CN117758071A - Method for recovering molybdenum from copper smelting smoke dust - Google Patents
Method for recovering molybdenum from copper smelting smoke dust Download PDFInfo
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- CN117758071A CN117758071A CN202410131641.4A CN202410131641A CN117758071A CN 117758071 A CN117758071 A CN 117758071A CN 202410131641 A CN202410131641 A CN 202410131641A CN 117758071 A CN117758071 A CN 117758071A
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- Prior art keywords
- copper
- molybdenum
- acid leaching
- filtrate
- smoke dust
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- 239000010949 copper Substances 0.000 title claims abstract description 89
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000000428 dust Substances 0.000 title claims abstract description 59
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 58
- 239000011733 molybdenum Substances 0.000 title claims abstract description 57
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000003723 Smelting Methods 0.000 title claims abstract description 49
- 239000000779 smoke Substances 0.000 title claims abstract description 46
- 238000002386 leaching Methods 0.000 claims abstract description 65
- 239000002253 acid Substances 0.000 claims abstract description 54
- 239000000706 filtrate Substances 0.000 claims abstract description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 17
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 239000011133 lead Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004073 vulcanization Methods 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 239000002893 slag Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000011549 displacement method Methods 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 27
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 239000008267 milk Substances 0.000 claims description 10
- 210000004080 milk Anatomy 0.000 claims description 10
- 235000013336 milk Nutrition 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 9
- 239000004571 lime Substances 0.000 claims description 9
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910000358 iron sulfate Inorganic materials 0.000 claims 3
- 230000032683 aging Effects 0.000 claims 1
- 230000005070 ripening Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 244000089742 Citrus aurantifolia Species 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 description 4
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 229940000489 arsenate Drugs 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical class [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering molybdenum from copper smelting smoke dust, wherein the smoke dust contains arsenic, copper, iron, lead, zinc and molybdenum elements, and the recovery method comprises the following steps: step S1, leaching the smoke dust in an acid leaching solution to obtain an acid leaching filtrate and acid leaching filter residues containing lead; s2, neutralizing the acid leaching filtrate obtained in the step S1 with alkali, adding a catalyst, and oxidizing to obtain arsenic slag and arsenic-precipitated filtrate; s3, precipitating copper from the filtrate obtained in the step S2 by using a displacement method to obtain sponge copper precipitate and a filtrate obtained after copper precipitation; and S4, adding a vulcanizing agent into the copper-precipitating filtrate obtained in the step S3, and adjusting the PH value to be less than 4.1 to trigger a vulcanization reaction, so as to finally form molybdenum precipitate and recycling. The method has the advantages of high recovery rate and purity, high resource utilization benefit, low cost and the like, can efficiently recover the molybdenum in the copper smelting smoke dust of the side-blown furnace, reduces the demand on external raw materials, and realizes the effective utilization of molybdenum resources.
Description
Technical Field
The invention relates to the technical field of copper smelting, in particular to a method for recovering molybdenum from copper smelting smoke dust.
Background
Copper smelting technology refers to a process of obtaining refined copper from copper ores through various process steps. Copper smelting can be carried out by a variety of different processes, some common copper smelting processes include: wet smelting: the method mainly comprises the technological methods of wet leaching, dissolution, extraction and the like, and is suitable for treating low-grade copper ores and copper-containing waste materials. Dry smelting: copper in copper ores or copper concentrate ores is extracted through the technological processes of sintering, smelting, electrolysis and the like, so that the method is a common smelting method; smelting in a flash furnace: smelting is carried out by utilizing high temperature and oxygen, copper in copper ores is separated, and the smelting method is an efficient smelting method; electrolytic method: copper in the copper-containing solution is separated out through an electrolysis process to obtain high-purity copper, and the high-purity copper is commonly used for refining high-grade copper leaching liquid. The side-blown furnace is a device commonly used in dry smelting, in which copper concentrate, coke and oxygen are injected into a high-temperature smelting furnace, copper and other metals in copper-containing materials are separated by using a molten state of cupola, in the process, oxygen is blown in to generate high temperature, and oxidation slag and molten materials are simultaneously oxidized, so that copper extraction and separation are facilitated.
In the process of smelting copper in the side-blown converter, a great amount of smoke dust is generated in the side-blown converter, and the discharged smoke dust contains copper, lead, zinc, arsenic, gold, silver and other valuable metals. In recent years, the grade of raw copper-smelting ores is continuously reduced, and accompanying ores containing multiple elements are increased, so that the components of copper smelting smoke are more complex, and therefore, the treatment of copper smoke becomes an important problem facing each smelting enterprise. Wet process is the most commonly used method for treating copper fume, and is mainly divided into three leaching systems of acid, neutral and alkaline, wherein the acid leaching process is more applied.
