CN104846197A - Method for directly removing iron in copper-lead matte oxygen pressure acid leaching process - Google Patents
Method for directly removing iron in copper-lead matte oxygen pressure acid leaching process Download PDFInfo
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- CN104846197A CN104846197A CN201510315614.3A CN201510315614A CN104846197A CN 104846197 A CN104846197 A CN 104846197A CN 201510315614 A CN201510315614 A CN 201510315614A CN 104846197 A CN104846197 A CN 104846197A
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- lead
- iron
- copper
- oxygen pressure
- deironing
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Abstract
The invention relates to a method for directly removing iron in the copper-lead matte oxygen pressure acid leaching process, belonging to the field of non-ferrous metals hydrometallurgical technology. The method comprises the following steps: based on the lead containing characteristic (Pb 10-50%) of the raw material, by controlling the adding volume of acid and the technical parameters of the oxygen pressure leaching process and directly using PbSO4 produced through reaction as a vitriol precipitation agent, precipitating iron precipitated in the form of vegasite and hematite into the slag, wherein the iron content in the liquid after leaching is less than 1g/L, and the leaching residue can be returned to the lead pyrometallurgy system to recycle lead, silver, sulfur and other valuable metals and elements. No new impurity is brought in the whole process, and no additional iron removing equipment is needed, so the production cost is saved and the process is shortened; the entrainment loss of the main metal can be avoided, and the solid-liquid separation operation is easy, and adaptability to raw materials is good.
Description
Technical field
The invention belongs to non-ferrous metal technical field of wet metallurgy, be specifically related to the method for directly deironing in a kind of lead copper matte oxygen pressure acidleach process.
Background technology
Lead copper matte (being commonly called as lead matte) is in plumbous pyrometallurgical smelting production process, and a kind of main by product containing copper and plumbous sulfides of reverberatory furnace, blast furnace, bottom convertor and top blast stove melting institute output, its main component is FeS, Cu
2s, PbS, and the gold and silver valuable metal and the dissipated metal such as selenium, tellurium that contain some.This product can adopt pyrogenic process and wet method two kinds of processing modes.Pyrogenic attack mode obtains blister copper by bessemerizing, then refining obtains cathode copper further, and the method exists the problems such as technical process is long, metal recovery rate is low, production cost is high, environmental pollution is serious.Wet processing adopts roasting--leaching--technical process of electrodeposition, and the method produces a large amount of low concentration sulphur dioxide flue gas in roasting process, and the investment of process low-concentration sulfur dioxide gas apparatus is comparatively large, and economy is not strong.
Kunming University of Science and Technology Jin Ping circle proposes a kind of method processing lead copper matte, namely adopts the method process lead matte of high temperature oxygen pressure acidleach, and leach liquor is used for electrodeposition and reclaims copper, and leached mud then returns pyrometallurgical smelting of lead system recoveries and utilizes the valuable element such as lead, silver, elemental sulfur.The paper " high silicon high iron is containing copper ashes oxygen pressure acidleach process " that author is published in " process engineering journal " (the 8th volume the 6th phase in 2008), take lead matte as raw material (Pb19.22%, Cu24.43%, Fe12.17%, S10.7%), adopt the method for high temperature oxygen pressure acidleach, extracting sulfuric acid copper solutions is used for electro deposited copper, in leaching process, iron mainly precipitates with the form of carphosiderite and rhombohedral iron ore,, there is the halfway problem of oxygen pressure acidleach process deironing in Fe<5g/L in leach liquor.
Chinese patent CN102719666B proposes a kind of method doing heavy alum agent deironing in Zinc hydrometallurgy process with lead sulfate: add in heavy alum operation the lead and yellow-collation ferrovanadium crystal seed that concentration is 8-10g/L, add lead sulfate and neutralizing agent again, iron is made to be precipitated into slag removing with the form of lead and yellow-collation ferrovanadium, but there is heavy alum process and need add neutralizing agent adjustment slurry pH, lead and yellow-collation siderotil need use high temperature high acidic oils iron, makes the problem that lead sulfate regenerates.
