CN117488092B - Molten pool smelting and flue gas treatment process for antimony-gold concentrate - Google Patents
Molten pool smelting and flue gas treatment process for antimony-gold concentrate Download PDFInfo
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- CN117488092B CN117488092B CN202311848394.1A CN202311848394A CN117488092B CN 117488092 B CN117488092 B CN 117488092B CN 202311848394 A CN202311848394 A CN 202311848394A CN 117488092 B CN117488092 B CN 117488092B
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- arsenic
- gold
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 239000003546 flue gas Substances 0.000 title claims abstract description 182
- 238000003723 Smelting Methods 0.000 title claims abstract description 101
- 239000012141 concentrate Substances 0.000 title claims abstract description 67
- KAPYVWKEUSXLKC-UHFFFAOYSA-N [Sb].[Au] Chemical compound [Sb].[Au] KAPYVWKEUSXLKC-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 140
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000000428 dust Substances 0.000 claims abstract description 91
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 52
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 44
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 44
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052737 gold Inorganic materials 0.000 claims abstract description 40
- 239000010931 gold Substances 0.000 claims abstract description 40
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 30
- 239000011707 mineral Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000002893 slag Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 12
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006004 Quartz sand Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 235000019738 Limestone Nutrition 0.000 claims abstract description 7
- 239000006028 limestone Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 26
- 239000002918 waste heat Substances 0.000 claims description 23
- 239000004744 fabric Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000011084 recovery Methods 0.000 abstract description 36
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 239000010970 precious metal Substances 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229960002594 arsenic trioxide Drugs 0.000 description 4
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 4
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 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
- 238000011946 reduction process Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ZVQHJJXXEAGYOP-UHFFFAOYSA-N [Sb]=O.[As] Chemical compound [Sb]=O.[As] ZVQHJJXXEAGYOP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- FTVVAESDJYIMNQ-UHFFFAOYSA-N antimony;sulfanylidenelead Chemical compound [Sb].[Pb]=S FTVVAESDJYIMNQ-UHFFFAOYSA-N 0.000 description 1
- LZYIDMKXGSDQMT-UHFFFAOYSA-N arsenic dioxide Inorganic materials [O][As]=O LZYIDMKXGSDQMT-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
Abstract
The invention discloses a smelting bath smelting and flue gas treatment process of antimony gold concentrate, which comprises the following steps: (1) Taking antimony gold concentrate, antimony oxide powder, quartz sand and limestone as raw materials, mixing the raw materials, and granulating in a granulator; (2) Heating mineral particles to 1000-1300 ℃, and introducing oxygen to perform molten pool smelting to obtain noble antimony, high-antimony slag and arsenic-antimony-containing flue gas; (3) Cooling the flue gas containing arsenic and antimony, and then recycling antimony-containing solids by using an electric dust collector; (4) And cooling the flue gas subjected to electric dust collection treatment, and then recovering arsenic-containing solids by using a bag dust collector. According to the smelting bath smelting and flue gas treatment process of the antimony-gold concentrate, gold is distributed in precious antimony produced by smelting, so that the recovery cost and recovery difficulty of precious metal gold in the antimony-gold concentrate are greatly reduced, the recovery process is simplified, and meanwhile, effective recovery of valuable metals and sulfur elements in flue gas is realized, so that the process has high economic value.
Description
Technical Field
The invention relates to the technical field of metal extraction engineering, in particular to a molten pool smelting and flue gas treatment process of antimony gold concentrate, which is convenient for recovering noble metals in antimony gold concentrate and can realize effective recovery of valuable metals in flue gas and purification of sulfur dioxide.
Background
The current molten pool smelting technology of the antimony gold concentrate (the mass fraction of the antimony sulfide in the concentrate is about 38-45%) is to granulate the antimony gold concentrate ingredients and then carry out molten pool smelting to obtain antimony slag and flue gas.
