CN102417991A - Method for recycling copper and preparing qualified molten iron by carrying out smelting, oxidation and chlorination-reduction on copper slag - Google Patents
Method for recycling copper and preparing qualified molten iron by carrying out smelting, oxidation and chlorination-reduction on copper slag Download PDFInfo
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- CN102417991A CN102417991A CN2011103802570A CN201110380257A CN102417991A CN 102417991 A CN102417991 A CN 102417991A CN 2011103802570 A CN2011103802570 A CN 2011103802570A CN 201110380257 A CN201110380257 A CN 201110380257A CN 102417991 A CN102417991 A CN 102417991A
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- copper
- slag
- molten iron
- copper ashes
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000010949 copper Substances 0.000 title claims abstract description 99
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 95
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002893 slag Substances 0.000 title claims abstract description 39
- 230000003647 oxidation Effects 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- 238000003723 Smelting Methods 0.000 title abstract description 6
- 238000004064 recycling Methods 0.000 title abstract 4
- 239000003245 coal Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000010792 warming Methods 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 61
- 239000002956 ash Substances 0.000 claims description 61
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 21
- 239000003546 flue gas Substances 0.000 claims description 21
- 230000004927 fusion Effects 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 239000000796 flavoring agent Substances 0.000 claims description 5
- 235000019634 flavors Nutrition 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000002918 waste heat Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- -1 sulfurous gas Chemical compound 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005864 Sulphur Substances 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 9
- 238000005660 chlorination reaction Methods 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 4
- 239000000779 smoke Substances 0.000 abstract 2
- 239000012320 chlorinating reagent Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052840 fayalite Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 241000580063 Ipomopsis rubra Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a method for recycling copper and preparing qualified molten iron by carrying out smelting, oxidation and chlorination-reduction on copper slag. The method comprises the following steps of: warming the copper slag discharged at high temperature, adding a chlorinating agent and additive, after the copper slag is fully molten, introducing oxide gas into the copper slag, and carrying out oxidation chlorination desulphurization decoppering to obtain molten liquid; carrying out stepped cooling on high-temperature smoke formed during oxidation chlorination desulphurization decoppering and then recycling copper in the smoke; under the inert gas atmosphere, introducing powdered coal to cause the powdered coal to be mixed with the slag under the stirring action of inert gas and be subjected to melting reduction reaction, and standing until the slag and molten iron are separated, thereby obtaining high-temperature qualified molten iron. By applying the method provided by the invention, the defect that sulphur content and copper content in the molten iron in the traditional copper slag direct melting reduction ironmaking process are high can be effectively overcome, and high-efficiency recycling of copper resource in the copper slag is realized, thus the method provided by the invention has better industrialization prospect.
Description
Technical field
The present invention relates to the method that a kind of hot copper ashes melt oxidation chlorination-reduction is reclaimed copper and made qualified molten iron, belong to the resource and environment field.
Background technology
The China Steel rate of industrial development was very fast in recent years, its with a very important position in world's steel industry, and the Iron and Steel Production total amount occupies first place, the world always during the last ten years.But; China's iron ore resource situation can not satisfy the demand of steel industry far away, and domestic iron ore resource distributes and to have the defective that lean ore is many, the symbiotic complex ore of multielement is more and iron ore resource lacks, grade is low, and in addition additional national steel looks forward to that production capacity is huge, the iron ore demand rises year by year, import is interdependent; Under the economic setting that iron ore price skyrockets; Cause China's ironmaking cost to increase severely, weakened the profit margin of steel industry, had a strong impact on the development of China Steel industry.
Therefore, the supplemental resources of seeking a kind of iron ore can yet be regarded as as iron-smelting raw material and is solved an effective settling mode of Chinese iron ore resource chronic shortage.