In copper electrolytic deposition process, along with the carrying out of electrodeposition, iron ion can accumulate gradually and cause the electric conductivity of electrolytic solution to reduce, bath resistance, viscosity and density increase, suspension content in the reduction of anode slime speed, electrolytic solution is increased, strengthen the pollution of electrolytic solution and suspended substance anticathode copper, cause Cathode Copper Quality to reduce; Meanwhile, Fe in electrolytic solution
2+and Fe
3+oxidation--reduction process power consumption repeatedly between anode and negative electrode, makes current efficiency reduce and ton copper power consumption increases, and affects the quality of normal electrolysis production and reduction cathode copper.Therefore, iron purification must be carried out to electrolytic solution.In enterprise's general control electrolytic solution, total iron content is at≤2.5g/L, to ensure that current efficiency is more than 90%.
Zhu collects and has elaborated the method for several cleaning copper electrolyte deironing in a book " modern copper hydrometallurgy " (in the October, 2002) of writing: traditional method regularly takes out part waste electrolyte open circuit, developed now the technology of ion-exchange and membrane technique deironing.Ion exchange method and membrane technique need to add new equipment, add production cost.In addition, also have solvent extraction except iron processes, the method also needs to add new equipment, adds production cost, can bring new impurity into simultaneously.
The paper " progress of cleaning copper electrolyte deironing " that Xie Xiaofeng etc. are published in " material Leader A: a summary section " (volume the 8th phase August the 28th in 2014), set forth cleaning copper electrolyte method for removing iron, mainly contain jarosite process, goethite process and ferric hydroxide precipitate method etc.
Jarosite process is entered in slag with jarosite form by iron, but brought new impurity K into system simultaneously
+, Na
+or NH
4 +.
And goethite process, valuable metal can be caused large with scum loss amount, and neutralizing agent consumption is many simultaneously, and in large-scale application process, shortcoming is comparatively obvious.
Ferric hydroxide precipitate method is separated out with ferric hydroxide colloid by iron, and its shortcoming to cause main metal entrainment loss serious, and solid-liquid separation operational difficulty, particularly when solution iron content is too high, production process even may be caused to carry out.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides the method for directly deironing in a kind of lead copper matte oxygen pressure acidleach process, the method takes full advantage of in lead copper matte oxygen pressure acidleach process, generation PbSO during raw material leaded reaction
4characteristic, do not add any heavy chalybeate, neutralizing agent and crystal seed, directly utilize PbSO
4do heavy alum agent, iron is precipitated into slag with lead and yellow-collation siderotil form, and utilize High Temperature High Pressure to make another part iron enter slag with the form of rhombohedral iron ore, make liquid iron content <1g/L after leaching, copper-bath after leaching can obtain acceptable cathodic copper products by direct electrowinning, and leached mud can return pyrometallurgical smelting of lead system to reclaim the valuable element such as lead, silver, sulphur wherein.Whole process does not bring new impurity into, and deironing completes in still, and not needing additionally increases equipment for removing ferric ion, has saved production cost, has shortened technical process, can not cause main metal entrainment loss, and solid-liquid separation operation is easy.
In order to achieve the above object, the present invention proposes following technical scheme:
A method for directly deironing in lead copper matte oxygen pressure acidleach process, concrete processing mode is as follows:
(1) by after high lead copper matte fragmentation, ball milling, clear water pulp is used;
(2) ore pulp, dilute sulphuric acid or waste solution of copper electrolysis are distinguished continuous pump in autoclave, control liquid-solid ratio 4 ~ 6:1;
(3) 99.2% industrial pure oxygen is passed in autoclave continuously;
(4) pressurization temperature in the kettle 150 ~ 170 DEG C, still internal pressure 1.0 ~ 1.5Mpa, extraction time 1.0 ~ 2.0h, eventually acid 5 ~ 15g/L technical qualification is controlled.