During the smelting process of the molten pool, part of antimony sulfide in the antimony gold concentrate reacts as follows and enters smoke gas: direct volatilization: sb (Sb) 2 S 3 (solid) =sb 2 S 3 (gas), gas phase oxidation: 2Sb 2 S 3 (gas) +9O 2 =2Sb 2 O 3 (gas) +6SO 2 (gas), oxidation and volatilization: 2Sb 2 S 3 (liquid) +9O 2 =2Sb 2 O 3 (gas) +6SO 2 Part of the antimony sulfide in the antimony gold concentrate enters smelting slag through the following peroxidation reaction into antimony higher oxides: sb (Sb) 2 S 3 (liquid) +5O 2 =Sb 2 O 4 (liquid) +3SO 2 (gas), 2Sb 2 S 3 (liquid) +11O 2 =2Sb 2 O 5 (liquid) +6SO 2 (gas). Precious metals in the antimony-gold concentrate are basically all enriched in smelting slag (antimony slag), the smelting slag is reduced and smelted to obtain crude antimony, the crude antimony is blown to further obtain a precious antimony phase containing gold, and finally, the precious antimony phase is separated to realize the effective recovery of antimony and precious metal gold. Therefore, the existing molten pool smelting process generally only produces high antimony slag and flue gas, precious metals (gold) in the antimony concentrate are basically all enriched in the smelting slag (antimony slag), and if the precious metals are to be recovered, the complex reduction process of the antimony slag is required in the subsequent process, so that the recovery difficulty and the process complexity of the precious metals in the antimony concentrate are greatly improved.
Meanwhile, besides antimony and noble metals, other metals such as arsenic and sulfur dioxide exist in the smelted flue gas, so that the smelted flue gas has a certain recovery value in the aspects of economic value and environmental protection requirements, but the existing molten pool smelting process also has the problems of poor collection efficiency and poor effect of antimony when the flue gas is treated.
Disclosure of Invention
The invention provides a smelting and flue gas treatment process of an antimony gold concentrate molten pool, which is used for solving the technical problems that the existing smelting process of antimony gold concentrate needs multiple processes and complex processes to recover noble metal gold in the antimony gold concentrate, the recovery cost of the noble metal gold is high, the difficulty is high, and the recovery effect of arsenic and other metals in flue gas generated by smelting is poor.
In order to solve the technical problems, the invention adopts the following technical scheme:
a smelting bath smelting and flue gas treatment process of antimony gold concentrate comprises the following steps:
(1) Taking antimony gold concentrate, antimony oxide powder, quartz sand and limestone as raw materials, mixing the raw materials, and granulating by using a granulator to obtain mineral particles;
(2) Heating the mineral particles to 1000-1300 ℃, introducing oxygen to perform molten pool smelting, and immediately reacting antimony sulfide existing in antimony oxide and antimony gold concentrate in the molten pool smelting process to form a metal antimony phase, wherein the metal antimony phase complements gold existing in the antimony gold concentrate to form precious antimony, and finally obtaining precious antimony, high antimony slag and arsenic-antimony-containing flue gas; in the noble antimony, the mass of gold accounts for 60% -70% of the total mass of gold in the antimony gold concentrate;
(3) Cooling the flue gas containing arsenic and antimony, then collecting dust by using an electric dust collector, and recovering antimony-containing solid from the electric dust collector;
(4) Cooling the flue gas subjected to electric dust collection treatment, collecting dust by using a bag dust collector, and recovering arsenic-containing solids from the bag dust collector.
As described in the background art of the invention, the existing smelting process of a molten pool aiming at the antimony gold concentrate generally only uses antimony gold concentrate without adding antimony oxide when smelting, so that enough antimony oxide does not exist in a system, so that antimony sulfide existing in the antimony gold concentrate cannot be interacted with the antimony oxide in time, a metal antimony phase molten pool is difficult to form, gold existing in the antimony gold concentrate cannot be trapped, a large amount of gold enters high antimony slag, recovery can be realized through a complex reduction process, and recovery difficulty and cost are increased. The invention uses antimony oxide powder and antimony gold concentrate as raw materials, the two are granulated together with quartz sand and limestone to form mineral particles and smelting, in the smelting process, antimony sulfide and antimony trioxide directly react to generate metallic antimony phases due to the existence of sufficient antimony trioxide in the mineral particles, the formed metallic antimony phases can immediately trap and form noble metal gold in the antimony gold concentrate, and compared with the existing molten pool smelting process which only can produce flue gas and antimony slag, the molten pool smelting process directly produces noble antimony enriched with noble metal gold (the quality of gold complemented by the noble antimony can account for 60% -70% of the total mass of gold in the antimony gold concentrate), and the component separation of the produced noble antimony products can be directly carried out in the subsequent steps, so that the recovery of the gold in the antimony slag can be realized, the processes of reduction and blowing of the antimony slag are omitted, the recovery cost and the recovery difficulty of the noble metal gold in the antimony gold concentrate are greatly reduced, and the recovery flow is simplified, and the molten pool smelting process has extremely high economic value. Meanwhile, aiming at the flue gas generated by smelting a molten pool, the invention utilizes the characteristic that the vapor pressure of the arsenic-antimony oxide has obvious difference at different temperatures, and realizes the effective recovery of valuable metals in the flue gas by cooling twice before and after and adopting different dust collection devices to collect dust, thereby respectively recovering arsenic-containing solids (white arsenic) and antimony-containing solids (antimony white).