According to statistics, produce the copper ashes that one ton of copper produces 2.2 tons, China's copper output in 2007 is 3,500,000 tons, 7,700,000 tons of the amounts of corresponding output copper ashes, and the copper output of China in 2008 is about 3,710,000 tons, is 8,160,000 tons through the amount of calculating the output copper ashes.Iron content is about 40% in the copper ashes, calculates to know that iron has higher reclamation in the copper ashes and be worth.
Chalybeate is mainly 2FeOSiO mutually in the metallurgy of copper slag
2(fayalite) and Fe
3O
4(magnetite), reclaim the iron method at present in the copper ashes and mainly contain three kinds:
The first, oxide treatment is carried out in copper ashes cooling back under molten state, with 2FeOSiO in the copper ashes
2(fayalite) changes Fe into
3O
4(magnetite) cools off crushing-magnetic selection to handling the back copper ashes thereafter, and rich iron phase and its recrement are separated, and makes the iron enrichment.Relevant document proves; Reclaim iron in the copper ashes through this method; Can make that the enrichment of iron in magnetite reaches more than 85% in the slag, but there is following shortcoming in this kind method: the one, oxidizing reaction later stage magnetite is separated out mutually in a large number, and slag viscosity and fusing point raise; Hinder reaction and proceed to assemble mutually and grow up, cause iron yield lower with magnetite; The 2nd, fe source remakes to iron-smelting raw material reduces behind magnetic concentration in the copper ashes, and treatment scheme is complicated; The 3rd, with high-temperature fusion oxide treatment again after the copper ashes cooling, caused the waste of heat in the process.The tapping temperature of copper ashes is 1150～1250 ℃, and the specific heat capacity of copper ashes is approximately 1.1kJkg
-1K
-1, when calculating copper ashes by 25 ℃ of tapping temperature cool to room temperature, the heat of China's copper smelting plant loss in 2008 is approximately: 1.1 * 10
13～1.2 * 10
13KJ carries out economy with thermal value and accounts, according to the calorific value of mark coal: 29271.2kJkg
-1Calculate, combine to mark at present the price of coal, annual China extends to world wide because of the financial loss that the calorific loss of copper ashes causes is at least 2.1 hundred million Renminbi with it, and its financial loss is more huge;
The second, adopt stage grinding stage grading technology; There is the shortcoming that iron recovery is low in the slag (less than 60%) in this method; Reason be the slag chalybeate mutually in magnetic oxygenated iron level less, only 20～30%, main chalybeate phase ferrosilicate gets into mine tailing in the magnetic separation process;
Three, utilize melting reduction method, with 2FeOSiO in the copper ashes
2(fayalite) and Fe
3O
4Directly melting and reducing is a metallic iron, and realizes that under molten state slag iron separates.But there is gained molten iron copper behind the copper ashes melting and reducing, the sulphur content shortcoming of higher (the sulphur average content is higher than 0.6%, copper average content be higher than 1%) in this technology.
Summary of the invention
The present invention is on copper ashes method for melting reduction iron making basis; Make full use of sulphur and in copper ashes, have characteristics; Solve and directly to utilize the high shortcoming of copper ashes ironmaking technique of fusion and reduction gained molten steel sulfur content, a kind of copper ashes melt oxidation chlorination-reduction recovery copper is provided and makes the method for qualified molten iron.
The present invention realizes through following technical proposal: a kind of copper ashes melt oxidation chlorination-reduction is reclaimed copper and is made the method for qualified molten iron, following each step of process:
(1) the high temperature copper ashes of coming out of the stove is warming up to 1500～1600 ℃ to reduce viscosity coefficient of dross; And be Lvization Ji ︰ copper ashes=1 ︰ 4～20 by mass ratio, mix with chlorizating agent, be that Tian Jia Ji ︰ copper ashes=1 ︰ 4～10 adds fusion 40～60min behind the additives by mass ratio again; After treating the abundant fusion of copper ashes;, carry out oxidation chlorination desulfurization decopper(ing) and handle to wherein feeding oxidizing gas 30～90min with pressure 0.5～1.5MPa, obtain melt liquid; The high-temperature flue gas that forms during this time is through reclaiming the copper in the flue gas behind the gradient cooling;
(2) under inert gas atmosphere, in step (1) gained melt liquid, feed fine coal with pressure 0.3～1.0MPa, make fine coal under the stirring of inert gas effect, mix with slag fusion reduction reaction takes place, treat that fine coal feeding amount is with mass ratio C/Fe
X+(x=2,3) stop when being 1.4～1.9 ︰ 1 feeding, leave standstill treat slag and molten iron separate after, obtain the qualified molten iron of high temperature.