However, research in the prior art focuses on how to remove arsenic in smoke dust, and a systematic study is lacking in the recovery of some useful metals contained in the smoke dust, and in some patents, a recovery process of metals in copper smelting smoke dust is mentioned, for example, a treatment process of copper smelting smoke dust is mentioned in patent document CN105543489B, and the method mainly recovers metals such as copper, zinc, lead, bismuth and the like from the smoke dust and reduces arsenic in the smoke dust, however, through detection, we find that molybdenum is contained in the smoke dust generated by side-blown furnace copper smelting, the molybdenum content is 0.5-1.5%, and the recovery value is high, but in the prior art, no recovery scheme related to molybdenum is available in the recovery treatment method of copper smelting smoke dust, so that a large amount of resources are wasted.
Disclosure of Invention
The application provides a method for recycling molybdenum from copper smelting smoke dust, which solves the problems that in the prior art, molybdenum is not effectively recycled and utilized in a copper smelting smoke dust treatment method, so that resource waste and the like are caused.
The invention adopts the technical scheme that: the method for recovering molybdenum from copper smelting smoke dust, wherein the smoke dust contains arsenic, copper, iron, lead, zinc and molybdenum elements, and the recovery method comprises the following steps: step S1, leaching the smoke dust in an acid leaching solution to obtain an acid leaching filtrate and acid leaching filter residues containing lead; s2, neutralizing the acid leaching filtrate obtained in the step S1 with alkali, adding a catalyst, and oxidizing to obtain arsenic slag and arsenic-precipitated filtrate; s3, precipitating copper from the filtrate obtained in the step S2 by using a displacement method to obtain sponge copper precipitate and a filtrate obtained after copper precipitation; and S4, adding a vulcanizing agent into the copper-precipitating filtrate obtained in the step S3, and adjusting the PH value to be less than 4.1 to trigger a vulcanization reaction, so as to finally form molybdenum precipitate and recycling.
Further, in the step S1, sulfuric acid is used for acid leaching of the smoke dust, concentrated sulfuric acid is used for curing the smoke dust first, dilute sulfuric acid is used for acid leaching of the smoke dust after curing, and the solution is continuously stirred in the acid leaching process.
Further, the curing time is 0.5-1h, the acidity of the dilute sulfuric acid is 1.00-1.50mol/L, the concentration of the dilute sulfuric acid is 100-400g/L, the acid leaching temperature is 70-90 ℃, the acid leaching time is 2-4h, and the stirring speed is 300-400r/min.
In step S2, lime milk is added into the acid leaching filtrate for neutralization, and the catalyst is ferrous sulfate solution to obtain gypsum and ferric arsenate precipitate.
Further, preparing a lime milk aqueous solution for neutralization according to the ratio of lime milk to water of 1:3, wherein the concentration of the ferrous sulfate solution is 200g/L.
Further, in step S3, iron powder is added to the filtrate after arsenic precipitation to reduce copper ions to sponge copper precipitate.
Further, the content of the iron powder is 1.5 times of the copper content in the solution.
Further, in the step S4, ferric sulfate solution is obtained at the same time, and the ferric sulfate solution is concentrated and crystallized to obtain ferric sulfate.
Further, sodium hypochlorite is synchronously added during acid leaching, and the volume ratio of the sodium hypochlorite to the acid leaching filtrate is 1:50.
further, the vulcanizing agent is a 10% sodium hydrosulfide aqueous solution.
Compared with the prior art, the method for recycling the molybdenum in the side-blown copper smelting smoke dust has the advantages of high recycling rate and purity, high resource utilization benefit, low cost and the like, can efficiently recycle the molybdenum in the side-blown copper smelting smoke dust, reduces the demand on external raw materials, realizes the effective utilization of molybdenum resources, removes metal ions with larger influence on the purification of the metal molybdenum in filtrate, sorts, filters and recycles the metal ions, reduces the emission of harmful substances in the smoke dust, and has positive significance on environmental protection.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a treatment process of copper smelting dust provided by the invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a method for recovering molybdenum from copper smelting dust, which aims to recover molybdenum from copper smelting dust, and raw materials used in the method can be directly purchased in the market or prepared by a person skilled in the art through a conventional method.
