CN105506295A - Combined As removing and purifying method - Google Patents
Combined As removing and purifying method Download PDFInfo
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- CN105506295A CN105506295A CN201511012638.8A CN201511012638A CN105506295A CN 105506295 A CN105506295 A CN 105506295A CN 201511012638 A CN201511012638 A CN 201511012638A CN 105506295 A CN105506295 A CN 105506295A
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- arsenic
- dearsenification
- flue dust
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- distillation
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000000779 smoke Substances 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 19
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000000859 sublimation Methods 0.000 claims abstract description 13
- 230000008022 sublimation Effects 0.000 claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 10
- 229910052785 arsenic Inorganic materials 0.000 claims description 61
- 239000003500 flue dust Substances 0.000 claims description 60
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 49
- 238000004821 distillation Methods 0.000 claims description 26
- 238000000746 purification Methods 0.000 claims description 23
- 238000010792 warming Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000000428 dust Substances 0.000 claims description 13
- 229960002594 arsenic trioxide Drugs 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052745 lead Inorganic materials 0.000 claims description 7
- 241001062472 Stokellia anisodon Species 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000003818 cinder Substances 0.000 claims description 2
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims 1
- 238000003723 Smelting Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 13
- 238000009835 boiling Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 241001417490 Sillaginidae Species 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
-
- 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
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a combined As removing and purifying method. The method comprises the steps of mixing As containing smoke of different grades to the degree that an As2O3 is smaller than 10%, and a valuable metal grade is larger than 15%; preparing into a proper slag form; sintering to remove As of one of half raw material to form sintered blocks, producing first oxidability enriching smoke with 25-30% of As2O3, then briquetting the other half of raw material and inputting into a blast furnace with the sintered blocks, and producing the first reducibility enriching smoke with 18-40% of As2O3; then performing equal proportion burdening and sublimation and As removing on the first oxidability enriching smoke and the first reducibility enriching smoke to produce secondary enriching smoke with the As2O3 as high as 70-80%, after As removing, returning residues to a first enriching system for reuse, thus realizing a high As removing rate and metal separation rate of the large-scale As containing raw material smelting; finally sublimating the secondary enriching smoke according temperature sections to purify As2O3.
Description
Technical field
The present invention relates to arsenic-containing smoke dust in non-ferrous metal to smelt and a kind of method of associating dearsenification purification arsenic of synthetical recovery, particularly high-arsenic dust.
Background technology
In non-ferrous metal metallurgy industry, source and the channel of arsenic-containing smoke dust are different, and the grade containing arsenic is also different, such as, the content of As O lower from 1% ~ 5% not etc., and content high reach 30% ~ 70%, the content of its valuable metal is not by 5% ~ 50% etc. yet.For the large-scale comprehensive recovery arsenic-containing smoke dust enterprise that scale reaches several ten thousand tons/year, the average arsenic content of its raw material is generally between 2% ~ 25%.For thermal process, from metal separation rate, the highest in existing method is distillation dearsenification method, but this method is only suitable for raw material containing arsenic grade higher than the situation of 25%, otherwise production cost can be caused too high.And point temperature section sublimation purification white arsenic method also can only to be applicable to containing arsenic grade, higher than the smoke raw material of 70%, otherwise production cost also can be caused too high.The processing method of neither one system high efficiency concentration and separation purification is gone back at present for large-scale arsenic-containing smoke dust and valuable metal raw material.
Summary of the invention
The present invention seeks to as large-scale recovery is containing arsenic and valuable metal raw material, a kind of system, efficient, economically viable method of smelting the associating dearsenification purification arsenic of enrichment arsenic, distillation secondary enrichment arsenic and a point temperature section sublimation purification arsenic about sintering oxidation enrichment arsenic, blast furnace reduction are provided.
For reaching above-mentioned purpose, the technical solution used in the present invention is: a kind of method of associating dearsenification purification arsenic, it comprises the steps:
1) classification of arsenic-containing smoke dust raw material, a point grade are deposited.
2) according to the different grade of valuable metal in various arsenic-containing smoke dust and required treatment capacity, various arsenic-containing smoke dust of arranging in pairs or groups is formed prepares burden into stove, make valuable metal grade Pb+Sn+Bi >=15%, general 30% ~ 40% is good, iron calcium silicate slag type is mass ratio Fe:SiO: CaO=10 ~ 12:10:7 ~ 8, and containing arsenic grade 3% ~ 10%.