The chlorizating agent of said step (1) is CaCl
2, NaCl, BaCl
2And/or AlCl
3
The additive of said step (1) is CaF
2And/or BaF
2
For reducing the chloridizing volatilization of chalybeate phase, after adding additive, be that CaO ︰ copper ashes=0.35～0.42 ︰ 1 adds CaO by mass ratio again in the said step (1).
The oxidizing gas of said step (1) is air, oxygen-rich air or oxygen.
The rare gas element of said step (2) is nitrogen or argon gas.
The pulverized coal particle size of said step (2) is 40～60 orders.
The washing of said step (2) is to remove contained obnoxious flavour in the flue gas, like sulfurous gas, oxynitride.
The high-temperature flue gas that forms during said step (2) melting and reducing enters atmosphere again through secondary combustion, waste heat recovery, dust removal process and washing.
Through above-mentioned each step, molten iron sulphur, that copper content reduces effect is comparatively obvious.The desulfurization decopper(ing) is accomplished in step (1), and the reaction that takes place in the process is:
xFeS+(x+1/2)O
2=Fe
xO+xSO
2 (1)
CuS+O
2=CuO+SO
2 (2)
Cu
2S+O
2=Cu
2O+SO
2 (3)
CaCl
2+1/2O
2+?xSiO
2=?CaO·xSiO
2+Cl
2 (4)
Cl
2+Cu
2S=2CuCl+1/2S
2 (5)
Cl
2+Cu
2O=2CuCl+1/2O
2 (6)
After treating that oxidation chlorination desulfurization decopper(ing) reaction is accomplished, under inert atmosphere, fine coal is sprayed into to slag, iron content component generation fusion reduction reaction in the slag, react and be:
[C]+Fe
3O
4=3(FeO)+CO （7）
[C]+?Fe
2O
3=2(FeO)+CO （8）
[C]+(FeO)=[Fe]+CO （9）
CO+(FeO)=[Fe]+CO
2 （10）
CO
2+[C]=2CO （11）
The high-temperature flue gas that produces is overflowed from slag blanket, causes the disturbance in molten bath; The violent disturbance in molten bath has increased contacting of molten slag layer and reductive agent (coal dust) and molten slag layer top high-temperature area, has strengthened molten copper slag reduction kinetics condition.The molten iron that generates since himself proportion be higher than slag and be deposited to rapidly bottom the molten bath; Thick high-temperature slag covers the top of iron bath; Thereby make the molten iron that restores avoid oxidized once more possibility, also insulation effect has been played in the molten bath simultaneously, realized that slag iron separates.Along with constantly carrying out of reaction, intermittently improve the position that stirring of inert gas is robbed, make it the stirring in molten bath is reached best.Reaction is emitted by iron notch and slag notch respectively smelting the high temperature liquid iron and the slag that after accomplishing.
