CN108456785A - A kind of method and device using copper ashes dechlorination - Google Patents
A kind of method and device using copper ashes dechlorination Download PDFInfo
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- CN108456785A CN108456785A CN201810102514.6A CN201810102514A CN108456785A CN 108456785 A CN108456785 A CN 108456785A CN 201810102514 A CN201810102514 A CN 201810102514A CN 108456785 A CN108456785 A CN 108456785A
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- 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
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Abstract
The present invention discloses a kind of method and device using copper ashes dechlorination, wherein method, including step：Solution of zinc sulfate containing chlorine and the copper ashes containing elemental copper are added in the first reactive tank, mixed liquor is obtained, adjusts the pH value of the mixed liquor, and blast air into the mixed liquor at a predetermined temperature, obtain slot ore pulp；The slot ore pulp is transferred to the second reactive tank, dechlorination reaction is carried out in predefined conditions, then the slot ore pulp after dechlorination is subjected to dense separation, obtains the cuprous copper ashes underflow of chloride containing.The present invention blasts air progress Oxidation Leaching and obtains Cu by controlling certain temperature and acidity2+, provide Cu2+Ion is not required to that copper sulphate additionally is added.It is realized with concentrator, filter press in dechlorination process and is recycled inside dechlorination copper ashes and sheet frame liquid, achieved the effect that be enriched with copper ashes containing chlorine, reduce copper ashes press filtration number and caustic times, reduce reagent consumption, reduce production cost, there is significant economic benefit.
Description
Technical field
The present invention relates to zinc abstraction field more particularly to a kind of method and devices using copper ashes dechlorination.
Background technology
In Zinc Hydrometallurgy Process, chlorine is a kind of harmful impurity element, when the mass concentration of chlorine in zinc abstraction system is higher
When（>300 mg/L), by heavy corrosion Pb-Ag anode plates, increase electrolysis energy consumption, deteriorates groove face environment, while can also reduce
Cathode zinc tablet quality.
Currently, the common chlorine removal methods of zinc abstraction system have two kinds of pyrogenic process and wet method, pyrogenic process mainly to use multiple hearth furnace
It roasts to remove the chlorine in zinc smoke, there are problems that generated gas pollutes the environment in roasting process, it is wet
The removal methods of method section chlorine have the methods of silver salt method, stannous chloride, and that there are silver salt method reagent costs is high, silver raising recovery rate is low asks
Topic.
Therefore, the existing technology needs to be improved and developed.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of methods and dress using copper ashes dechlorination
It sets, it is intended to solve in existing zinc hydrometallurgy production, chlorine removal methods are complicated for operation, and cost is higher and dechlorination effect is poor asks
Topic.
Technical scheme is as follows：
A method of utilizing copper ashes dechlorination, including step：
A, sulfuric chlorohydrin zinc solution will be contained and initial copper ashes is added in the first reactive tank and obtains mixed liquor, at a predetermined temperature to described
Air is blasted in mixed liquor and adjusts pH to 2 ~ 3, and slot ore pulp is obtained by the reaction；
B, the slot ore pulp is transferred to the second reactive tank of sealing, dechlorination reaction is carried out under conditions of 50 ~ 80 DEG C, then will take off
Slot ore pulp after chlorine is separated by solid-liquid separation, and dechlorination solution of zinc sulfate and stannous chloride copper ashes are obtained.
The method using copper ashes dechlorination, wherein further include step after the step B：
C, the content of chlorine in the stannous chloride copper ashes is detected, when the content accounting of chlorine in the stannous chloride copper ashes is small
When 7%, then the stannous chloride copper ashes is added in the first reactive tank equipped with the zinc solution containing sulfuric chlorohydrin, repeats step A-
Step B carries out dechlorination to the zinc solution containing sulfuric chlorohydrin；
D, when the content accounting of chlorine in the stannous chloride copper ashes be more than or equal to 7% when, then by the stannous chloride copper ashes successively into
Row washing, alkali cleaning processing, obtain washing copper ashes after rear liquid and alkali cleaning containing chlor-alkali.