Wherein, the content range of elements in the copper smelting smoke dust is shown in table 1:
table 1: elemental content range in copper smelting smoke
Referring to fig. 1, the method for recovering molybdenum according to the present invention comprises:
step S1, leaching the smoke dust in an acid leaching solution to obtain an acid leaching filtrate and acid leaching filter residues containing lead;
s2, neutralizing the acid leaching filtrate obtained in the step S1 with alkali, adding a catalyst, and oxidizing to obtain arsenic slag and arsenic-precipitated filtrate;
s3, precipitating copper from the filtrate obtained in the step S2 by using a displacement method to obtain sponge copper precipitate and a filtrate obtained after copper precipitation;
and S4, adding a vulcanizing agent into the copper-precipitating filtrate obtained in the step S3, and adjusting the PH value to be less than 4.1 to trigger a vulcanization reaction, so as to finally form molybdenum precipitate and recycling.
Specifically, the invention adopts hydrometallurgy technology to carry out acid leaching reaction on smoke dust and sulfuric acid, in the step S1, metal in the smoke dust reacts with sulfuric acid, wherein in the smoke dust, each metal element exists in the form of CuO (copper oxide) and Fe 2 O 3 (iron oxide), feO (ferrous oxide), znO (zinc oxide), as 2 O 5 (arsenic pentoxide), moO 2 (molybdenum oxide), and the like.
In step S1, the acid leaching filter residue mainly contains the following metal reaction formulas in acid leaching:
CuO+H 2 SO 4 →CuSO 4 +H 2 o, copper oxide (CuO) and dilute sulfuric acid (H) 2 SO 4 ) The reaction produced copper sulfate (CuSO) 4 ) And water (H) 2 O）；
Fe 2 O 3 +3H 2 SO 4 = Fe 2 (SO 4 ) 3 +3H 2 O, ferric oxide and dilute sulfuric acid (H) 2 SO 4 ) Reaction to produce ferric sulfate (Fe) 2 (SO 4 ) 3 ) Water (H) 2 O）；
FeO+H 2 SO 4 =FeSO 4 +H 2 O, ferrous oxide and dilute sulfuric acid (H) 2 SO 4 ) Reaction to produce ferrous sulfate (FeSO) 4 ) Water (H) 2 O）；
ZnO+H 2 SO 4 =ZnSO 4 +H 2 O, zinc oxide (ZnO) and dilute sulfuric acid (H) 2 SO 4 ) The reaction generates zinc sulfate (ZnSO) 4 ) Water (H) 2 O）；
In operationIn the process, the smoke dust is subjected to countercurrent leaching, acid leaching filter residues formed by acid leaching are precipitated, acid leaching filtrate and acid leaching filter residues are obtained after filtration, the acid leaching filter residues mainly comprise lead bismuth residues and contain a small amount of copper and arsenic, and the acid leaching filtrate obtained in the step S1 is continuously processed in the step S2; more specifically, it is considered that part of molybdenum in the smoke dust is treated with FeO.MoO 2 ·Fe 2 O 3 The acid leaching in this embodiment is performed in two steps, and the concentrated sulfuric acid is used to leach the smoke dust, dilute the sulfuric acid after curing for a certain period of time, and then use the dilute sulfuric acid to leach continuously, and continuously stir during the leaching process, so that the leaching efficiency of molybdenum can be ensured, and simultaneously, in order to improve the leaching effect of molybdenum, sodium hypochlorite can be added into the sulfuric acid, and the sodium hypochlorite is added into the pickle liquor to promote the dissolution of molybdenum, so that the molybdenum is more easily dissolved by the sulfuric acid, and simultaneously, part of MoO is destroyed 3 Make it more reactive, and FeO and Fe 2 O 3 Then reactions will occur during the pickling process.
The present invention has no particular limitation on the parameters such as time and temperature in the acid leaching process, and those skilled in the art can adjust the parameters according to the actual production situation, smoke situation and processing requirements, and in a preferred embodiment, each operation requirement of the leaching process in step S1 is as follows: A. copper smelting smoke dust: uniformly mixing smoke dust; B. water quality requirements: production water; C. dilute sulfuric acid concentration: 100-400g/L; D. curing time: 0.5-1h; E. sodium hypochlorite addition ratio: 10-100kg/t (tailings); F. smoke dust: dilute acid; 1:5-10; G. leaching temperature: 70-90 ℃; H. stirring speed: 300r-400/min; I. reaction time: 2-4h.