The present invention makes full use of come out of the stove sulphur thing in high temperature sensible heat and the slag of copper ashes of high temperature and is prone to the characteristics that oxidation removal, copper thing are easy to chloridizing volatilization mutually mutually; Utilize hot copper ashes melt oxidation chlorination-reduction recovery copper and make qualified molten iron, beneficial effect and advantage that the present invention possesses are:
(1) adopt the melt oxidation method to carry out the copper ashes desulfurization, carry out because of being reflected under the liquid environment in the process, its dynamic conditions is better, and the copper ashes desulphurization reaction carries out comparatively thorough;
(2) the high temperature copper ashes directly carries out melting and reducing, and heat scatters and disappears less, has effectively utilized the high temperature sensible heat of the copper ashes of coming out of the stove;
(3) efficiently solve in the direct ironmaking technique of fusion and reduction of present copper ashes sulphur, the higher shortcoming of copper content in the molten iron, and realized the high efficiente callback of copper resource in the copper ashes, the good industrialized prospect is arranged.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
To combine embodiment further to illustrate content of the present invention below, but these instances do not limit protection scope of the present invention.
Embodiment 1
(1) with high temperature come out of the stove copper ashes (component: FeO=48.5%, Fe
3O
4=5.7%, CaO=2.83%, SiO
2=28.62%, S=0.51%) be warming up to 1600 ℃ reducing viscosity coefficient of dross, and be Lvization Ji ︰ copper ashes=1 ︰ 4, with chlorizating agent CaCl by mass ratio
2Mixing, is that Tian Jia Ji ︰ copper ashes=1 ︰ 10 adds CaF by mass ratio again
2Back fusion 40min for reducing the chloridizing volatilization of chalybeate phase, is that CaO ︰ copper ashes=0.35 ︰ 1 adds CaO by mass ratio again; After treating the abundant fusion of copper ashes;, carry out oxidation chlorination desulfurization decopper(ing) and handle to aerating oxygen 50min wherein with pressure 1MPa, obtain melt liquid; The high-temperature flue gas that forms during this time is through reclaiming the copper in the flue gas behind the gradient cooling;
(2) under nitrogen, in step (1) gained melt liquid, feeding granularity with pressure 0.3MPa is 40 purpose fine coal, makes fine coal under the nitrogen stirring action, mixes with slag reduction reaction takes place, and treats that fine coal feeding amount is with mass ratio C/Fe
X+(x=2,3) stop when being 1.6 ︰ 1 feeding, leave standstill treat slag and molten iron separate after, obtain qualified molten iron of high temperature and slag; The high-temperature flue gas that forms is during this time removed contained obnoxious flavour in the flue gas through secondary combustion, waste heat recovery, dust removal process and washing, like sulfurous gas, oxynitride, enters atmosphere again.
Molten iron S content is 0.028% through analysis, utilizes the copper ashes ironmaking technique of fusion and reduction than before under the prerequisite that molten bath basicity reduces significantly, and sulphur content also reduces significantly.
Embodiment 2
(1) with high temperature come out of the stove copper ashes (component: FeO=48.3%, Fe
3O
4=5.9%, CaO=2.77%, SiO
2=28.54%, S=0.50%) be warming up to 1550 ℃ reducing viscosity coefficient of dross, and be Lvization Ji ︰ copper ashes=1 ︰ 10, with NaCl and BaCl by mass ratio
2Mixing, is that Tian Jia Ji ︰ copper ashes=1 ︰ 8 adds BaF by mass ratio again
2Back fusion 55min for reducing the chloridizing volatilization of chalybeate phase, is that CaO ︰ copper ashes=0.42 ︰ 1 adds CaO by mass ratio again; After treating the abundant fusion of copper ashes;, carry out oxidation chlorination desulfurization decopper(ing) and handle to bubbling air 90min wherein with pressure 0.5MPa, obtain melt liquid; The high-temperature flue gas that forms during this time is through reclaiming the copper in the flue gas behind the gradient cooling;
(2) under argon gas, in step (1) gained melt liquid, feeding granularity with pressure 0.8MPa is 50 purpose fine coal, makes fine coal under the argon gas stirring action, mixes with slag reduction reaction takes place, and treats that fine coal feeding amount is with mass ratio C/Fe
X+(x=2,3) stop when being 1.4 ︰ 1 feeding, leave standstill treat slag and molten iron separate after, obtain qualified molten iron of high temperature and slag; The high-temperature flue gas that forms is during this time removed contained obnoxious flavour in the flue gas through secondary combustion, waste heat recovery, dust removal process and washing, like sulfurous gas, oxynitride, enters atmosphere again.