The method using copper ashes dechlorination, wherein further include step after the step D：
E, when the mass concentration that chlorine in rear liquid is washed containing chlor-alkali be less than 20g/L when, then by it is described wash rear liquid containing chlor-alkali and be transferred to contain
Chlor-alkali is washed in rear liquid storage tank, is handled for alkali cleaning；
F, it when the mass concentration for washing chlorine in rear liquid containing chlor-alkali is more than or equal to 20g/L, then washes rear liquid by described containing chlor-alkali and takes
Go out.
The method using copper ashes dechlorination, wherein washing process specifically includes described in the step D：
D1, a certain amount of water is added into rinsing bowl, then a certain amount of stannous chloride copper ashes is added in rinsing bowl
It sizes mixing, obtains the first ore pulp；
D2, first ore pulp is separated by solid-liquid separation, after being washed liquid and washing after copper ashes.
The method using copper ashes dechlorination, wherein alkali cleaning, which is handled, in the step D includes：
D3, the stannous chloride copper ashes after washing is added in alkaline bath, a certain amount of water is added into alkaline bath and sizes mixing；
Then sodium hydroxide or sodium carbonate are added into alkaline bath and adjusts pH to 8 ~ 9.5, obtains the second ore pulp；
D4, second ore pulp is separated by solid-liquid separation, obtains after alkali cleaning copper ashes after liquid and alkali cleaning.
The method using copper ashes dechlorination, wherein the content of elemental copper is big in initial copper ashes described in the step A
In 30%.
The method using copper ashes dechlorination, wherein the matter containing bivalent cupric ion in slot ore pulp described in the step A
Measure a concentration of 2 ~ 3g/L.
The method using copper ashes dechlorination, wherein the sulphur containing chlorine being added in the first reactive tank described in the step A
Sour zinc solution is 3 with initial copper ashes liquid-solid ratio:1~8:1.
The method using copper ashes dechlorination, wherein the water being added in the step D1 is solid with stannous chloride copper ashes liquid
Than being 5:1~8:1.
A kind of device using copper ashes dechlorination, wherein including：First reactive tank, what is connect with first reactive tank is useless
Liquid head tank, copper ashes head tank, the second reactive tank, the waste liquid head tank, copper ashes head tank are located at first reactive tank
Top；The dechlorination concentrator being connect with second reactive tank, liquid storage tank after the dechlorination being connect with dechlorination concentrator top,
The high chlorine copper ashes plate and frame filter press being connect with dechlorination concentrator lower part；The liquid outlet of the high chlorine copper ashes plate and frame filter press with
Liquid storage tank connects after the dechlorination；
The device using copper ashes dechlorination further includes：Washed reaction slot, the washing sheet frame pressure being connect with the washed reaction slot
Filter, liquid storage tank after the washing being connect with the washing plate and frame filter press liquid outlet, liquid storage tank and the washing after the washing
Slot connects；Alkali cleaning reactive tank, the alkali cleaning plate and frame filter press being connect with the alkali cleaning reactive tank go out with the alkali cleaning plate and frame filter press
Liquid storage tank after the alkali cleaning of liquid mouth connection, liquid storage tank is connect with the alkaline bath after the alkali cleaning；Alkali cleaning copper ashes surge tank, the alkali
Copper ashes surge tank is washed to connect with the copper ashes head tank.
Advantageous effect：The present invention is using the copper containing elemental copper obtained after one section of purification copper-cadmium slag pretreatment of zinc hydrometallurgy
Slag is added sulfuric acid and controls pH value of solution in predetermined value, a small amount of copper in copper ashes is soaked with solution of zinc sulfate of the system containing chlorine
Go out, obtains Cu2+, Cu2+Again Cu is formed with the elemental copper in copper ashes+, Cu+With Cl-Cu is obtained by the reaction2Cl2Precipitation carries out dechlorination.It should
Method has many advantages, such as that production cost is low, easy to operate, technique controlling difficulty is small, dechlorination effect is good.