3) step 2) be made into enter stove batching half send into sintering oven sintering dearsenification, formed agglomerate, once oxidation enrichment flue dust.The once oxidation enrichment flue dust volatilized during sintering is generally containing As O 20% ~ 40%, and sintered material arsenic-removing rate is greater than 80%.
4) step 2) be made into enter stove batching second half be pressed into agglomerate, and sinter with sintering oven and send into blast furnace reduction together with the agglomerate that formed and smelt, form blast-furnace cinder, thick alloy, a reductibility enrichment flue dust, a reductibility enrichment flue dust is generally containing As O 15% ~ 30%, and the arsenic-removing rate of blast furnace batching is greater than 90%.
5) by a reductibility enrichment flue dust of the once oxidation enrichment flue dust of above-mentioned sintering oven output and blast furnace output, a flue dust batching is carried out by wherein arsenic content equal proportion, its ratio containing arsenic also can carry out proportioning in the ratio of 0.2 ~ 0.8:0.8 ~ 0.2, but effect is good with equal proportion.
6) send into chain-arranged type or kiln type or shaft furnace formula distillation dearsenification stove after flue dust batching granulation step 5) obtained and carry out distillation dearsenification, output is containing As O 70% ~ 80%, the secondary enrichment flue dust of Pb<0.8%, Sb1% ~ 5% and distillation dearsenification residue.The arsenic-removing rate of distillation dearsenification generally can reach 70% ~ 80%, metal separation rate: Pb>98%, Sb>80%.
7) by the secondary enrichment flue dust of aforementioned output, (secondary enrichment flue dust comprises 5% ~ 20% lower-boiling impurity, as SnCl
4boiling point 115 DEG C, AsCl boiling point 130 DEG C, AlCl boiling point 180 DEG C, SbCl boiling point 223 DEG C) in temperature 200 ~ 230 DEG C of temperature sections, the low boilers in secondary enrichment flue dust is volatilized completely, and send synthetical recovery operation by the low boilers volatilized collection, reclaim valuable element; Then be warming up to 280 DEG C, a large amount of sublimation purification As O, continue about 120 minutes, continue to be warming up to 320 DEG C, continue sublimation purification As O, continue 30 ~ 60 minutes, then continue to be warming up to 380 DEG C, continue about 20 minutes, finally be warming up to 450 DEG C, continue about 20 minutes, wait until that smokeless rear sublimation purification process finishes, the pure white arsenic of output is sold as product, and the sublimation purification residue of output returns feed proportioning system together with the distillation dearsenification residue of step 6) output.Usually point temperature section sublimation purification so carried out is containing the secondary distillation enrichment flue dust of As O 70% ~ 80%, arsenic-removing rate can reach 80% ~ 85%, the As O grade obtained up to 96% ~ 99%, metal separation rate: Pb>99.5%, Sb>96%.
Being improved to further of such scheme, described step 6) can be: a flue dust batching is put into muffle furnace, and by distillation arsenic removing method secondary enrichment dearsenification, this distillation arsenic removing method is: first increase muffle furnace temperature to 280 DEG C, time length 120-150 minute, smolders until flue dust material loses; Then muffle furnace temperature to 320 DEG C, after 25-30 minute, waits to lose and smolders, adjust muffle furnace temperature to 380 DEG C again, after 25-30 minute, wait to lose and smolder, then adjust muffle furnace temperature to 450 DEG C again, after 25-30 minute, wait to lose and smolder, finally adjust muffle furnace temperature to 500 DEG C, after 30-35 minute, lose and smolder, namely complete.
In such scheme, described step 6) also can be: 110 DEG C of oven dry after shake granulation of being prepared burden by a flue dust, put into the insulating steel tube that bottom is equipped with leakproof screen cloth, by the dearsenification of hot blast distillation dearsenification program, hot blast distillation dearsenification program is: first hot blast is warming up to 280 DEG C, air quantity 500l/min scalar, 120 minutes time; Then, hot blast is warming up to 310 DEG C, keeps air quantity, 20 minutes time; Hot blast being warming up to 380 DEG C keeps air quantity constant again, 20 minutes time; Then hot blast is warming up to 450 DEG C, air quantity is constant, 15 minutes time; Finally hot blast is warming up to 500 DEG C, air quantity remains unchanged, and time 10-15 minute, loses and smolder, and namely completes dearsenification process.