Preferably, the weight ratio of the antimony oxide to the antimony sulfide in the mineral particles is (0.25:1) - (0.35:1). The adding amount of the antimony oxide determines the complement effect of the metallic antimony relative to the noble metal gold in the smelting process, and if the adding amount of the antimony oxide in the raw materials is less and the mass ratio is too low, the metallic antimony phase is difficult to effectively generate in the smelting process of a molten pool, so that the gold in the antimony gold concentrate cannot be effectively trapped; if the antimony oxide is added in a large amount and the mass ratio is too high, the mass ratio of gold in the precious antimony finally produced by smelting in a molten pool is reduced, and the subsequent gold separation difficulty of the precious antimony is increased, so that the inventor determines the weight ratio of the antimony oxide to the antimony sulfide after intensive research and repeated experiments.
Preferably, when the mineral particles are heated in the step (2), the mineral particles are gradually heated to a relatively low temperature of 600-800 ℃, in this stage, antimony sulfide and antimony oxide powder existing in the antimony gold concentrate start to fully react and form the metallic antimony phase due to the presence of the antimony oxide powder in the mineral particles, and are further heated to 1000-1300 ℃ for melting in a molten pool, so that the antimony sulfide and the antimony oxide fully react to generate the metallic antimony phase, and the metallic antimony phase complements gold existing in the antimony gold concentrate to form precious antimony, and finally the precious antimony, high antimony slag and arsenic-antimony-containing flue gas are obtained.
Preferably, in the step (3), before the arsenic-and antimony-containing flue gas is collected by an electric dust collector, the arsenic-and antimony-containing flue gas is cooled to 300-450 ℃; in the step (4), before the flue gas subjected to electric dust collection is collected by using a bag dust collector, the flue gas subjected to electric dust collection is cooled to 120-150 ℃.
Preferably, in the step (4), when the flue gas subjected to the electric dust collection treatment is cooled, the flue gas is cooled to 120-150 ℃ within 0.2 s. When the flue gas subjected to electric dust collection treatment is cooled, the cooling rate and the final cooling temperature are the key points of whether the arsenic-containing solids can be successfully recovered and whether the arsenic-containing solids can be effectively recovered, if the cooling rate is too slow, the arsenic-containing solids can possibly generate the phenomenon of sticking and connecting blocks in the cooling process, equipment is blocked, and the arsenic-containing solids recovery process is blocked.
Preferably, the flue gas containing arsenic and antimony generated by smelting in the step (2) is collected through a flue and is conveyed to a waste heat boiler to heat the waste heat boiler and realize cooling of the flue gas, and before the flue gas containing arsenic and antimony is collected by an electric dust collector, water vapor is supplemented into the flue gas containing arsenic and antimony, so that the volume fraction of the water vapor in the flue gas containing arsenic and antimony before the flue gas containing arsenic and antimony is introduced into the electric dust collector is 6% -10%. When the prior art is used for treating the antimony-containing flue gas, the problems of poor collection effect and poor efficiency of the antimony-containing solid exist, but the cause and the solution of the phenomenon are not disclosed in the prior art; the inventor finds that when the electric dust collector is used for collecting dust of the stibium-containing flue gas, the volume proportion of water vapor in the flue gas has great influence on the electric dust collection effect, and the invention supplements water vapor to the flue gas additionally, changes the volume proportion of the water vapor in the flue gas, improves the conductivity of stibium-containing solid in the flue gas, thereby improving the electric dust collection recovery effect and efficiency of the stibium-containing solid; after repeated experiments and intensive researches of the inventor, an optimal range of the volume fraction of the water vapor in the flue gas is determined, and below the range, the conductivity of the antimony-containing solid in the flue gas is poor, the antimony recovery rate is low, and when the water vapor content is higher than the range, the content of the antimony in the recovered arsenic-containing solid is low.