In the Leaching reaction middle and later periods, utilize the PbSO that the PbS reaction in raw material generates
4do heavy alum agent, reaction formula is:
PbS+0.5O
2+H
2SO
4＝PbSO
4+S
0+H
2O
Iron first leaches postprecipitation, and reaction formula is:
FeS+0.5O
2+H
2SO
4＝FeSO
4+S
0+H
2O
2FeSO
4+0.5O
2+H
2SO
4＝Fe
2(SO
4)
3+H
2O
3Fe
2(SO
4)
3+PbSO
4+12H
2O＝PbFe
6(SO
4)
4(OH)
12↓+6H
2SO
4
In addition, at high temperature under high pressure, iron also can enter slag with the form of rhombohedral iron ore.
Fe
2(SO
4)
3+3H
2O＝Fe
2O
3↓+3H
2SO
4
Iron precipitation discharges sulfuric acid simultaneously, continues the sulfide leaching copper, therefore makes leaching process have certain selectivity, can reach the object of separation of iron while leaching copper.
(5) ore pulp is leached after entering flash drum and regulating tank pressure release cooling, enter thickening pond and carry out concentration and settlement, sedimentation underflow adopts chamber-type press filter to carry out solid-liquor separation, filtrate is used for copper electrodeposition, electrodeposition waste back-cycling leaches, and filter residue then returns plumbous smelting system and reclaims the valuable metal such as lead, silver, sulphur.
Hinge structure of the present invention has the following advantages:
(1) copper leaching rate is high, and metal recovery rate is high;
(2) utilize the characteristic of the leaded height of raw material and leaching process High Temperature High Pressure, do heavy alum agent with the lead sulfate reacting generation in still, do not add heavy ferron, do not add crystal seed, do not add neutralizing agent, avoid bringing into of impurity.
(3) the method technical process is short, and scale is changeable, has stronger practicality;
(4) the method direct deironing can reach follow-up electrodeposition requirement, without the need to leach liquor deironing again in autoclave.
(5) leach liquor is containing Fe<1g/L, and electrodeposition carries copper when returning circulating leaching, and iron can not accumulate.
Accompanying drawing explanation
Fig. 1 is the schema of directly deironing in a kind of lead copper matte oxygen pressure of the present invention acidleach process.
Embodiment
As shown in Figure 1, below in conjunction with embodiments of the invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
Lead copper matte main chemical compositions is: Pb48.93%, Cu6.25%, Fe9.89%, S9.06%.Being transported to after surge tank is sized mixing by high lead copper matte after ball milling pumps in autoclave; Deployed dilute sulphuric acid pumps in still simultaneously, passes into 99.2% industrial pure oxygen and enters in still, and control acid adding amount is 0.8 times of the theoretical acid consumption of Cu, Pb in raw material; Control liquid temperature in the kettle 170 DEG C, still internal pressure 1.5Mpa, extraction time 2.0h, eventually sour 5.1g/L.The leaching ore pulp obtained, leach liquor iron content 937mg/L after solid-liquor separation.
Embodiment 2
Lead copper matte main chemical compositions is: Pb30.03%, Cu20.25%, Fe5.29%, S12.37%.Being transported to after surge tank is sized mixing by high lead copper matte after ball milling pumps in autoclave; Pump in still by electrodeposition waste liquid simultaneously, pass into 99.2% industrial pure oxygen and enter in still, control acid adding amount is 0.9 times of the theoretical acid consumption of Cu, Pb in raw material; Control temperature in the kettle 160 DEG C, still internal pressure 1.2Mpa, extraction time 1.5h, eventually sour 10.5g/L.Leach liquor iron content 656.7mg/L after the leaching pulp liquid-solid isolation obtained.
Embodiment 3
Lead copper matte main chemical compositions is: Pb10.78%, Cu34.8%, Fe0.22%, S15.76%.Being transported to after surge tank is sized mixing by high lead copper matte after ball milling pumps in autoclave; Pump in still by electrodeposition waste liquid simultaneously, pass into 99.2% industrial pure oxygen and enter in still, control acid adding amount is 1.0 times of the theoretical acid consumption of Cu, Pb in raw material; Control temperature in the kettle 150 DEG C, still internal pressure 1.0Mpa, extraction time 1.0h, eventually sour 14.8g/L.Leach liquor iron content 450.7mg/L after the leaching pulp liquid-solid isolation obtained.