The different grades accounting for total amount half are mixed to containing arsenic raw material high level matches with low level and are less than 10% containing As O amount by the present invention, and general 3% ~ 8% is good, is made into suitable slag type and is pressed into agglomerate, prepares to carry out reducing and smelting into blast furnace.Second half raw material high level matches with low level is less than 10% to arsenic content, general 2% ~ 5% is good, be made into suitable slag type, first enter the dearsenification of sintering oven sintering and become agglomerate (arsenic-removing rate is generally 65% ~ 90%), output containing the once oxidation enrichment flue dust of As O 25% ~ 30%, its valuable metal is plumbous, antimony equal size 5% ~ 50% not etc.Then aforementioned agglomerate is entered blast furnace and carries out reducing and smelting (arsenic-removing rate is generally 90% ~ 95%) together with pressure agglomerate, output is containing As O 18% ~ 40%, and valuable metal is plumbous, antimony equal size 15% ~ 50% reductibility enrichment flue dust not etc.Then, the once oxidation enrichment flue dust that the reductibility enrichment flue dust produced by aforementioned blast furnace and sintering oven produce, by its arsenic content equal proportion batching carry out distilling dearsenification output containing As O up to 70% ~ 80% secondary enrichment flue dust, after dearsenification, residue returns an enrichment system and uses (namely again as blast furnace and sintering oven raw material) again.Like this, the dearsenification carried out through blast furnace and sintering oven and the prepare burden combination of the secondary enrichment dearsenification carried out of flue dust is achieved and smelts high arsenic-removing rate containing arsenic raw material and high metal separation rate on a large scale.Finally, by above-mentioned secondary enrichment flue dust by a point temperature section sublimation purification white arsenic, reclaim lower boiling valuable metal on the one hand, made white arsenic grade bring up to more than 98% on the other hand, reach the relevant content standard of product, to have opened a way arsenic in product mode.
The inventive method is applicable to the industrial waste (comprise the raw material that contain arsenic waste material or title secondary resource that be rich in other valuable metal elements) of middle-low grade containing arsenic in the various source of large-scale recovery process; have very high comprehensive arsenic-removing rate and metal separation rate, be a kind of efficiently feasible systematicness, comprehensive processing method with regard to Fire arsenic removal.
Accompanying drawing explanation
Fig. 1 is the inventive method schema.
Embodiment
Embodiment 1: bulk cargo muffle furnace method
1. join SINTERING PRODUCTION materials, make wherein containing Pb+Sn+Bi30%, Fe10.5%, SiO 10%, CaO6.5%, As O 10%, weight is 100T siccative.Mixed through forklift heap, enter diameter 3.2m disc-type granulating machine after hammer crushing crusher machine, granulation diameter 3mm ~ 6mm.Enter 1.5m wide × the long chain-arranged type sintering dearsenification stove of 25m.After sintering dearsenification, produce agglomerate 60.5T, back powder 23.2T, once oxidation enrichment flue dust 16.2T, unknown loss 0.1T, agglomerate is identical with back powder composition.The agglomerate of output is smelted for the aftermentioned blast furnace reduction that enters, and back powder is then directly done again to sinter into sintering oven batching.
The chemical examination composition of output agglomerate and back powder:
Pb+Sb+Bi30.92%；As?O?4.2%；Fe12.5%；SiO?11.9%；CaO7.70%
Output sintering oven once oxidation enrichment flue dust composition:
Pb+Sn+Bi25.4%As?O?40.0%
2. join pressure agglomerate batching, make wherein containing Pb+Sn+Bi28%; Fe11.0%; SiO 10%; CaO6.2%; As O 10%, weight 60T.
3. by above-mentioned agglomerate 60.5T and pressure agglomerate material 60T, by 1:1 mass ratio batching, altogether 120.5T, drop into 5.6m2 blast furnace reduction and smelt.Because blast furnace volume is comparatively large, the new material dropped into wants time delay within 6 ~ 8 hours, just to start fusing smelting.By the production capacity of 5.6m2 blast furnace, 7 tons of material/hour calculating, the material of this crowd of 120.5T can continue smelting 17 hours, so within the 12nd hour after feeding intake, get first time flue dust sample 2Kg, second time sample 2Kg is got after 14th hour, get third time sample 2Kg after 16th hour, mix three sub-samplings, obtain blast furnace reductibility enrichment smoke sample 6Kg.