Description of the drawings
Fig. 1 is the flow chart of the method preferred embodiment of the present invention using copper ashes dechlorination.
Fig. 2 is the schematic device of the present invention using copper ashes dechlorination.
Specific implementation mode
The present invention provides a kind of method and device using copper ashes dechlorination, for make the purpose of the present invention, technical solution and
Effect is clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific embodiment described herein
It is only used to explain the present invention, be not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is a kind of flow chart of method using copper ashes dechlorination of the invention, as shown, including step
Suddenly：
S1, it sulfuric chlorohydrin zinc solution and initial copper ashes will be contained will be added in the first reactive tank and obtain mixed liquor, at a predetermined temperature to institute
It states and blasts air in mixed liquor and adjust pH to 2 ~ 3, slot ore pulp is obtained by the reaction；
Specifically, the copper ashes that will be obtained after one section of purification copper-cadmium slag pretreatment of zinc hydrometallurgy（Containing 30% elemental copper）, with wet method
Solution of zinc sulfate containing chlorine in zinc metallurgy system, according to liquid-solid ratio 3:1~8:1（Such as 4:1）It is anti-to be added to first with blast coil
It answers in slot, forms mixed liquor, sulfuric acid is added, the pH value of mixed liquor is adjusted to 2.0 ~ 3.0, control temperature in the first reactive tank and exist
50~80℃（Such as 75 DEG C）, fresh air is blasted into slot, the elemental copper in Oxidation Leaching copper ashes makes Cu in solution2+Concentration reaches
Sulfuric acid is continuously replenished in 2 ~ 3g/L in the process, and pH value in reactive tank is kept to export Cu 2.0 ~ 3.0, and according to the first reactive tank2+It is dense
Degree adjusts blow rate required size, obtains slot ore pulp.
S2, the second reactive tank that the slot ore pulp is transferred to sealing, dechlorination reaction is carried out under conditions of 50 ~ 80 DEG C,
The slot ore pulp after dechlorination is separated by solid-liquid separation again, obtains dechlorination solution of zinc sulfate and stannous chloride copper ashes.
Specifically, dechlorination will be carried out in the slot ore pulp overflow to the second reactive tank in the first reactive tank in the step S1
It reacts, control temperature is at 50 ~ 80 DEG C in reaction process（Such as 70 DEG C）, pH2.0 ~ 3.0, the reaction time is 20 ~ 35min（Such as
30min）, after the completion of reaction, then by the slot ore pulp overflow after dechlorination to a volume 100m3Concentrator carry out solid-liquid point
From dechlorination solution of zinc sulfate and stannous chloride copper ashes.
Reaction principle according to the present invention：
Air is blasted into the first reactive tank, and adjusts acidity, controls temperature, and the simple substance in copper ashes is leached using air oxidation
Copper forms Cu2+, the Cu in the second reactive tank2+It is reacted with elemental copper and generates Cu+, Cu+With the Cl in zinc solution containing sulfuric chlorohydrin-Instead
Cu should be generated2Cl2Precipitation.
Cu+H++O2=Cu2++H2O
Cu2++Cu=Cu+
2Cu++2Cl-=Cu2Cl2
Preferably, further include step after step S2 of the present invention：
S3, the content of chlorine in the stannous chloride copper ashes is detected, when the content accounting of chlorine in the stannous chloride copper ashes
When less than 7%, then the stannous chloride copper ashes is added in the first reactive tank equipped with the zinc solution containing sulfuric chlorohydrin, repeats step
A- steps B carries out dechlorination to the zinc solution containing sulfuric chlorohydrin；
S4, when the content accounting of chlorine in the stannous chloride copper ashes be more than or equal to 7% when, then successively by the stannous chloride copper ashes
It is washed, alkali cleaning processing, obtains washing copper ashes after rear liquid and alkali cleaning containing chlor-alkali.