Preferably, the flue gas containing arsenic and antimony generated by smelting in the step (2) is collected through a flue and is conveyed to a waste heat boiler to heat the waste heat boiler and realize cooling of the flue gas, the residence time of the flue gas containing arsenic and antimony in the flue is controlled to be 6-8 s, and the temperature of the flue gas containing arsenic and antimony in the flue is ensured to be maintained above 600 ℃. The physical properties of the antimony oxide and the antimony sulfide lead to the fact that the antimony oxide and the antimony sulfide are easy to volatilize into smoke in the smelting process, the volatilized antimony oxide and the antimony sulfide cannot completely react to cause the loss of smelting raw materials and further cause the reduction of smelting effects, so that the residence time of the smoke in a flue is strictly controlled, and the volatilized antimony oxide and the antimony sulfide still have enough time to further react in the flue, thereby playing roles of reducing the loss of raw materials and improving the smelting effects. Maintaining the temperature of the arsenic-and antimony-containing flue gas in the flue at above 600 ℃ can promote the continuous reaction of antimony oxide and antimony sulfide in the flue.
Preferably, in the step (3), when the flue gas containing arsenic and antimony is collected by using an electric dust collector, the temperature of the flue gas containing arsenic and antimony is maintained at 300-450 ℃. The temperature range can avoid the phenomenon of sticking and connecting blocks of arsenic-containing substances caused by gradual cooling of flue gas in the electric dust collection process, thereby maintaining the normal operation of equipment and ensuring the deep recovery of arsenic.
Preferably, in the step (4), when the flue gas subjected to the electric dust collection treatment is collected by using a bag dust collector, the temperature of the flue gas subjected to the electric dust collection treatment is maintained at 120-150 ℃. The invention prevents the influence of condensation of water vapor in the flue gas caused by the too low flue gas temperature on the dust collection efficiency and effect of the cloth bag by limiting the temperature range of the flue gas in the dust collection process of the cloth bag.
Preferably, in the step (4), after the flue gas subjected to electric dust collection treatment is cooled, dust is collected and arsenic-containing solid is recovered, the flue gas subjected to cloth bag dust collection treatment is conveyed to an acid making system for acid making. Step (3) and step (4) realize the effective recovery of antimony and arsenic in the flue gas, and simultaneously improve SO in the flue gas 2 The content of the sulfur dioxide in the flue gas is removed, so that the flue gas meets the requirements of the acid making process on the concentration and purity of sulfur dioxide, and pure sulfuric acid can be prepared by using the flue gas.
Compared with the prior art, the invention has the advantages that:
according to the smelting bath smelting and flue gas treatment process of the antimony-gold concentrate, on one hand, the reasonable optimization selection of raw materials is utilized, so that antimony sulfide and antimony oxide react in time to generate a metallic antimony phase in the smelting process, gold in mineral particles is trapped and forms noble antimony, gold is distributed in the noble antimony generated by smelting, the recovery convenience of noble metals is greatly improved, on the other hand, the effective recovery of valuable metals in arsenic-containing and antimony-containing flue gas and the purification of sulfur dioxide in the flue gas are realized, the treated flue gas meets the smelting emission standard of the antimony concentrate, and the efficient recovery of each element of the antimony-gold concentrate is realized from multiple aspects: firstly, through the design of smelting raw materials, precious metals such as gold are collected, the precious metals such as gold are distributed in precious antimony and high antimony slag generated by smelting, and the recovery of the precious metals is facilitated. Meanwhile, the invention can also effectively prevent the phenomenon of adhesion and connection of arsenic in the recovery process, thereby improving the recovery effect of arsenic and avoiding the problem of blockage of equipment and adverse effect on production.
Drawings
FIG. 1 is a flow chart of a bath smelting and flue gas treatment process for antimony gold concentrate of example 1;
FIG. 2 is a schematic diagram showing the structure of a bath smelting apparatus for antimony gold concentrate according to example 1.
