CN106119547A - A kind of method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid - Google Patents
A kind of method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid Download PDFInfo
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- CN106119547A CN106119547A CN201610577048.8A CN201610577048A CN106119547A CN 106119547 A CN106119547 A CN 106119547A CN 201610577048 A CN201610577048 A CN 201610577048A CN 106119547 A CN106119547 A CN 106119547A
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- copper
- acid
- sulfuric acid
- making system
- filtering residue
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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
- 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
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacturing & Machinery (AREA)
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- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses the method reclaiming copper in the outer waste discharge acid of a kind of Copper making system for preparing sulfuric acid.The method comprises the following steps: S1, uses electrodialysis plant to process the spent acid of row outside Copper making system for preparing sulfuric acid, obtains containing copper at the liquid of interior heavy metal and the dilute sulfuric acid containing arsenic；S2, carries out vulcanization reaction by the liquid containing heavy metal and vulcanizing agent, controls solution potential value, makes copper be precipitated out with the form of sulfide and separate with other heavy metals；S3, carries out solid-liquid separation by the product after S2 vulcanization reaction, obtains filtrate and filtering residue；And S4, filtering residue is returned copper metallurgy industry.Application technical scheme, uses electrodialytic technique to be separated with arsenic by the copper in spent acid, solves the problem that the outer waste discharge acid sulfuration process of traditional Copper making system for preparing sulfuric acid is difficult to separate copper, arsenic；It addition, the filtering residue of vulcanization reaction is mainly composed of copper sulfide, filtering residue returns copper metallurgy industry and achieves the efficient recovery of most copper element in spent acid.
Description
Technical field
The present invention relates to chemical field, reclaim copper in particular in the outer waste discharge acid of a kind of Copper making system for preparing sulfuric acid
Method.
Background technology
The flue gas that copper pyrometallurgy produces contains substantial amounts of SO2, usual supporting flue gas system for preparing sulfuric acid to utilize Sulphur ressource,
Meet environmental requirement.After the scrubbed purification of flue gas during smelting, make SO by the effect of catalyst2Change into SO3, and pass through concentrated sulphuric acid
Absorb SO3It is converted into sulfuric acid product.In flue gas washing purification process, arsenic in flue gas, fluorine, chlorine, heavy metal flue dust etc. are miscellaneous
Matter enters in washing acid, when impurity enriched to a certain extent time outside system, discharge a certain amount of spent acid.Copper making Sulphuric acid
In the outer waste discharge acid of system, copper content is higher, and some engineering is up to 5～10g/l.
Outside copper blast furnace off-gas system for preparing sulfuric acid, spent acid many employings chemical precipitation method of row processes at present, i.e. by adding
Arsenic in spent acid, copper, heavy metal, sulphuric acid etc. are converted into precipitation from liquid phase separation out by medicament, the wastewater to reach standard row after process
Put.Chemical precipitation method technical maturity, invest relatively low, treatment effect is stable, but needs to add a large amount of medicament, output is given up in a large number simultaneously
Slag, labor intensity is big, and operating environment is poor.The waste residue of chemical precipitation method output contains arsenic, copper, zinc, lead and other elements, therefore belongs to danger more
, there is the risk of secondary pollution in danger refuse.And copper precipitates with arsenic in chemical precipitation method simultaneously, it is difficult to separating, copper cannot
Realize reclaiming.Therefore, in the case of environmental requirement increasingly stringent, the method is urgently improved or substitutes.
Summary of the invention
It is desirable to provide the method reclaiming copper in the outer waste discharge acid of a kind of Copper making system for preparing sulfuric acid, to solve existing skill
In art, the outer waste discharge acid treatment process of Copper making system for preparing sulfuric acid is difficult to technical problem copper, arsenic separated.
To achieve these goals, according to an aspect of the invention, it is provided arrange outside a kind of Copper making system for preparing sulfuric acid
The method reclaiming copper in spent acid.The method comprises the following steps: S1, uses electrodialysis plant to process outside Copper making system for preparing sulfuric acid
The spent acid of row, obtains containing copper at the liquid of interior heavy metal and the dilute sulfuric acid containing arsenic；S2, by the liquid containing heavy metal and sulfur
Agent carries out vulcanization reaction, controls solution potential value, makes copper be precipitated out with the form of sulfide and separate with other heavy metals；
S3, carries out solid-liquid separation by the product after S2 vulcanization reaction, obtains filtrate and filtering residue；And S4, filtering residue is returned Copper making system
System.
Further, vulcanizing agent is sodium sulfide and/or NaHS.
Further, S3 use pressure filter carry out solid-liquid separation.
Further, farther include the tail gas of vulcanization reaction in S2 is carried out the step of absorption process.
Further, use sodium carbonate or sodium hydroxide solution that tail gas is carried out absorption process.
Further, discharge including to after the filtrate recycle obtained in S3 or process.Further, reuse refers to that filtrate is used
Make the supplementary water of hydrometallurgy system, or the supplementary water for acid making system purification section, process and specifically include use lime method
Process.