Specifically, after the step S2, the content of chlorine in obtained stannous chloride copper ashes is detected, according to chlorine
Change the content of chlorine in cuprous copper ashes to judge, if recycled to it, when the content of chlorine in the stannous chloride copper ashes
When accounting is less than 7%, then the stannous chloride copper ashes is added in the first reactive tank equipped with the zinc solution containing sulfuric chlorohydrin, is repeated
Step S1- steps S2 carries out dechlorination to the zinc solution containing sulfuric chlorohydrin, realizes the inside recycling to copper ashes, reduces copper ashes
Press filtration number, reduces production cost.
Further, when the content accounting of chlorine in the stannous chloride copper ashes is more than or equal to 7%（Such as 9%）When, just stop cycle
It uses, because chlorinity increases the effect for influencing whether dechlorination in the copper ashes underflow of stannous chloride.At this point, to the stannous chloride
Copper ashes successively by washing and alkali cleaning, obtain cuprous oxide and chlorine.
Preferably, further include step after step S4 of the present invention：
S5, when the mass concentration that chlorine in rear liquid is washed containing chlor-alkali be less than 20g/L when, then by it is described wash rear liquid containing chlor-alkali and be transferred to contain
Chlor-alkali is washed in rear liquid storage tank, is handled for alkali cleaning；
S6, when the mass concentration for washing chlorine in rear liquid containing chlor-alkali is more than or equal to 20g/L, then wash rear liquid by described containing chlor-alkali and take
Go out.
Specifically, copper ashes after liquid and alkali cleaning is obtained after being washed containing chlor-alkali after alkali cleaning, is washed in rear liquid containing chlor-alkali to described
The mass concentration of chlorine is detected, and when the mass concentration for washing chlorine in rear liquid containing chlor-alkali is less than 20g/L, then described will contain chlorine
Liquid, which is transferred to, after alkali cleaning washes containing chlor-alkali in rear liquid storage tank, is handled for alkali cleaning, and realization recycles liquid after alkali cleaning, reduces alkali cleaning
The usage amount of Shi Shui.When the mass concentration for washing chlorine in rear liquid containing chlor-alkali is more than or equal to 20g/L, stop recycling institute
It states and washes rear liquid taking-up containing chlor-alkali.
Preferably, wherein, the washing process is specially to be added to the stannous chloride copper ashes and water to the step S4
Rinsing bowl is sized mixing, and the first ore pulp is obtained, and control sizes mixing liquid-solid ratio 5:1~8:1, stirring evenly makes the first ore pulp without caking,
First ore pulp is squeezed into filter press and is separated by solid-liquid separation, liquid stream is stored up into liquid after washing after obtained sheet frame liquid is washed
Slot can be used as washing next time and size mixing with water, recycles；Obtained slag（The cuprous copper ashes of chloride containing）, it is transferred to alkali cleaning
In slot, a certain amount of water is added and sizes mixing, control sizes mixing liquid-solid ratio 5:1~8:1, stir evenly, then be added NaOH or
Na2CO3, NaOH or Na is controlled according to alkali cleaning terminal pH8.0 ~ 9.52CO3Addition.Wait for that alkali cleaning terminal pH stablizes 8.0 ~ 9.5
Afterwards, the second ore pulp is obtained, second ore pulp, which is squeezed into filter press, to be separated by solid-liquid separation, and obtains washing rear liquid and alkali cleaning containing chlor-alkali
Copper ashes.