Output blast furnace reductibility enrichment flue dust composition is:
Pb+Sn+Bi40.15%As?O?31.2%
4. get above-mentioned sintering once oxidation enrichment flue dust 100g, get blast furnace reductibility enrichment flue dust 128.2g, batching mixes to obtain running sample, puts it in iron pan, controls bed thickness and is less than 6mm.
Sample average grade:
Pb+Sn+Bi33.6%As?O?35.06%
5. charging tray in bulk is put into muffle furnace, by distillation dearsenification program secondary enrichment dearsenification, obtains dearsenification alkaline residue 149.0g, the heavy 79.2g of secondary enrichment flue dust, actual collection weight 78.0g, loss 1.2g,
Chemical examination composition:
Dearsenification alkaline residue: Pb+Sn+Bi48.72%As O 13.4%
Secondary enrichment flue dust: Pb+Sn+Bi5.2%As O 76.0%
Wherein, this distillation dearsenification program is specially: first increase muffle furnace temperature to 280 DEG C, about 120 minutes time length, smolders until flue dust material loses; Then, after arsenic amount residual in high-arsenic dust pellet drops to 15-20%, then muffle furnace temperature to 320 DEG C, after 25 minutes, wait to lose and smolder, then adjust muffle furnace temperature to 380 DEG C, after 25 minutes, wait to lose and smolder, adjust muffle furnace temperature to 450 DEG C again again, after 25 minutes, wait to lose and smolder, finally adjust muffle furnace temperature to 500 DEG C, after 30 minutes, lose and smolder, namely complete.
get above-mentioned secondary enrichment flue dust 50g, spread in iron pan, bed thickness is less than 6mm, inserts in muffle furnace and first volatilizees completely by low boilers temperature 200 ~ 230 DEG C, then purify by above-mentioned distillation dearsenification program, obtain following product:
(1) lower boiling flue dust: bag collection weightening finish 8.95g, accounting 17.9%, actual collection low-boiling-point substance 7.0g, bodies lost weight 1.95g.
Chemical examination composition: As O 15%, all the other do not do detailed assay for low-boiling point material.
(2) high-purity arsenic trioxide flue dust, bag collection weightening finish 32.95g, accounting 65.9%, actual collection 30.5g loss amount 2.45g.
Chemical examination composition: As O 98.0%, Pb+Sb+Bi0.8%
(3) residual slag 8.1g, accounting 16.2%.
Chemical examination composition: As O 53%, Pb+Sb+Bi28.8%.
7. the residual slag that 6. dearsenification alkaline residue step 5. obtained and step obtain returns feed proportioning system recycling.
Embodiment 2: granulation shaft furnace process
1. join SINTERING PRODUCTION materials, make wherein containing Pb+Sn+Bi30%, Fe10.5%, SiO 10%, CaO6.5%, As O 10%, weight is 100T siccative.Mixed through forklift heap, enter diameter 3.2m disc-type granulating machine after hammer crushing crusher machine, granulation diameter 3mm ~ 6mm.Enter 1.5m wide × the long chain-arranged type sintering dearsenification stove of 25m.After sintering dearsenification, produce agglomerate 60.5T, back powder 23.2T, once oxidation enrichment flue dust 16.2T, unknown loss 0.1T, agglomerate is identical with back powder composition.The agglomerate of output is smelted for the aftermentioned blast furnace reduction that enters, and back powder is then directly done again to sinter into sintering oven batching.
The chemical examination composition of output agglomerate and back powder:
Pb+Sb+Bi30.92%；As?O?4.2%；Fe12.5%；SiO?11.9%；CaO7.70%
Output sintering oven once oxidation enrichment flue dust composition:
Pb+Sn+Bi25.4%As?O?40.0%
2. join pressure agglomerate batching, make wherein containing Pb+Sn+Bi28%; Fe11.0%; SiO 10%; CaO6.2%; As O 10%, weight 60T.