In a preferred embodiment, the concentrated sulfuric acid is used for a period of 30 minutes, and dilute sulfuric acid with an acidity of 1.00-1.50mol/L is used for leaching, preferably the volume ratio of sodium hypochlorite to acid leaching filtrate is 1:50.
in the step S2, the acid leaching filtrate obtained in the step S1 is subjected to purification treatment, and in the step, lime milk and the acid leaching filtrate are added for neutralization, wherein the reaction formula is as follows: as As 2 O 5 +3Ca(OH) 2 →Ca 3 (AsO 4 ) 2 +3H 2 O; adding a catalyst for oxidation, wherein ferrous sulfate is selected as the catalyst to generate a more indissolvable ferric arsenate precipitate, so that arsenic is further removed, and the reaction formula is as follows:
Fe 2+ is oxidized to Fe 3+ ；
2Fe 3+ +3Ca(OH) 2 →2Fe(OH) 3 ↓+3Ca 2+ ；
AsO 4 3- +Fe(OH) 3 →FeAsO 4 ↓+3OH - ;
Arsenic pentoxide (As) 2 O 5 ) The ferric salt (ferrous sulfate) formed by acid leaching in the acid leaching filtrate can also be used as a catalyst (namely ferrous sulfate) to react with the calcium arsenate salt precipitation to generate ferric arsenate precipitation, and calcium sulfate (CaSO) 4 ) The precipitate, namely gypsum, can be used for efficiently adsorbing and removing arsenate, so that the concentration of arsenate in wastewater is reduced, the obtained arsenic slag is filtered, and a filtrate after arsenic precipitation is obtained.
Preferably, the operation requirements of the arsenic removal and purification process in step S2 are: A. reaction temperature: 70-90 ℃; B. stirring speed: 60-100r/min; C. ferrous sulfate: preparing ferrous sulfate aqueous solution with the concentration of 200g/L; the addition rate is 0.1-0.5L/h; D. air flow rate: 0.16m 3 /h; E. lime milk: preparing a lime milk aqueous solution: lime milk and water are mixed according to the proportion of 1:3, the addition rate is 0.5m 3 /h。
In the step S3, copper ions in the arsenic-precipitated filtrate obtained in the step S2 are reduced into metallic copper by adding iron powder, wherein the chemical reaction formula is Fe+Cu 2+ →Fe 2+ +Cu, the iron powder reduces copper ions to elemental copper, and reacts to form ferrous ions (Fe 2+ ) And copper (Cu), the sponge copper obtained is filtered out, the step can not only purify the acid leaching filtrate, but also can improve the concentration of ferric sulfate in the acid leaching filtrate, and the sponge copper is filtered without wasting ironAnd obtaining a copper-precipitated filtrate which is a high-concentration ferric sulfate solution.
Preferably, in step S3, the operation requirements of the sponge copper extraction process are: A. heating filtrate: the temperature is 70-90 ℃; B. filtering and removing impurities by pressing: iron powder (iron powder is added according to about 1.5 times of the copper content in the solution) is added; C. reaction time: until no bubbles are generated in the reaction; D. and (3) a filter pressing procedure: separating sponge copper; E. and (3) reserving filtrate after copper deposition: for the next step of vulcanization preparation, the temperature is controlled between 70 and 90 ℃.
In the step S4, molybdenum in the solution is extracted by adding sodium bisulfide, the concentration of the sodium bisulfide is diluted to 10% by water, then the sodium bisulfide solution is slowly added into the copper-precipitating filtrate, the PH of the solution needs to be strictly controlled in the process, and the PH value of the solution is controlled below 4.1 in the process of adding the sodium bisulfide, so that the PH in the solution is prevented from being too high, and iron ions in the solution are prevented from being hydrolyzed. The reaction is as follows, moO 2 +2H 2 SO 4 =Mo(SO 4 ) 2 +2H 2 O, molybdenum reacts with sulfuric acid to generate molybdenum sulfate under the acid leaching effect in the step 1, and the molybdenum sulfate and sodium hydrosulfide trigger the vulcanization reaction to generate molybdenum sulfide sediment: naHS+H 2 O→NaOH+H 2 S↑，Mo 4+ +S 2- →MoS 2 Reaction of molybdenum sulfate with sodium hydrosulfide, and reaction of molybdenum ion with sulfur ion to generate molybdenum disulfide precipitate (MoS 2 ) Filtering molybdenum disulfide to obtain crude molybdenum for recovery; at the same time, a small part of molybdenum trioxide reacts with dilute sulfuric acid to generate molybdenum sulfate Mo (SO) 4 ) 3 And water H 2 O，Mo 6+ React with sulfur ions to form molybdenum trisulfide precipitate (MoS 3 ) Molybdenum trisulfide is leached along with molybdenum disulfide to give crude molybdenum.
Preferably, in step S4, the operation requirements of the vulcanization extraction process are: A. filtrate treatment: the temperature is 70-90 ℃; B. and (3) preparing a vulcanizing agent: preparing aqueous solution with concentration of 10% by sodium hydrosulfide; C. rate of vulcanizer addition: adding sodium hydrosulfide according to the content of molybdenum in the real-time solution; D. and (3) a filter pressing procedure: and separating crude molybdenum.