Molten iron S content is 0.037% through analysis, utilizes the copper ashes ironmaking technique of fusion and reduction than before under the prerequisite that molten bath basicity reduces significantly, and sulphur content also reduces significantly.
Embodiment 3
(1) the high temperature copper ashes of coming out of the stove is warming up to 1500 ℃ reducing viscosity coefficient of dross, and is Lvization Ji ︰ copper ashes=1 ︰ 20, with AlCl by mass ratio
3Mixing, is that Tian Jia Ji ︰ copper ashes=1 ︰ 4 adds addition of C aF by mass ratio again
2And BaF
2Back fusion 60min, treat the abundant fusion of copper ashes after,, carry out oxidation chlorination desulfurization decopper(ing) and handle to wherein feeding oxygen-rich air 30min with pressure 1.5MPa, obtain melt liquid; The high-temperature flue gas that forms during this time is through reclaiming the copper in the flue gas behind the gradient cooling;
(2) under nitrogen, in step (1) gained melt liquid, feeding granularity with pressure 1.0MPa is 60 purpose fine coal, makes fine coal under the nitrogen stirring action, mixes with slag reduction reaction takes place, and treats that fine coal feeding amount is with mass ratio C/Fe
X+(x=2,3) stop when being 1.9 ︰ 1 feeding, leave standstill treat slag and molten iron separate after, obtain qualified molten iron of high temperature and slag; The high-temperature flue gas that forms is during this time removed contained obnoxious flavour in the flue gas through secondary combustion, waste heat recovery, dust removal process and washing, like sulfurous gas, oxynitride, enters atmosphere again.
Molten iron S content is 0.027% through analysis, utilizes the copper ashes ironmaking technique of fusion and reduction than before under the prerequisite that molten bath basicity reduces significantly, and sulphur content also reduces significantly.
Claims (9)
1. a copper ashes melt oxidation chlorination-reduction is reclaimed copper and is made the method for qualified molten iron, it is characterized in that through following each step:
(1) the high temperature copper ashes of coming out of the stove is warming up to 1500～1600 ℃; And be Lvization Ji ︰ copper ashes=1 ︰ 4～20 by mass ratio; Mixing with chlorizating agent, is that Tian Jia Ji ︰ copper ashes=1 ︰ 4～10 adds fusion 40～60min behind the additives by mass ratio again, treat the abundant fusion of copper ashes after; With pressure 0.5～1.5MPa to wherein feeding oxidizing gas 30～90min, during the high-temperature flue gas that forms through reclaiming the copper in the flue gas behind the gradient cooling;
(2) under inert gas atmosphere, in step (1) gained melt liquid, feed fine coal with pressure 0.3～1.0MPa, treat that fine coal feeding amount is with mass ratio C/Fe
X+(x=2,3) stop when being 1.4～1.9 ︰ 1 feeding, leave standstill treat slag and molten iron separate after, obtain the qualified molten iron of high temperature.
2. method according to claim 1 is characterized in that: the chlorizating agent of said step (1) is CaCl
2, NaCl, BaCl
2And/or AlCl
3
3. method according to claim 1 is characterized in that: the additive of said step (1) is CaF
2And/or BaF
2
4. method according to claim 1 is characterized in that: after adding additive, be that CaO ︰ copper ashes=0.35～0.42 ︰ 1 adds CaO by mass ratio again in the said step (1).
5. method according to claim 1 is characterized in that: the oxidizing gas of said step (1) is air, oxygen-rich air or oxygen.