Application technical scheme, uses electrodialytic technique to be separated with arsenic by the copper in spent acid, solves tradition
The outer waste discharge acid sulfuration process of the Copper making system for preparing sulfuric acid problem that is difficult to separate copper, arsenic；It addition, the filtering residue master of vulcanization reaction
Wanting composition is copper sulfide, and filtering residue returns copper metallurgy industry and achieves the efficient recovery of most copper element in spent acid, improves money
Source utilization ratio.
Accompanying drawing explanation
The Figure of description of the part constituting the application is used for providing a further understanding of the present invention, and the present invention shows
Meaning property embodiment and explanation thereof are used for explaining the present invention, are not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid according to an embodiment of the present invention
Schematic flow sheet.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can phases
Combination mutually.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
According to a kind of typical embodiment of the present invention, it is provided that copper is reclaimed in the outer waste discharge acid of a kind of Copper making system for preparing sulfuric acid
Method.The method comprises the following steps: S1, uses electrodialysis plant to process the spent acid of row outside Copper making system for preparing sulfuric acid,
Arrive containing copper at the liquid of interior heavy metal and the dilute sulfuric acid containing arsenic；S2, is carried out the liquid containing heavy metal with vulcanizing agent
Vulcanization reaction, controls solution potential value, makes copper be precipitated out with the form of sulfide and separate with other heavy metals；S3, by S2 sulfur
Change reacted product and carry out solid-liquid separation, obtain filtrate and filtering residue；And S4, filtering residue is returned copper metallurgy industry.
Wherein, electrodialysis be a kind of selective penetrated property utilizing film the ion that charge characteristics in water is different is separated into
And realize the technique that compound separates.The critical piece of electrodialysis plant is anions and canons exchange membrane, dividing plate and three, electrode
Point.Zwitterion is optionally by anion and cation exchange membrane, thus realizes dividing of sulphuric acid in spent acid, arsenic, fluorine, chlorine and heavy metal
From.Sulphuric acid, arsenic, fluorine, chlorine rest in concentrated phase, and heavy metal enters in light phase.
Though the existing ripe application of electrodialytic technique, but it is mainly used in the industries such as food, chemical industry, pharmacy, due to strong acid
The difficulty of the electrodialytic membranes research and development under the conditions of property is relatively big, mainly the stability of membrane structure and high concentration of hydrogen ion pair separation property
The impact of energy, and range of application is wide, is the most not yet widely studied and applies, and does not also answer in smelting spent acid process
Example.
Application technical scheme, uses electrodialytic technique to be separated with arsenic by the copper in spent acid, solves tradition
The outer waste discharge acid sulfuration process of the Copper making system for preparing sulfuric acid problem that is difficult to separate copper, arsenic；It addition, the filtering residue master of vulcanization reaction
Wanting composition is copper sulfide, and filtering residue returns copper metallurgy industry and achieves the efficient recovery of most copper element in spent acid, improves money
Source utilization ratio.
In the present invention, vulcanizing agent can be sodium sulfide and/or NaHS, hydrogen sulfide, Iron sulfuret. etc., its theoretical addition
Amount is pressed chemical reaction equilibrium and is calculated, can be by adding the regulation valve on pipeline and reactive tank outlet solution current potential in Practical Project
Value is chain to be adjusted addition.Preferably, vulcanizing agent is sodium sulfide and/or NaHS, and this vulcanizing agent is readily available.Adopt
Use this vulcanizing agent, relate generally to react as follows:
Na2S+H2SO4=Na2SO4+H2S
H2S+CuSO4=CuS (black precipitate)+H2SO4
Preferably, S3 uses pressure filter carry out solid-liquid separation, can be to use vertical or chamber-type press filter.According to this
The typical embodiment of bright one, this processing method also includes the tail gas of vulcanization reaction in S2 is carried out the step of absorption process.
Preferably, use alkaline process absorption technique that tail gas is processed, use sodium carbonate or sodium hydroxide solution washing tail gas, absorb it
In hydrogen sulfide.
According to a kind of typical embodiment of the present invention, farther include to S3 obtains state filtrate recycle or process after
Discharge, wherein, reuse refers to that filtrate is used as the supplementary water of hydrometallurgy system, or supplementing for acid making system purification section
Water, processes and specifically includes use lime method process.
According to a kind of typical embodiment of the present invention, as it is shown in figure 1, processing step is as follows: S1, use electrodialysis plant
Process the spent acid of row outside Copper making system for preparing sulfuric acid, obtain containing copper at the liquid of interior heavy metal and the dilute sulfuric acid containing arsenic；
S2, carries out vulcanization reaction in vulcanization reaction device by the liquid containing heavy metal and sodium sulfide, controls solution potential value, make copper with
The form of sulfide is precipitated out and separates with other heavy metals；S3, uses pressure filter to carry out the product after S2 vulcanization reaction solid
Liquid separates, and obtains filtrate and filtering residue；And S4, filtering residue is returned to copper metallurgy industry, the described filtrate recycle obtained in S3 or place
Discharge after reason.Furthermore it is also possible to include that the tail gas to vulcanization reaction carries out absorbing the step of discharge.Enter below in conjunction with embodiment
One step explanation beneficial effects of the present invention, the technological means being not described in following example all can use in prior art
Routine techniques means realize.