Involved chemical equation is as follows in above-mentioned alkaline cleaning procedure：
Cu2Cl2+OH-=Cu2O+Cl-+H2O
The present invention is passed through using the copper ashes and the solution of zinc sulfate containing chlorine that are generated after one section of purification copper-cadmium slag pretreatment of zinc hydrometallurgy
Certain temperature and acidity are controlled, air progress Oxidation Leaching is blasted and obtains Cu2+, due to generating Cu2+Ion, therefore de-
It is not required to that copper sulphate additionally is added in chlorine reaction process.It is realized with concentrator in dechlorination process and is recycled inside dechlorination copper ashes, reached
To enrichment effect of the copper ashes containing chlorine, copper ashes press filtration number and caustic times are reduced, reduces reagent consumption, reduces and be produced into
This, has significant economic benefit.
The present invention also provides a kind of devices using copper ashes dechlorination comprising：First reactive tank 3, it is anti-with described first
Waste liquid head tank 2, copper ashes head tank 1, the second reactive tank 4 that slot connects are answered, the waste liquid head tank, copper ashes head tank are located at institute
State the top of the first reactive tank；The dechlorination concentrator 5 being connect with second reactive tank is connect with dechlorination concentrator top
Dechlorination after liquid storage tank 11, the high chlorine copper ashes plate and frame filter press 6 being connect with dechlorination concentrator lower part；The high chlorine copper ashes plate
The liquid outlet of frame filter press is connect with liquid storage tank after the dechlorination；
The device using copper ashes dechlorination further includes：Washed reaction slot 7, the washing sheet frame pressure being connect with the washed reaction slot
Filter 8, liquid storage tank 12 after the washing being connect with the washing plate and frame filter press liquid outlet, liquid storage tank and the water after the washing
Washing trough connects；Alkali cleaning reactive tank 9, the alkali cleaning plate and frame filter press 10 being connect with the alkali cleaning reactive tank, with the alkali cleaning sheet frame pressure
Liquid storage tank 13 after the alkali cleaning of filter liquid outlet connection, liquid storage tank is connect with the alkaline bath after the alkali cleaning；Alkali cleaning copper ashes is sized mixing
Slot 14, the alkali cleaning copper ashes surge tank are connect with the copper ashes head tank.
A kind of method and device using copper ashes dechlorination of the invention is explained below by specific embodiment：
Embodiment 1
The solution of zinc sulfate of the 500mg/L containing chlorine is continuously squeezed into the dischargeable capacity 30m with blast coil3The first reactive tank
In, control liquid inventory 10m3/h；Initial copper ashes is continuously added into the first reactive tank（Copper ashes is containing the fresh of 30% elemental copper
Copper ashes）, wherein the solution of zinc sulfate is 3 by liquid-solid ratio with the copper ashes:1 ratio is added；Sulfuric acid is added to adjust
PH2.0, temperature 50 C, the air blast into slot, the elemental copper in Oxidation Leaching copper ashes generate slot ore pulp, while making Cu in solution2+It is dense
Degree reaches 2g/L, and sulfuric acid is continuously replenished in aeration step, keeps pH in reactive tank to maintain 2.0, and gone out according to the first reactive tank
Mouth Cu2+Concentration regulating air volume；By the volume 30m of the first reactive tank slot ore pulp overflow to no blast coil3Second reaction
Slot, control temperature carry out dechlorination reaction at 50 DEG C, pH2.0；By the slot ore pulp overflow after dechlorination to a volume 100m3It is dense
Close machine carries out dense separation（It is separated by solid-liquid separation）, the supernatant after dechlorination returns to soaking system and test in zinc roasting mine, containing Cu2Cl2Copper ashes bottom
Stream is continuously squeezed into the first reactive tank, is carried out circulation collection slag and is contained chlorine；
When thickener underflow copper ashes is enriched to 7% containing chlorine, Cu will be enriched with2Cl2Copper ashes is squeezed into high chlorine copper ashes plate and frame filter press and is carried out
It is separated by solid-liquid separation, liquid returns to soaking system and test in zinc roasting mine, to being enriched with Cu2Cl2Copper ashes is washed, and can be added in rinsing bowl in advance