Legend description:
1. a melting tank furnace; 11. a feed opening; 12. a siphon port; 13. a smoke port; 14. a slag hole; 15. an oxygen lance; 2. a flue; 3. a waste heat boiler; 31. a flue gas inlet; 32. a flue gas outlet; 41. a pipe; 42. an atomizing nozzle; 43. and a controller.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In this example, as well as in other examples and comparative examples, the method for determining and analyzing gold in antimony gold concentrate was carried out with reference to the standard document "YS/T556.9-2009"; in this example, as well as in other examples and comparative examples, the method for measuring and analyzing gold in crude antimony (noble antimony) was carried out with reference to the standard document "YS/T1582.2-2022".
Example 1:
the smelting bath smelting and flue gas treatment process of the antimony gold concentrate in the embodiment is shown in fig. 1, and specifically comprises the following steps:
(1) The method comprises the steps of taking antimony gold concentrate, antimony oxide powder, quartz sand and limestone as raw materials, mixing the raw materials, and granulating in a granulator to obtain mineral particles, wherein the mass ratio of antimony oxide to antimony sulfide in the mineral particles is 0.25:1.
(2) Adding mineral particles and a certain amount of water into a melting furnace, and introducing O 2 Smelting in a molten pool at 1200 ℃, wherein antimony sulfide and antimony oxide fully react to generate a metallic antimony phase at a relatively low temperature stage of 600-800 ℃ in a gradual heating process due to the existence of antimony oxide in mineral particles, and after the temperature is raised to 1200 ℃, the antimony sulfide and the antimony oxide further fully react to generate the metallic antimony phase, and the metallic antimony is trapped relative to gold in the mineral particles and forms precious antimony, so that metallic phase precious antimony, slag phase high-antimony slag and arsenic and antimony-containing flue gas are obtained; wherein, gold enriched by noble antimony accounts for 61% of the total input mass.
(3) Introducing the flue gas containing arsenic and antimony generated by smelting into a waste heat boiler through a flue to cool, and using a water content adjusting device to input water into the waste heat boiler, wherein the water is changed into water vapor at high temperature, so that the volume fraction of the water vapor in the flue gas before the flue gas containing arsenic and antimony is introduced into an electric dust collector to carry out electric dust collection is 6%; the flue gas temperature is ensured to be above 600 ℃ in the flue, and the flue gas stays in the flue for about 7s, in the embodiment, the control of the stay time of the flue gas in the flue is realized by designing the length of the flue gas and matching with the flow rate of the flue gas, the structure of the smelting device of the molten pool of the antimony gold concentrate is shown in figure 2, and the length of the flue gas is 30m; after the temperature of the flue gas is reduced to 300 ℃, the flue gas is introduced into an electric dust collector for electric dust collection, and pure antimony white (the antimony content is 80%) is recovered from the electric dust collector, and the recovery rate of the antimony in the flue gas is 90%.
(4) Cooling the flue gas subjected to electric dust collection to 120 ℃ in 0.2s by using a quenching tower, introducing the flue gas into a cloth bag dust collector for cloth bag dust collection, and recovering white arsenic from the cloth bag dust collector to obtain the flue gas with the arsenic recovery rate of 99.98%.
(5) Introducing the flue gas subjected to bag dust removal into a sulfuric acid system for acid making, and carrying out acid making purification on the flue gas before acid making, wherein the acid making purification adopts a purification flow of a first-stage efficient scrubber, a packing tower, a second-stage efficient scrubber and an electric demister, and dilute acid washing adopts closed circulation purification; the (3+2) two-to-two-absorption acid preparation process flow is adopted for acid preparation, the III I-V IV II process flow is adopted for conversion, and SO in the final flue gas is adopted 2 The conversion absorption rate is more than 99.9 percent, and the flue gas directly reaches the emission standard of antimony smelting.
