏维尔利环保科技股份有限公司 The film filtration concentrated processing method of landfill leachate nanofiltration concentrate second level minimizing

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111041227A (en) * 2019-11-27 2020-04-21 曲靖师范学院 Method for removing arsenic, iron and organic matters from zinc sulfate solution obtained after germanium precipitation of zinc oxide smoke leachate
CN111041227B (en) * 2019-11-27 2021-11-09 曲靖师范学院 Method for removing arsenic, iron and organic matters from zinc sulfate solution obtained after germanium precipitation of zinc oxide smoke leachate

Similar Documents

Publication Publication Date Title
CN103556180B (en) Reclaim from copper-cadmium slag copper, cadmium method and from rich cadmium solution of zinc sulfate, reclaim the device of cadmium
CN102851707A (en) Technology for recovering production of electrolytic zinc powder and lead powder from smelting ash through alkali leaching method
CN104018184A (en) Brand new method of producing electrolytic manganese metal
CN113913626A (en) Method for removing impurity iron in zinc hydrometallurgy solution by ultrasonic and ozone oxidation
CN107162276A (en) A kind of method for removing chromium of ferric trichloride etching waste liquor
CN105753038B (en) A kind of production technology of feed grade monohydrate zinc sulphate
CN105567976A (en) Method for treating vanadium extracting industrial acid wastewater and comprehensively recycling valuable metal
US4030990A (en) Process for recovering electrolytic copper of high purity by means of reduction electrolysis
CN111455189A (en) Method for leaching copper from tin-copper slag
CN102191378B (en) Electrolyte preparation process for electrolyzing manganese
CN110306063A (en) A method of organic matter in the heavy germanium solution of removing wet zinc-making system tannic acid
CN113707352B (en) Method for treating radioactive comprehensive wastewater
CN101333604A (en) Deironing agent of low grade natural manganese dioxide ore for manganese leaching liquid and deironing process
CN102851508B (en) Method for producing electrolytic lead powder through alkali immersion rotational flow electrolysis of wet electrolytic zinc acid dipping residues
CN110512075B (en) Method for deeply purifying and removing cadmium from cobalt-manganese sulfate mixed liquid
CN104962747B (en) A kind of method of Copper making flue dust dearsenification
CN116815248A (en) Method for removing chloride ions in solution in zinc hydrometallurgy process
CN113620492B (en) Method for removing TOC in high-salt water generated by titanium chloride
CN110607444B (en) Novel treatment method for copper and tin slag removal
CN1295978A (en) Process for preparing manganor manganic oxide used for soft magnetic ferrite
CN114107697A (en) Lead removal method for nickel chloride solution
JP5102523B2 (en) Indium recovery method
CN112047811B (en) Arsenic removal method for arsenic-containing ethylene glycol mother liquor
CN114059077B (en) Treatment method of arsenic filter cake
CN215887184U (en) Equipment for recovering zinc in tin smelting smoke dust

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20191008