CN115354155A - System and method for microwave dearsenification of arsenic-containing material - Google Patents
System and method for microwave dearsenification of arsenic-containing material Download PDFInfo
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- CN115354155A CN115354155A CN202210808780.7A CN202210808780A CN115354155A CN 115354155 A CN115354155 A CN 115354155A CN 202210808780 A CN202210808780 A CN 202210808780A CN 115354155 A CN115354155 A CN 115354155A
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 198
- 239000000463 material Substances 0.000 title claims abstract description 144
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000003245 coal Substances 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000012805 post-processing Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 50
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 43
- 239000003546 flue gas Substances 0.000 claims description 43
- 239000010949 copper Substances 0.000 claims description 40
- 239000000428 dust Substances 0.000 claims description 37
- 230000008569 process Effects 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 19
- 229960002594 arsenic trioxide Drugs 0.000 claims description 16
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 238000002386 leaching Methods 0.000 claims description 13
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000002817 coal dust Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000003077 lignite Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 229910000967 As alloy Inorganic materials 0.000 abstract description 10
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 abstract description 9
- 229940000489 arsenate Drugs 0.000 abstract description 7
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003068 static effect Effects 0.000 abstract description 4
- 239000011133 lead Substances 0.000 description 33
- 239000004744 fabric Substances 0.000 description 32
- 229910052802 copper Inorganic materials 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 230000001276 controlling effect Effects 0.000 description 16
- 239000012071 phase Substances 0.000 description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 12
- 235000011941 Tilia x europaea Nutrition 0.000 description 12
- 239000004571 lime Substances 0.000 description 12
- 239000008267 milk Substances 0.000 description 12
- 210000004080 milk Anatomy 0.000 description 12
- 235000013336 milk Nutrition 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000002184 metal Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 238000003723 Smelting Methods 0.000 description 8
- 239000000779 smoke Substances 0.000 description 8
- 238000007664 blowing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910000413 arsenic oxide Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 238000000265 homogenisation Methods 0.000 description 5
- 238000004137 mechanical activation Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- 230000007480 spreading Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 1
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 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
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- C22B7/001—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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a system and a method for microwave dearsenification of an arsenic-containing material, wherein the system for microwave dearsenification of the arsenic-containing material comprises the following steps: comprises a drying device, a feeding device, a microwave generator and a post-processing device which are communicated in sequence; the feeding device comprises a feeding machine and a ball mill; the post-treatment device comprises cooling equipment and a tail gas treatment device; and the inlet and the outlet of the cooling equipment are respectively communicated with the microwave generator and the tail gas treatment device. According to the invention, a small amount of coal powder is added according to the content of arsenate and arsenic alloy in the material, arsenic in the arsenate and arsenic alloy can be reduced into metallic arsenic, and then weak oxidation is assisted, so that in order to solve the problem of nonuniform local heating caused by inconsistent wave absorbing characteristics of the material, the problem of uniform heating of the material is realized by adopting the working procedures of material pretreatment, material granularity control and material mixing, the temperature can be better controlled, and the efficient static dearsenification by microwaves is realized.
Description
Technical Field
The invention belongs to the field of non-ferrous smelting arsenic-containing solid waste resource utilization, and particularly relates to a system and a method for microwave dearsenification of arsenic-containing materials.
Background
Arsenic is a main associated element in non-ferrous metal minerals, and the amount of arsenic brought into a non-ferrous smelting system in China is as much as one hundred thousand tons every year. Generally, the arsenic-containing materials produced by non-ferrous metallurgy mainly comprise: 1) White smoke dust, black copper powder, arsenic sulfide slag and the like produced by the copper smelting system; 2) Lead electrolysis anode mud, secondary zinc oxide smoke dust, lead matte converting smoke dust and the like produced by the lead-zinc smelting system; 3) Liquated slag and rare slag produced by a tin smelting system, roasting smoke dust and the like of the liquated slag and the rare slag; 4) Arsenic caustic sludge produced by an antimony smelting system and the like.
