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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
copper
acid
sulfuric acid
making
liquid
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
CN201610577048.8A
Other languages
Chinese (zh)
Inventor
魏甲明
高飞
马小乐
岳焕玲
周翠芳
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.)
China ENFI Engineering Corp
Original Assignee
China ENFI Engineering Corp
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 China ENFI Engineering Corp filed Critical China ENFI Engineering Corp
Priority to CN201610577048.8A priority Critical patent/CN106119547A/en
Publication of CN106119547A publication Critical patent/CN106119547A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/04Obtaining arsenic
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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

A kind of method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid
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.
CN201610577048.8A 2016-07-20 2016-07-20 A kind of method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid Pending CN106119547A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610577048.8A CN106119547A (en) 2016-07-20 2016-07-20 A kind of method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610577048.8A CN106119547A (en) 2016-07-20 2016-07-20 A kind of method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid

Publications (1)

Publication Number Publication Date
CN106119547A true CN106119547A (en) 2016-11-16

Family

ID=57290351

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610577048.8A Pending CN106119547A (en) 2016-07-20 2016-07-20 A kind of method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid

Country Status (1)

Country Link
CN (1) CN106119547A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553248A (en) * 2013-10-23 2014-02-05 中南大学 Heavy metal waste acid and wastewater resource recycling method and device
CN103695961A (en) * 2013-12-06 2014-04-02 西北矿冶研究院 Method for recycling rhenium, arsenic and copper from sulfuric acid wastewater of copper smelting flue gas purification system
CN103773963A (en) * 2014-01-28 2014-05-07 白银有色集团股份有限公司 Method for efficiently recovering copper and rhenium from copper smelting waste acid
CN103898559A (en) * 2014-03-28 2014-07-02 安庆师范学院 Method for removing As and Sb out of copper electrolyte by utilizing ionic liquid electrodialysis
CN104030510A (en) * 2014-06-10 2014-09-10 安可珍 Method for recycling acid and heavy metal in gold smelting acid wastewater
CN104745820A (en) * 2013-12-31 2015-07-01 北京有色金属研究总院 Process for recovering valuable metals from scrap copper smelting slag and copper processing acid pickling waste liquid
CN105441685A (en) * 2015-12-28 2016-03-30 中南大学 Method for recycling valuable metals in peracid waste fluid produced during copper anode mud treating process

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553248A (en) * 2013-10-23 2014-02-05 中南大学 Heavy metal waste acid and wastewater resource recycling method and device
CN103695961A (en) * 2013-12-06 2014-04-02 西北矿冶研究院 Method for recycling rhenium, arsenic and copper from sulfuric acid wastewater of copper smelting flue gas purification system
CN104745820A (en) * 2013-12-31 2015-07-01 北京有色金属研究总院 Process for recovering valuable metals from scrap copper smelting slag and copper processing acid pickling waste liquid
CN103773963A (en) * 2014-01-28 2014-05-07 白银有色集团股份有限公司 Method for efficiently recovering copper and rhenium from copper smelting waste acid
CN103898559A (en) * 2014-03-28 2014-07-02 安庆师范学院 Method for removing As and Sb out of copper electrolyte by utilizing ionic liquid electrodialysis
CN104030510A (en) * 2014-06-10 2014-09-10 安可珍 Method for recycling acid and heavy metal in gold smelting acid wastewater
CN105441685A (en) * 2015-12-28 2016-03-30 中南大学 Method for recycling valuable metals in peracid waste fluid produced during copper anode mud treating process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘少武 等: "《硫酸工作手册》", 30 April 2001, 东南大学出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN111056675B (en) * 2019-12-19 2022-03-29 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

Similar Documents

Publication Publication Date Title
CN105439355B (en) Waste acid resource reclaim and deep treatment method and device
CN103194615B (en) Lead hydrometallurgical technology through utilizing lead sulfate
CN104445095B (en) A kind of method of smelting dirty acid purification
CN102502993B (en) Method for treating acidic heavy metal wastewater and recycling treated wastewater
CN106045170A (en) Treatment method of waste acid outwards discharged from smelting sulfuric acid production system
CN102784713B (en) Method for recycling multiple elements of liquid after cyanided tailing flotation
CN103880113B (en) Utilize the method for modified coal ash circular treatment effluent containing heavy metal ions
CN103496802A (en) Chromium and manganese recovery method in electrolytic manganese chromium wastewater treatment process
CN103551037B (en) Sour separation and concentration method in dirty acid
CN102642953B (en) Treatment method for high-salinity heavy-metal-containing production sewage
CN106215863B (en) A kind of heavy metal absorbent of purification diluted sulfric acid and its application
CN102936070A (en) Method for treating mercury-containing wastewater during PVC (Polyvinyle Chloride) production through two-step process
CN105174556A (en) High-acidity high-iron heavy metal wastewater quality-divided resource recycling method
CN104438287B (en) The recycling processing method of a kind of arsenic sulfide waste residue and device thereof
CN110117052A (en) A kind of absorption process of sulfide precipitation system hydrogen sulfide tail gas
CN106119547A (en) A kind of method reclaiming copper in the outer waste discharge acid of Copper making system for preparing sulfuric acid
CN104815759A (en) Technological method and device for copper and molybdenum separation waste water cyclic utilization
CN102897885B (en) The method of sulfuric acid industry Two-way Cycle jet-type arsenic removal
CN103304090A (en) Device and method for recycling waste sulfate in sulfate acid-making system
CN104787927B (en) A kind of lead-zinc smelting flue gas washing acid water purifies reuse method
CN105463204A (en) Purifying and regenerating method for gold bearing mineral containing cyanating solution
CN102476853A (en) Treatment method of lead-containing wastewater
CN106882884B (en) A kind of method of chloride ion in recycling waste water
CN104876365A (en) High-concentration cyanogen-contained tailing slurry treatment method for gold industry
CN109306408B (en) Method for removing arsenic from ilmenite smoke dust and recycling valuable metals

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into 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: 20161116