Embodiment 1
Outside certain smeltery's acid making system, the spent acid composition of row is as shown in table 1.
Table 1
| Sequence number | Title | Unit | Data |
| 1 | Spent acid amount | m3/d | 240 |
| 2 | Sulfuric acid concentration in spent acid | % | 90 |
| 3 | Containing arsenic concentration in spent acid | mg/l | 12000 |
| 4 | Copper ion concentration | mg/l | 6000 |
| 5 | Iron concentration | mg/l | 300 |
| 6 | Plumbum ion concentration | mg/l | 100 |
| 7 | Zinc ion concentration | mg/l | 300 |
| 8 | Fluorine | mg/l | 1000 |
| 9 | Chlorine | mg/l | 2000 |
According to the technological process shown in Fig. 1, the processing step of the present embodiment is as follows:
S1, uses electrodialysis plant to process the spent acid of row outside Copper making system for preparing sulfuric acid, obtains containing copper at an interior huge sum of money
The liquid belonged to and the dilute sulfuric acid containing arsenic；Wherein copper coin have 90% and enters above in the liquid containing heavy metal, and arsenogen have
90% enters above in dilute sulfuric acid, thus realizes copper arsenic and separate；Dilute sulfuric acid otherwise processed containing arsenic；
S2, carries out vulcanization reaction by the liquid containing heavy metal and sodium sulfide, controls solution potential value 0～150mV, makes copper
It is precipitated out with the form of sulfide and separates with other heavy metals；Copper removal efficiency is up to more than 98%；
S3, uses pressure filter to carry out solid-liquid separation the product after S2 vulcanization reaction, obtains filtrate and filtering residue；Filtrate is separately
Process；
S4, returns filtering residue to copper metallurgy industry.
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect:
Use electrodialytic technique to be separated with arsenic by the copper in spent acid, solve and arrange outside traditional Copper making system for preparing sulfuric acid
The problem that spent acid sulfuration process is difficult to separate copper, arsenic；It addition, the filtering residue of vulcanization reaction is mainly composed of copper sulfide, filtering residue returns
Return copper metallurgy industry and achieve the efficient recovery of most copper element in spent acid, improve the level of resources utilization.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (7)
1. the method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid, it is characterised in that comprise the following steps:
S1, uses electrodialysis plant to process the spent acid of row outside Copper making system for preparing sulfuric acid, obtains containing copper in interior heavy metal
Liquid and the dilute sulfuric acid containing arsenic；
S2, carries out vulcanization reaction by the described liquid containing heavy metal and vulcanizing agent, controls solution potential value, makes copper with sulfide
Form be precipitated out and separate with other heavy metals；
S3, carries out solid-liquid separation by the product after described S2 vulcanization reaction, obtains filtrate and filtering residue；And
S4, returns described filtering residue to copper metallurgy industry.
Method the most according to claim 1, it is characterised in that described vulcanizing agent is sodium sulfide and/or NaHS.
Method the most according to claim 1, it is characterised in that use pressure filter to carry out solid-liquid separation in described S3.
Method the most according to claim 1, it is characterised in that farther include the tail gas of vulcanization reaction in described S2 is entered
The step that row absorption processes.
Method the most according to claim 4, it is characterised in that use sodium carbonate or sodium hydroxide solution that described tail gas is entered
Row absorption processes.
Method the most according to claim 1, it is characterised in that farther include the described filtrate to obtaining in described S3 and return
With or process after discharge.
Method the most according to claim 6, it is characterised in that reuse refers to that the described liquid containing heavy metal is used as wet method
The supplementary water of smelting system, or the supplementary water for acid making system purification section, process and specifically include use lime method process.
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Cited By (4)
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| CN111056675A (en) * | 2019-12-19 | 2020-04-24 | 北京矿冶科技集团有限公司 | Method for recycling and recovering waste acid |
| CN113354171A (en) * | 2021-05-13 | 2021-09-07 | 西北矿冶研究院 | Process method for deep dearsenization from copper smelting waste acid |
| CN114230054A (en) * | 2021-12-06 | 2022-03-25 | 国投金城冶金有限责任公司 | Comprehensive recovery method of valuable elements in acidic wastewater containing copper chloride and arsenic |
| CN115490306A (en) * | 2022-08-11 | 2022-12-20 | 长沙矿冶研究院有限责任公司 | Treatment method of waste acid containing arsenic |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111056675A (en) * | 2019-12-19 | 2020-04-24 | 北京矿冶科技集团有限公司 | Method for recycling and recovering waste acid |
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| CN113354171A (en) * | 2021-05-13 | 2021-09-07 | 西北矿冶研究院 | Process method for deep dearsenization from copper smelting waste acid |
| CN114230054A (en) * | 2021-12-06 | 2022-03-25 | 国投金城冶金有限责任公司 | Comprehensive recovery method of valuable elements in acidic wastewater containing copper chloride and arsenic |
| CN114230054B (en) * | 2021-12-06 | 2024-01-30 | 国投金城冶金有限责任公司 | Comprehensive recovery method of valuable elements in acid wastewater containing copper and arsenic |
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