The structure of the smelting device of the molten pool of the antimony gold concentrate is shown in fig. 2, the smelting device comprises a waste heat boiler 3, a flue 2 and a smelting furnace 1 provided with a feed opening 11, a siphon opening 12, a flue gas opening 13 and a slag opening 14, wherein an oxygen lance 15 is arranged at the bottom of the smelting furnace 1; the flue gas port 13 of the melting tank furnace 1 is communicated with one end of the flue 2, and the length of the flue 2 is designed, so that the residence time of the flue gas in the flue 2 is controlled by matching with the flow rate of the flue gas, and the flue 2 is vertically upwards, and the length is 30m; the other end of the flue 2 is communicated with a flue gas inlet 31 of the waste heat boiler 3; the waste heat boiler 3 is provided with a moisture adjusting device including a pipe 41, an atomizing nozzle 42, and a controller 43, and the moisture adjusting device inputs water into the waste heat boiler 3 through the pipe 41 and the atomizing nozzle 42, and the process is controlled by the controller 43. Flue gas generated by the melting tank furnace 1 enters the flue 2 through a flue gas port 13, and antimony oxide and antimony sulfide in the flue 2 further react; the flue gas enters the waste heat boiler 3 through the flue 2, water is supplemented through the water content adjusting device, the volume fraction of water vapor in the flue gas is 6%, and the flue gas enters the flue gas treatment device through the flue gas outlet 32 of the waste heat boiler for subsequent cooling, dust collection and other operations.
Example 2:
the smelting bath smelting and flue gas treatment process of the antimony gold concentrate comprises the following steps of:
(1) The method comprises the steps of taking antimony gold concentrate, antimony oxide powder, quartz sand and limestone as raw materials, mixing the raw materials, and granulating in a granulator to obtain mineral particles, wherein the mass ratio of antimony oxide to antimony sulfide in the mineral particles is 0.35:1.
(2) Adding mineral particles and a certain amount of water into a melting furnace, and introducing O 2 And N 2 Smelting in a molten pool at 1200 ℃, wherein antimony sulfide and antimony oxide fully react to generate a metallic antimony phase at a relatively low temperature stage of 600-800 ℃ in a gradual heating process due to the existence of antimony oxide in mineral particles, and after the temperature is raised to 1200 ℃, the antimony sulfide and the antimony oxide further fully react to generate the metallic antimony phase, and the metallic antimony is trapped relative to gold in the mineral particles and forms precious antimony, so that metallic phase precious antimony, slag phase high-antimony slag and arsenic and antimony-containing flue gas are obtained; wherein, gold enriched by noble antimony accounts for 62.3 percent of the total input mass.
(3) Introducing the flue gas containing arsenic and antimony generated by smelting into a waste heat boiler through a flue to cool, and using a water content adjusting device to input water into the waste heat boiler, wherein the water is changed into water vapor at high temperature, so that the volume fraction of the water vapor in the flue gas before the flue gas containing arsenic and antimony is introduced into an electric dust collector to carry out electric dust collection is 10%; the temperature of the flue gas is ensured to be above 600 ℃ in the flue, and the flue gas stays in the flue for about 7 s; after the temperature of the flue gas is reduced to 300 ℃, the flue gas is introduced into an electric dust collector for electric dust collection, and purer antimony white (the antimony content is 78%) is recovered from the electric dust collector, and the recovery rate of antimony in the flue gas is 99%.
(4) Cooling the flue gas subjected to electric dust collection to 130 ℃ in 0.2s by using a quenching tower, introducing the flue gas into a cloth bag dust collector for cloth bag dust collection, and recovering white arsenic from the cloth bag dust collector to obtain the flue gas with the arsenic recovery rate of 99.97%.
(5) Introducing the flue gas subjected to bag dust removal into a sulfuric acid system for acid making, and carrying out acid making purification on the flue gas before acid making, wherein the acid making purification adopts a purification flow of a first-stage efficient scrubber, a packing tower, a second-stage efficient scrubber and an electric demister, and dilute acid washing adopts closed circulation purification; the (3+2) two-to-two-absorption acid preparation process flow is adopted for acid preparation, the III I-V IV II process flow is adopted for conversion, and SO in the final flue gas is adopted 2 The conversion absorption rate is more than 99.9 percent, and the flue gas directly reaches the emission standard of antimony smelting.
The bath smelting apparatus for antimony gold concentrate of this example is the same as that of example 1.
Example 3:
the smelting bath smelting and flue gas treatment process of the antimony gold concentrate comprises the following steps of:
(1) The method comprises the steps of taking antimony gold concentrate, antimony oxide powder, quartz sand and limestone as raw materials, mixing the raw materials, and granulating in a granulator to obtain mineral particles, wherein the mass ratio of antimony oxide to antimony sulfide in the mineral particles is 0.3:1.