In steps S1 to S4, the obtained precipitate is filtered and removed through a filter pressing procedure, wherein the filter pressing procedure refers to an operation procedure of using pressure to promote liquid to permeate through a filter medium in a solid-liquid separation process so as to separate solid particles from the liquid, and parameters of the filter pressing procedure are set as follows: A. feed pressure: 0.6-1kg; B. volume of press filtration: 100L; C. pressure filtration: 1-5kg.
It should be noted that, in step S4, zn is filtered out simultaneously with molybdenum in the sulfidation reaction, and the crude molybdenum contains part of zinc sulfide, and it is necessary to separate after extracting the crude molybdenum and zinc, and the separation method is as follows: the obtained crude molybdenum product is dissolved by dilute sulfuric acid, the obtained molybdenum sulfide does not react with the dilute sulfuric acid, zinc sulfide reacts with the dilute sulfuric acid to generate zinc sulfate and hydrogen sulfide gas, so that the separation of molybdenum and zinc is achieved, and the obtained zinc sulfate is subjected to electrodeposition to obtain a zinc product.
The invention provides a method for recovering molybdenum in side-blown furnace copper smelting smoke dust, which utilizes sulfuric acid to leach out the molybdenum in the smoke dust through a hydrometallurgy technology and recovers the molybdenum through a vulcanization process, thereby realizing the efficient recovery of the molybdenum.
The foregoing description of the preferred embodiment of the invention is not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A method for recovering molybdenum from copper smelting dust, wherein the dust contains arsenic, copper, iron, lead, zinc and molybdenum elements, and the method is characterized by comprising the following steps:
step S1, leaching the smoke dust in an acid leaching solution to obtain an acid leaching filtrate and acid leaching filter residues containing lead;
s2, neutralizing the acid leaching filtrate obtained in the step S1 with alkali, adding a catalyst, and oxidizing to obtain arsenic slag and arsenic-precipitated filtrate;
s3, precipitating copper from the filtrate obtained in the step S2 by using a displacement method to obtain sponge copper precipitate and a filtrate obtained after copper precipitation;
and S4, adding a vulcanizing agent into the copper-precipitating filtrate obtained in the step S3, and adjusting the PH value to be less than 4.1 to trigger the vulcanization reaction, so as to finally form crude molybdenum precipitate and recycling.
2. The method for recovering molybdenum from copper smelting dust according to claim 1, wherein step S1 is to use sulfuric acid for acid leaching of the dust, the dust is first ripened with concentrated sulfuric acid, the dust is then acid leached with dilute sulfuric acid after the ripening, and the solution is continuously stirred during the acid leaching.
3. The method for recovering molybdenum from copper smelting dust according to claim 2, wherein the aging period is 0.5-1h, the acidity of the dilute sulfuric acid is 1.00-1.50mol/L, the concentration of the dilute sulfuric acid is 100-400g/L, the acid leaching temperature is 70-90 ℃, the acid leaching period is 2-4h, and the stirring speed is 300-400r/min.
4. The method for recovering molybdenum from copper smelting dust according to claim 2, wherein in step S2, lime milk is added to the acid leaching filtrate for neutralization, and the catalyst is a ferrous sulfate solution, so as to obtain gypsum and ferric arsenate precipitate.
5. The method for recovering molybdenum from copper smelting dust according to claim 4, wherein an aqueous lime milk solution is prepared in a ratio of lime milk to water of 1:3 for neutralization, and the concentration of the ferrous sulfate solution is 200g/L.
6. The method for recovering molybdenum from copper smelting dust according to claim 2, wherein in step S3, iron powder is added to the filtrate after arsenic precipitation to reduce copper ions to sponge copper precipitate.
7. The method for recovering molybdenum from copper smelting dust according to claim 6, wherein the content of the iron powder is 1.5 times the content of copper in the solution.
8. The method for recovering molybdenum from copper smelting dust as defined in claim 6, wherein step S4 is performed simultaneously to obtain an iron sulfate solution, and the iron sulfate solution is concentrated and crystallized to obtain iron sulfate.
9. The method for recovering molybdenum from copper smelting dust according to claim 1, wherein sodium hypochlorite is synchronously added during acid leaching, and the volume ratio of the sodium hypochlorite to the acid leaching filtrate is 1:50.
10. the method for recovering molybdenum from copper smelting dust according to claim 1, wherein the sulfidizing agent is a 10% sodium hydrosulfide aqueous solution.
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