5m3Water will be enriched with Cu2Cl2Copper ashes is added in rinsing bowl and sizes mixing, and obtains the first ore pulp, controls liquid-solid ratio 5 of sizing mixing:1, stirring
To ore pulp uniformly without caking, the first ore pulp is squeezed into washing plate and frame filter press and is separated by solid-liquid separation, sheet frame liquid（After washing
Liquid）Liquid storage tank after into washing recycles, and is enriched with Cu2Cl2Copper ashes enters in alkaline bath；5m can be added in alkaline bath in advance3
Water will be enriched with Cu2Cl2Copper ashes is added in alkaline bath and sizes mixing, and controls liquid-solid ratio 5 of sizing mixing:1, stirring is to ore pulp uniformly without knot
Then NaOH is added in block, NaOH additions are controlled according to alkali cleaning terminal pH8.0.Stablize after 8.0 after terminal pH, obtains the
Second ore pulp is squeezed into alkali cleaning plate and frame filter press and is separated by solid-liquid separation by two ore pulps.Sheet frame liquid（Rear liquid is washed containing chlor-alkali）Into
Liquid storage tank recycles afterwards, and enrichment chlorine opens a way liquid after cl concn reaches 20g/L in liquid after alkali cleaning.Slag phase analysis tune after alkali cleaning
It in stock tank, squeezes into the first reactive tank, recycles after being sized mixing with zinc solution containing sulfuric chlorohydrin.
Embodiment 2
By the solution of zinc sulfate of the 1000mg/L containing chlorine, the dischargeable capacity 30m with blast coil is continuously squeezed into3The first reactive tank
In, control liquid inventory 20m3/h；Initial copper ashes is continuously added into the first reactive tank（Copper ashes is containing the fresh of 30% elemental copper
Copper ashes, the copper ashes after thickener underflow copper ashes containing chlorine and alkali cleaning）, wherein the solution of zinc sulfate presses liquid-solid ratio with the copper ashes
It is 8:1 ratio is added；Sulfuric acid is added and adjusts pH3.0,80 DEG C of temperature, the air blast into slot, the list in Oxidation Leaching copper ashes
Matter copper generates slot ore pulp, while making Cu in solution2+Concentration reaches 3g/L, and sulfuric acid is continuously replenished in aeration step, makes in reactive tank
PH maintains 3.0, and exports Cu according to the first reactive tank2+Concentration regulating air volume；Extremely by the first reactive tank slot ore pulp overflow
Volume 30m without blast coil3The second reactive tank, control temperature at 80 DEG C, pH3.0, carry out dechlorination reaction；After dechlorination
The overflow of slot ore pulp is to a volume 100m3Concentrator carry out dense separation（It is separated by solid-liquid separation）, the supernatant return after dechlorination
Zinc roasts soaking system and test in mine, contains Cu2Cl2Copper ashes underflow continuously squeeze into the first reactive tank, carry out circulation collection slag contain chlorine；
When thickener underflow copper ashes is enriched to 10% containing chlorine, Cu will be enriched with2Cl2Copper ashes squeeze into high chlorine copper ashes plate and frame filter press into
Row is separated by solid-liquid separation, and liquid returns to soaking system and test in zinc roasting mine, to being enriched with Cu2Cl2Copper ashes is washed, and can be added in rinsing bowl in advance
Enter 5m3Water will be enriched with Cu2Cl2Copper ashes is added in rinsing bowl and sizes mixing, and obtains the first ore pulp, controls liquid-solid ratio 8 of sizing mixing:1, it stirs
It mixes to ore pulp uniformly without caking, the first ore pulp is squeezed into washing plate and frame filter press and is separated by solid-liquid separation, sheet frame liquid（After washing
Liquid）Liquid storage tank after into washing recycles, and is enriched with Cu2Cl2Copper ashes enters in alkaline bath；5m can be added in alkaline bath in advance3
Water will be enriched with Cu2Cl2Copper ashes is added in alkaline bath and sizes mixing, and controls liquid-solid ratio 8 of sizing mixing:1, stirring is to ore pulp uniformly without knot
Then Na is added in block2CO3, Na is controlled according to alkali cleaning terminal pH9.52CO3Addition.Stablize after 8.0 after terminal pH, obtains
Second ore pulp is squeezed into alkali cleaning plate and frame filter press and is separated by solid-liquid separation by the second ore pulp.Sheet frame liquid makes into rear liquid storage tank cycle
With enrichment chlorine opens a way liquid after liquid chlorine concentration reaches 20g/L after alkali cleaning.After alkali cleaning in slag phase analysis surge tank, with sulphur containing chlorine
Sour zinc solution is squeezed into after sizing mixing in the first reactive tank, is recycled.