(2) Adding mineral particles and a certain amount of water into a melting furnace, and introducing O 2 And N 2 Smelting in a molten pool at 1200 ℃, wherein antimony sulfide and antimony oxide fully react to generate a metallic antimony phase at a relatively low temperature stage of 600-800 ℃ in a gradual heating process due to the existence of antimony oxide in mineral particles, and after the temperature is raised to 1200 ℃, the antimony sulfide and the antimony oxide further fully react to generate the metallic antimony phase, and the metallic antimony is trapped relative to gold in the mineral particles and forms precious antimony, so that metallic phase precious antimony, slag phase high-antimony slag and arsenic and antimony-containing flue gas are obtained; wherein, gold enriched by noble antimony accounts for 61.7 percent of the total input mass.
(3) Introducing the flue gas containing arsenic and antimony generated by smelting into a waste heat boiler through a flue to cool, and using a water content adjusting device to input water into the waste heat boiler, wherein the water is changed into water vapor at high temperature, so that the volume fraction of the water vapor in the flue gas before the flue gas containing arsenic and antimony is introduced into an electric dust collector to carry out electric dust collection is 8%; the temperature of the flue gas is ensured to be above 600 ℃ in the flue, and the flue gas stays in the flue for about 7 s; after the temperature of the flue gas is reduced to 380 ℃, the flue gas is introduced into an electric dust collector for electric dust collection, and purer antimony white (the antimony content is 80%) is recovered from the electric dust collector, and the recovery rate of antimony in the flue gas is 98.7%.
(4) Cooling the flue gas subjected to electric dust collection to 150 ℃ in 0.2s by using a quenching tower, introducing the flue gas into a cloth bag dust collector for cloth bag dust collection, and recovering white arsenic from the cloth bag dust collector to obtain the flue gas with the arsenic recovery rate of 99.83%.
(5) Introducing the flue gas subjected to bag dust removal into a sulfuric acid system for acid making, and carrying out acid making purification on the flue gas before acid making, wherein the acid making purification adopts a purification flow of a first-stage efficient scrubber, a packing tower, a second-stage efficient scrubber and an electric demister, and dilute acid washing adopts closed circulation purification; the (3+2) two-to-two-absorption acid preparation process flow is adopted for acid preparation, the III I-V IV II process flow is adopted for conversion, and SO in the final flue gas is adopted 2 The conversion absorption rate is more than 99.9 percent, and the flue gas directly reaches the emission standard of antimony smelting.
The bath smelting apparatus for antimony gold concentrate of this example is the same as that of example 1.
Comparative example 1:
compared with the embodiment 1, the smelting process of the smelting pool and the flue gas treatment process of the antimony gold concentrate of the comparative example are different in that in the step (1) of the comparative example, the antimony gold concentrate and quartz sand are mixed and then granulated in a granulator, and no antimony oxide powder is added. Other apparatus, steps, parameters were as in example 1.
Through detection, the precious antimony obtained in the smelting bath smelting and flue gas treatment process step (2) of the antimony-gold concentrate of the comparative example occupies relatively low content in the product, an effective metal phase is difficult to form, the system cannot stably operate, and the gold enriched in the precious antimony only occupies 31.3% of the total input mass.
Comparative example 2:
compared with the embodiment 1, the specific steps of the smelting bath and flue gas treatment process of the antimony gold concentrate of the comparative example are different in that water is not input into the flue gas by using a water regulating device in the step (3) of the comparative example, so that before the flue gas is charged into an electric dust collector for electric dust collection, water vapor in the flue gas mainly comes from water added during granulation and water contained in smelting raw materials, and the volume fraction of the water vapor in the flue gas is 4%. Other apparatus, steps, parameters were as in example 1. According to detection, the antimony white content recovered from the electric dust collector in the step (3) of the comparative example is 70%, and the recovery rate of antimony in the flue gas is only 60%.
Comparative example 3:
compared with the embodiment 1, the smelting bath and flue gas treatment process of the antimony gold concentrate of the comparative example has the specific steps that before the flue gas is introduced into an electric dust collector for electric dust collection in the step (3), water is input into a waste heat boiler by utilizing a water regulating device, the water is changed into water vapor at high temperature, and the volume fraction of the water vapor in the flue gas is 12%. Other apparatus, steps, parameters were as in example 1. According to detection, the antimony white content recovered from the electric dust collector in the step (3) of the comparative example is 76%, and the recovery rate of antimony in the flue gas is 99.1%.
The above is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above examples. Modifications and variations which would be obvious to those skilled in the art without departing from the spirit of the invention are also considered to be within the scope of the invention.