The present invention is not adding heavy ferron, is not adding crystal seed, and can reach copper leaching rate under not adding the condition of neutralizing agent high, metal recovery rate is high, direct deironing can reach follow-up electrodeposition requirement, without the need to leach liquor deironing again in autoclave.
A kind of lead copper matte oxygen provided the embodiment of the present invention above presses the method for directly deironing in acidleach process, be described in detail, apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; Meanwhile, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (4)
1. a method for directly deironing in lead copper matte oxygen pressure acidleach process, is characterized in that: the method adopts following sequential steps to realize:
(1) by after lead copper matte fragmentation, ball milling, clear water pulp is used;
(2) by ore pulp and dilute sulphuric acid or waste solution of copper electrolysis respectively, continuous pump is in autoclave;
(3) oxygen is passed into continuously in autoclave, control the technical qualification of pressurization temperature in the kettle 150 ~ 170 DEG C, stagnation pressure 1.0 ~ 1.5Mpa, extraction time 1.0 ~ 2.0h, eventually acid 5 ~ 15g/L, stirring velocity 400 ~ 700r/min, make iron be precipitated into slag with the form of lead and yellow-collation siderotil and rhombohedral iron ore;
(4) leach ore pulp after entering flash drum and regulating tank pressure release cooling, adopt chamber-type press filter to carry out solid-liquid separation, filtrate is used for copper electrodeposition, and filter residue then returns plumbous smelting system and reclaims plumbous, silver, sulphur valuable metal.
2. the method for directly deironing in a kind of lead copper matte oxygen pressure acidleach process according to claim 1, it is characterized in that in step (1): material composition is Pb10 ~ 50%, Cu6 ~ 35%, Fe0.2 ~ 10%, S9 ~ 16% is lead copper matte.
3. the method for directly deironing in a kind of lead copper matte oxygen pressure acidleach process according to claim 1, it is characterized in that in step (2): control acid adding amount is 0.8 ~ 1.0 times of the theoretical acid consumption of Cu, Pb in raw material, the reaction that the middle and later periods leaches copper is participated in the acid produced during heavy iron, regulates slurry pH without the need to adding neutralizing agent.
4. the method for directly deironing in a kind of lead copper matte oxygen pressure acidleach process according to claim 1, it is characterized in that in step (4): deironing does not add lead and yellow-collation siderotil crystal seed, the lead sulfate that in ore pulp, a part of iron and reaction generate forms lead and yellow-collation ferrovanadium and is precipitated into slag, and another part iron generates hematite precipitation and enters slag.
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|---|---|---|---|
| CN201510315614.3A CN104846197A (en) | 2015-06-10 | 2015-06-10 | Method for directly removing iron in copper-lead matte oxygen pressure acid leaching process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107217140A (en) * | 2017-05-12 | 2017-09-29 | 江西铜业集团公司 | A kind of method by lead Selective Separation in lead copper matte |
| CN112662892A (en) * | 2020-12-15 | 2021-04-16 | 衢州华友钴新材料有限公司 | High-pressure nickel-iron doped separation method for pickle liquor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225476A (en) * | 2008-02-22 | 2008-07-23 | 昆明理工大学 | Process for reclaiming copper from lead copper matte |
-
2015
- 2015-06-10 CN CN201510315614.3A patent/CN104846197A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225476A (en) * | 2008-02-22 | 2008-07-23 | 昆明理工大学 | Process for reclaiming copper from lead copper matte |
Non-Patent Citations (2)
| Title |
|---|
| 金炳界: "铅冰铜氧压酸浸-电积提铜工艺及理论研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 金炳界: "铅冰铜氧压酸浸-电积提铜工艺及理论研究", 《中国博士学位论文全文数据库•工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107217140A (en) * | 2017-05-12 | 2017-09-29 | 江西铜业集团公司 | A kind of method by lead Selective Separation in lead copper matte |
| CN112662892A (en) * | 2020-12-15 | 2021-04-16 | 衢州华友钴新材料有限公司 | High-pressure nickel-iron doped separation method for pickle liquor |
| CN112662892B (en) * | 2020-12-15 | 2022-06-14 | 衢州华友钴新材料有限公司 | High-pressure nickel-iron doped separation method for pickle liquor |
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Application publication date: 20150819 |