In conclusion the present invention utilizes the copper ashes and zinc hydrometallurgy generated after one section of purification copper-cadmium slag pretreatment of zinc hydrometallurgy
Solution of zinc sulfate containing chlorine in system blasts air progress Oxidation Leaching and obtains Cu by controlling certain temperature and acidity2+,
Provide Cu2+Ion is not required to that copper sulphate additionally is added.In dechlorination process dechlorination copper ashes and sheet frame are realized with concentrator, filter press
It is recycled inside liquid, achievees the effect that be enriched with copper ashes containing chlorine, reduce copper ashes press filtration number and caustic times, reduce reagent and disappear
Consumption reduces production cost, has significant economic benefit.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of method using copper ashes dechlorination, which is characterized in that including step：
A, sulfuric chlorohydrin zinc solution will be contained and initial copper ashes is added in the first reactive tank and obtains mixed liquor, at a predetermined temperature to described
Air is blasted in mixed liquor and adjusts pH to 2 ~ 3, and slot ore pulp is obtained by the reaction；
B, the slot ore pulp is transferred to the second reactive tank of sealing, dechlorination reaction is carried out under conditions of 50 ~ 80 DEG C, then will take off
Slot ore pulp after chlorine is separated by solid-liquid separation, and dechlorination solution of zinc sulfate and stannous chloride copper ashes are obtained.
2. the method according to claim 1 using copper ashes dechlorination, which is characterized in that further include step after the step B
Suddenly：
C, the content of chlorine in the stannous chloride copper ashes is detected, when the content accounting of chlorine in the stannous chloride copper ashes is small
When 7%, then the stannous chloride copper ashes is added in the first reactive tank equipped with the zinc solution containing sulfuric chlorohydrin, repeats step A-
Step B carries out dechlorination to the zinc solution containing sulfuric chlorohydrin；
D, when the content accounting of chlorine in the stannous chloride copper ashes be more than or equal to 7% when, then by the stannous chloride copper ashes successively into
Row washing, alkali cleaning processing, obtain washing copper ashes after rear liquid and alkali cleaning containing chlor-alkali.
3. the method according to claim 2 using copper ashes dechlorination, which is characterized in that further include step after the step D
Suddenly：
E, when the mass concentration that chlorine in rear liquid is washed containing chlor-alkali be less than 20g/L when, then by it is described wash rear liquid containing chlor-alkali and be transferred to contain
Chlor-alkali is washed in rear liquid storage tank, is handled for alkali cleaning；
F, it when the mass concentration for washing chlorine in rear liquid containing chlor-alkali is more than or equal to 20g/L, then washes rear liquid by described containing chlor-alkali and takes
Go out.
4. the method according to claim 2 using copper ashes dechlorination, which is characterized in that at washing described in the step D
Reason specifically includes：
D1, a certain amount of water is added into rinsing bowl, then a certain amount of stannous chloride copper ashes is added in rinsing bowl
It sizes mixing, obtains the first ore pulp；
D2, first ore pulp is separated by solid-liquid separation, after being washed liquid and washing after copper ashes.