Claims (6)
1. The smelting bath smelting and flue gas treatment process for the antimony gold concentrate is characterized in that the smelting bath smelting and flue gas treatment process is completed by a smelting bath smelting device, the smelting bath smelting device comprises a waste heat boiler, a flue and a smelting bath furnace, and an oxygen lance is arranged at the bottom of the smelting bath furnace; the melting bath smelting and flue gas treatment process comprises the following steps:
(1) Mixing antimony gold concentrate, antimony oxide powder, quartz sand and limestone serving as raw materials, and granulating the raw materials by using a granulator to obtain mineral particles, wherein the weight ratio of antimony oxide to antimony sulfide in the mineral particles is (0.25:1) - (0.35:1);
(2) Heating the mineral particles to 1000-1300 ℃, introducing oxygen to perform molten pool smelting, and immediately reacting antimony sulfide existing in antimony oxide and antimony gold concentrate in the molten pool smelting process to form a metallic antimony phase, wherein the metallic antimony phase traps gold existing in the antimony gold concentrate to form noble antimony, and finally, noble antimony, high-antimony slag and arsenic-antimony-containing flue gas are obtained; in the noble antimony, the mass of gold accounts for 60% -70% of the total mass of gold in the antimony gold concentrate;
(3) Cooling the flue gas containing arsenic and antimony, then collecting dust by using an electric dust collector, and recovering antimony-containing solid from the electric dust collector; the flue gas containing arsenic and antimony generated by smelting a molten pool is collected through a flue and is conveyed to a waste heat boiler to heat the waste heat boiler and cool the flue gas, and before the flue gas containing arsenic and antimony is collected by an electric dust collector, water vapor is supplemented into the flue gas containing arsenic and antimony, so that the volume fraction of the water vapor in the flue gas containing arsenic and antimony before the flue gas containing arsenic and antimony is introduced into the electric dust collector is 8% -10%;
(4) Cooling the flue gas subjected to electric dust collection treatment, collecting dust by using a bag dust collector, and recovering arsenic-containing solids from the bag dust collector; before the flue gas subjected to electric dust collection is collected by using a bag dust collector, the flue gas subjected to electric dust collection is cooled to 120-150 ℃ within 0.2 s.
2. The process for smelting and treating flue gas in a molten bath of antimony-gold concentrate according to claim 1, wherein when the mineral particles are heated in step (2), the heating is gradually performed to a relatively low temperature of 600-800 ℃, in which stage antimony sulfide and antimony oxide powder present in the antimony-gold concentrate start to fully react and form the metallic antimony phase due to the presence of antimony oxide powder in the mineral particles, and further the heating is performed to 1000-1300 ℃ to perform the molten bath smelting, so that the antimony sulfide and antimony oxide fully react to form the metallic antimony phase, and the metallic antimony phase traps gold present in the antimony-gold concentrate to form precious antimony, high antimony slag and flue gas containing arsenic and antimony finally.
3. The process for smelting antimony gold concentrate in a molten pool and treating flue gas according to claim 1, wherein in the step (3), before arsenic-and antimony-containing flue gas is collected by an electric dust collector, the arsenic-and antimony-containing flue gas is cooled to 300-450 ℃.
4. The smelting bath and flue gas treatment process of antimony gold concentrate according to claim 1, wherein the flue gas containing arsenic and antimony generated in the smelting bath in the step (2) is collected through a flue and is conveyed to a waste heat boiler to heat the waste heat boiler and realize self cooling of the flue gas, the residence time of the flue gas containing arsenic and antimony in the flue is controlled to be 6-8 s, and the temperature of the flue gas containing arsenic and antimony in the flue is ensured to be maintained above 600 ℃.
5. The process for smelting antimony gold concentrate in a molten pool and treating flue gas according to any one of claims 1-4, wherein in the step (4), the temperature of the flue gas treated by electric dust collection is maintained at 120-150 ℃ during dust collection of the flue gas treated by electric dust collection by a bag dust collector.
6. The process for smelting antimony and treating flue gas in a molten pool according to any one of claims 1 to 4, wherein in step (4), the flue gas subjected to electric dust collection is cooled, dust is collected and arsenic-containing solids are recovered, and the flue gas subjected to dust collection in a cloth bag is conveyed to an acid making system for acid making.
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