6. method according to claim 1 is characterized in that: the rare gas element of said step (2) is nitrogen or argon gas.
7. method according to claim 1 is characterized in that: the pulverized coal particle size of said step (2) is 40～60 orders.
8. method according to claim 1 is characterized in that: the washing of said step (2) is to remove contained obnoxious flavour in the flue gas, like sulfurous gas, oxynitride.
9. method according to claim 1 is characterized in that: the high-temperature flue gas that forms during said step (2) melting and reducing enters atmosphere again through secondary combustion, waste heat recovery, dust removal process and washing.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952952A (en) * | 2012-09-26 | 2013-03-06 | 东北大学 | Method for directly restoring and recovering copper iron from smelting copper slag |
| CN103276222A (en) * | 2013-05-15 | 2013-09-04 | 大冶有色金属有限责任公司 | Technical method and device for treating diaphragm and freezing layer in subsiding electric furnace through pulverized coal in copper pyrometallurgical process |
| CN103572069A (en) * | 2013-11-18 | 2014-02-12 | 梧州漓佳铜棒有限公司 | Batching and smelting method for smelting blister copper by scrap copper |
| CN107475476A (en) * | 2017-06-28 | 2017-12-15 | 昆明理工大学 | A kind of method that copper-containing residue chlorination melting and reducing one-step method prepares the pig iron |
| CN111394593A (en) * | 2020-05-08 | 2020-07-10 | 中南大学 | Method for reducing fluorine and chlorine content in copper smelting flue gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555551A (en) * | 2009-05-22 | 2009-10-14 | 昆明理工大学 | Method for comprehensively recovering Fe, Cu and Si from copper smelting slag |
| CN101824505A (en) * | 2010-05-10 | 2010-09-08 | 昆明理工大学 | Method for producing low-sulfur molten iron in one step by smelting and reducing copper slag |
| CN101886154A (en) * | 2010-07-02 | 2010-11-17 | 昆明理工大学 | Method for preparing low-copper molten iron by mixed melting reduction of copper slag and iron ore |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555551A (en) * | 2009-05-22 | 2009-10-14 | 昆明理工大学 | Method for comprehensively recovering Fe, Cu and Si from copper smelting slag |
| CN101824505A (en) * | 2010-05-10 | 2010-09-08 | 昆明理工大学 | Method for producing low-sulfur molten iron in one step by smelting and reducing copper slag |
| CN101886154A (en) * | 2010-07-02 | 2010-11-17 | 昆明理工大学 | Method for preparing low-copper molten iron by mixed melting reduction of copper slag and iron ore |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952952A (en) * | 2012-09-26 | 2013-03-06 | 东北大学 | Method for directly restoring and recovering copper iron from smelting copper slag |
| CN102952952B (en) * | 2012-09-26 | 2014-08-20 | 东北大学 | Method for directly restoring and recovering copper iron from smelting copper slag |
| CN103276222A (en) * | 2013-05-15 | 2013-09-04 | 大冶有色金属有限责任公司 | Technical method and device for treating diaphragm and freezing layer in subsiding electric furnace through pulverized coal in copper pyrometallurgical process |
| CN103572069A (en) * | 2013-11-18 | 2014-02-12 | 梧州漓佳铜棒有限公司 | Batching and smelting method for smelting blister copper by scrap copper |
| CN103572069B (en) * | 2013-11-18 | 2015-06-03 | 海安县鹰球粉末冶金有限公司 | Batching and smelting method for smelting blister copper by scrap copper |
| CN107475476A (en) * | 2017-06-28 | 2017-12-15 | 昆明理工大学 | A kind of method that copper-containing residue chlorination melting and reducing one-step method prepares the pig iron |
| CN111394593A (en) * | 2020-05-08 | 2020-07-10 | 中南大学 | Method for reducing fluorine and chlorine content in copper smelting flue gas |
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| CN102417991B (en) | 2016-02-24 |
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