5. the method according to claim 2 using copper ashes dechlorination, which is characterized in that alkali cleaning processing packet in the step D
It includes：
D3, the stannous chloride copper ashes after washing is added in alkaline bath, a certain amount of water is added into alkaline bath and sizes mixing；
Then sodium hydroxide or sodium carbonate are added into alkaline bath and adjusts pH to 8 ~ 9.5, obtains the second ore pulp；
D4, second ore pulp is separated by solid-liquid separation, obtains after alkali cleaning copper ashes after liquid and alkali cleaning.
6. the method according to claim 1 using copper ashes dechlorination, which is characterized in that initial copper described in the step A
The content of elemental copper is more than 30% in slag.
7. the method according to claim 1 using copper ashes dechlorination, which is characterized in that slot ore pulp described in the step A
In the mass concentration containing bivalent cupric ion be 2 ~ 3g/L.
8. the method according to claim 1 using copper ashes dechlorination, which is characterized in that first is anti-described in the step A
It is 3 to answer the zinc solution containing sulfuric chlorohydrin being added in slot and initial copper ashes liquid-solid ratio:1~8:1.
9. the method according to claim 4 using copper ashes dechlorination, which is characterized in that the water that is added in the step D1 with
Stannous chloride copper ashes liquid-solid ratio is 5:1~8:1.
10. a kind of device using copper ashes dechlorination, which is characterized in that including：First reactive tank is connect with first reactive tank
Waste liquid head tank, copper ashes head tank, the second reactive tank, the waste liquid head tank, copper ashes head tank be located at it is described first react
The top of slot；The dechlorination concentrator being connect with second reactive tank, liquid after the dechlorination being connect with dechlorination concentrator top
Storage tank, the high chlorine copper ashes plate and frame filter press being connect with dechlorination concentrator lower part；The high chlorine copper ashes plate and frame filter press goes out
Liquid mouth is connect with liquid storage tank after the dechlorination；
The device using copper ashes dechlorination further includes：Washed reaction slot, the washing sheet frame pressure being connect with the washed reaction slot
Filter, liquid storage tank after the washing being connect with the washing plate and frame filter press liquid outlet, liquid storage tank and the washing after the washing
Slot connects；Alkali cleaning reactive tank, the alkali cleaning plate and frame filter press being connect with the alkali cleaning reactive tank go out with the alkali cleaning plate and frame filter press
Liquid storage tank after the alkali cleaning of liquid mouth connection, liquid storage tank is connect with the alkaline bath after the alkali cleaning；Alkali cleaning copper ashes surge tank, the alkali
Copper ashes surge tank is washed to connect with the copper ashes head tank.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810102514.6A CN108456785A (en) | 2018-02-01 | 2018-02-01 | A kind of method and device using copper ashes dechlorination |
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| CN201810102514.6A CN108456785A (en) | 2018-02-01 | 2018-02-01 | A kind of method and device using copper ashes dechlorination |
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| CN108456785A true CN108456785A (en) | 2018-08-28 |
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| CN201810102514.6A Pending CN108456785A (en) | 2018-02-01 | 2018-02-01 | A kind of method and device using copper ashes dechlorination |
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Cited By (3)
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| CN111549234A (en) * | 2020-05-07 | 2020-08-18 | 云南云铜锌业股份有限公司 | Method and system for dechlorinating zinc hydrometallurgy copper slag |
| CN112028208A (en) * | 2020-08-11 | 2020-12-04 | 云南云铜锌业股份有限公司 | Method for removing fluorine and chlorine in zinc smelting waste acid |
| CN114645300A (en) * | 2022-03-21 | 2022-06-21 | 吉首大学 | Preparation method for direct dechlorination of cuprous chloride and cyclic regeneration of copper |
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