3. by above-mentioned agglomerate 60.5T and pressure agglomerate material 60T, by 1:1 mass ratio batching, altogether 120.5T, drop into 5.6m2 blast furnace reduction and smelt.Because blast furnace volume is comparatively large, the new material dropped into wants time delay within 6 ~ 8 hours, just to start fusing smelting.By the production capacity of 5.6m2 blast furnace, 7 tons of material/hour calculating, the material of this crowd of 120.5T can continue smelting 17 hours, so within the 12nd hour after feeding intake, get first time flue dust sample 2Kg, second time sample 2Kg is got after 14th hour, get third time sample 2Kg after 16th hour, mix three sub-samplings, obtain blast furnace reductibility enrichment smoke sample 6Kg.
Output blast furnace reductibility enrichment flue dust composition is:
Pb+Sn+Bi40.15%As?O?31.2%
4. get sintering dearsenification once oxidation enrichment flue dust 1500g, then get blast furnace and produce a reductibility enrichment flue dust 1500g, all mix.Add spray about 14% water, with manually shake granulation in dish, sift out diameter 3mm-8mm pellet 2560g.
5. the pellet sifted out is put into baking oven, dry 6 hours at 110 DEG C, obtain dry weight 2201.6g.
6. get the mixing pellet dry weight 2000g that 5. step obtains, put into the insulating steel tube that bottom is equipped with leakproof screen cloth diameter 100mm.Granulosa piling height 141mm.
7. press the dearsenification of hot blast distillation dearsenification program, obtain the heavy 691.78g of secondary enrichment flue dust, weight accounting 34.59%, actual collection 690.0g, weight loss 1.78g, chemical examination composition: As O 74.0%, Pb+Sb+Bi6.8%; Another secondary enrichment arsenic-removing rate 72.0%, obtains residue weight 1308.22g, weight accounting 65.41%, and chemical examination composition is: As O 15.2%, Pb+Sb+Bi46.4%.
Wherein this hot blast distillation dearsenification program is: first hot blast is warming up to 280 DEG C, air quantity 500l/min scalar, 120 minutes time; Then, after arsenic amount residual in high-arsenic dust pellet drops to 15-20%, hot blast is warming up to 310 DEG C, keeps air quantity, 20 minutes time; Hot blast being warming up to 380 DEG C keeps air quantity constant again, 20 minutes time; Then hot blast is warming up to 450 DEG C, air quantity is constant, 15 minutes time; Finally hot blast is warming up to 500 DEG C, air quantity remains unchanged, and after 10 minutes time, loses and smolders, and namely completes dearsenification process.
8. get above-mentioned secondary enrichment flue dust 650g, test-type pair roller pressing granula machine extrudes granulating, after sieving, obtain 610g diameter 6mm granulation material.Put into the insulating steel tube that bottom is equipped with leakproof screen cloth diameter 50mm, granulosa piling height 172mm.Then by above-mentioned hot blast distillation dearsenification program purification white arsenic, following product is obtained:
(1) low boilers: bag collection weightening finish 118.95g, accounting 19.5%, actual collection low-boiling-point substance 117.0g, bodies lost weight 1.95g.
Chemical examination composition: As O 10.25%, all the other do not do detailed assay for low-boiling point material.
(2) high-purity arsenic trioxide flue dust, bag collection weightening finish 391.12g, accounting 65.9%, actual collection 390g loss amount 1.12g.
Chemical examination composition: As O 98.1%, Pb+Sb+Bi0.6%
(3) residual slag 99.93g, accounting 16.38%.
Chemical examination composition: As O 55.56%, Pb+Sb+Bi39.15%.
9. the residual slag that 8. dearsenification alkaline residue step 7. obtained and step obtain returns feed proportioning system recycling.
Claims (6)
1. a method for associating dearsenification purification arsenic, is characterized in that comprising the steps:
1) classification of arsenic-containing smoke dust raw material, a point grade are deposited;
2) according to the different grade of valuable metal in various arsenic-containing smoke dust and required treatment capacity, various arsenic-containing smoke dust of arranging in pairs or groups is formed prepares burden into stove, make valuable metal grade Pb+Sn+Bi >=15%, iron calcium silicate slag type is mass ratio Fe:SiO: CaO=10 ~ 12:10:7 ~ 8, and containing arsenic grade 3% ~ 10%;
3) step 2) half entering stove batching that is made into sends into the dearsenification of sintering oven sintering, and form agglomerate and once oxidation enrichment flue dust, the once oxidation enrichment flue dust volatilized is containing As O 20% ~ 40%, and sintered material arsenic-removing rate is greater than 80%;
4) by step 2) stove that enters that is made into prepares burden that second half is pressed into agglomerate, and sinter with sintering oven and send into blast furnace reduction together with the agglomerate that formed and smelt, form blast-furnace cinder, thick alloy and a reductibility enrichment flue dust, a reductibility enrichment flue dust is containing As O 15% ~ 30%, and the arsenic-removing rate of blast furnace batching is greater than 90%;
5) by a reductibility enrichment flue dust of the once oxidation enrichment flue dust of above-mentioned sintering oven output and blast furnace output, a flue dust batching is carried out in wherein arsenic content ratio 0.2 ~ 0.8:0.8 ~ 0.2;
6) flue dust batching step 5) obtained is sent into chain-arranged type or kiln type or shaft furnace formula distillation dearsenification stove and is carried out distillation dearsenification, and output is containing As
2o
3the secondary enrichment flue dust of 70% ~ 80%, Pb<0.8%, Sb1% ~ 5% and distillation dearsenification residue;
7) low boilers is wherein volatilized in temperature 200 ~ 230 DEG C of temperature sections by the secondary enrichment flue dust of aforementioned output completely, and send synthetical recovery operation by the low boilers volatilized collection, reclaim valuable element; Then be warming up to 280 DEG C, a large amount of sublimation purification As O, continue 120 minutes, continue to be warming up to 320 DEG C, continue sublimation purification As O, continue 30 ~ 60 minutes, then continue to be warming up to 380 DEG C, continue 20 minutes, finally be warming up to 450 DEG C, continue 20 minutes, wait until that smokeless rear sublimation purification process finishes, the pure white arsenic of output is sold as product, and the sublimation purification residue of output returns feed proportioning system and recycles together with the distillation dearsenification residue of step 6) output.
2. the method for a kind of associating dearsenification purification arsenic according to claim 1, it is characterized in that, by a reductibility enrichment flue dust of the once oxidation enrichment flue dust of sintering oven output and blast furnace output in step 6), carry out a flue dust batching by wherein arsenic content equal proportion.
3. the method for a kind of associating dearsenification purification arsenic according to claim 1, is characterized in that, described step 2) in iron calcium silicate slag type be mass ratio Fe:SiO: CaO=10 ~ 12:10:7 ~ 8.
4. the method for a kind of associating dearsenification purification arsenic according to claim 1, it is characterized in that, described step 6) is: a flue dust batching is put into muffle furnace, by distillation arsenic removing method secondary enrichment dearsenification, this distillation arsenic removing method is: first increase muffle furnace temperature to 280 DEG C, time length 120-150 minute, smolders until flue dust material loses; Then muffle furnace temperature to 320 DEG C, after 25-30 minute, waits to lose and smolders, adjust muffle furnace temperature to 380 DEG C again, after 25-30 minute, wait to lose and smolder, then adjust muffle furnace temperature to 450 DEG C again, after 25-30 minute, wait to lose and smolder, finally adjust muffle furnace temperature to 500 DEG C, after 30-35 minute, lose and smolder, namely complete.
5. the method for a kind of associating dearsenification purification arsenic according to claim 1, it is characterized in that, described step 6) is: 110 DEG C of oven dry after shake granulation of being prepared burden by a flue dust, put into the insulating steel tube that bottom is equipped with leakproof screen cloth, by the dearsenification of hot blast distillation dearsenification program, hot blast distillation dearsenification program is: first hot blast is warming up to 280 DEG C, air quantity 500l/min scalar, 120 minutes time; Then, hot blast is warming up to 310 DEG C, keeps air quantity, 20 minutes time; Hot blast being warming up to 380 DEG C keeps air quantity constant again, 20 minutes time; Then hot blast is warming up to 450 DEG C, air quantity is constant, 15 minutes time; Finally hot blast is warming up to 500 DEG C, air quantity remains unchanged, and time 10-15 minute, loses and smolder, and namely completes dearsenification process.
6. the method for a kind of associating dearsenification purification arsenic according to claim 1, it is characterized in that, by step 2 in described step 4)) stove that enters that is made into prepares burden that second half is pressed into agglomerate, and with sintering oven sinter the agglomerate formed prepare burden by 1:1 mass ratio after together with send into blast furnace reduction and smelt.
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