The main forms of arsenic include oxides (III, V) of arsenic, arsenates, arsenic alloys, arsenic sulfide, and the like. Besides arsenic element, the arsenic-containing materials contain a large amount of valuable metals such as lead, zinc, copper, cadmium, antimony, bismuth, gold, silver and the like, and have extremely high recovery value. At present, the methods for treating the arsenic-containing materials mainly comprise pyrogenic roasting dearsenification and wet leaching dearsenification, wherein the wet dearsenification mostly adopts water leaching, acid leaching and alkaline leaching, and the related arsenic removal methods comprise a precipitation method, an adsorption method, extraction, an ion exchange method, a biological method and the like. The wet leaching has the advantages of large or small scale, flexible product scheme and the like, but also has the problems of great loss of valuable metals in the dearsenification process, dispersion of arsenic trend, possibility of generating arsine in the process and the like. The arsenic removal by the fire method is mostly carried out by the roasting method, the equipment used for industrialization is usually a rotary kiln, and the main heat source is electricity, carbon or natural gas. After the roasting process of the roasted material to be dearsenified, arsenic in the material and the material carried by machinery enter smoke dust, so that the arsenic is difficult to be effectively separated from valuable metals in the roasted material.
The microwave is a special electromagnetic wave, the material is directly heated by the energy dissipation of the microwave in the material, the temperature rise is fast, no heat source gas is generated in the process, the process is clean and environment-friendly, and the smoke dust is mainly arsenic oxide and has low impurity content because the process is relatively static and the volatilized smoke gas has less mechanical entrainment.
The prior art CN103230660A discloses a green smelting method for rapidly removing arsenic from arsenic-containing tailing sand. The technology is that the arsenic-containing tailing sand is put into a closed high-temperature-resistant nonmetal container and is placed in a microwave oven chamber, the temperature is controlled to be 230-490 ℃, but in order to improve the microwave absorption efficiency, when materials with weak wave absorption, such as iron-free materials, need to be added with a large amount of wave absorbing agents.
The prior art CN103710532A discloses a method for removing arsenic from high arsenic iron ore by microwave, which comprises the following main procedures: 1) Crushing the high-arsenic iron ore until the granularity is less than 1mm; 2) Adding a proper amount of coal powder; 3) Uniformly mixing and placing in an industrial microwave oven for microwave roasting, controlling the temperature at 800-1200 ℃, and roasting for 5-30 min. But the added coal powder is as high as 5 to 10 percent, and the adding amount is large; the temperature controlled by microwave is very high, and the energy consumption is too high.
Disclosure of Invention
The invention aims to provide a system and a method for low-temperature microwave dearsenification of an arsenic-containing material, which have low energy consumption and uniform heating.
In order to solve the problems, the technical scheme of the invention is as follows:
a system for removing arsenic from arsenic-containing materials by microwave comprises a drying device, a feeding device, a microwave generator and a post-processing device which are sequentially communicated;
the feeding device comprises a feeding machine and a ball mill;
the post-treatment device comprises cooling equipment and a tail gas treatment device;
and the inlet and the outlet of the cooling equipment are respectively communicated with the microwave generator and the tail gas treatment device.
Preferably, the feeding device is any one of a disk feeder, a vibrating feeder, a trough feeder and a pendulum feeder.
Preferably, the feeder is a disk feeder.
The disc feeder mainly comprises a driving device, a feeder body, a belt conveyor for metering and a metering device, is particularly suitable for feeding arsenic-containing powder and coal powder, and is stable in material feeding and easy for accurate weighing and feeding in the process.
Preferably, the temperature reduction device comprises a settling chamber.
The temperature of the flue gas discharged from the microwave oven is relatively low, and if the flue gas is cooled by directly mixing air or spraying water, the temperature of the flue gas is too fast, so that the flue gas is not beneficial to trapping white arsenic smoke dust.
On one hand, the settling chamber has the function of cooling the flue gas by using the cavity and collecting dust in a subsequent cloth bag. On the other hand, partial white arsenic can be deposited to reduce the subsequent dust collection load of the cloth bag, so that the recovery rate of the white arsenic is improved.
Preferably, the tail gas treatment device comprises a bag-type dust collector, a leaching tower and a chimney which are sequentially communicated; the inlet of the bag-type dust collector is communicated with the settling chamber, and the outlet of the bag-type dust collector is communicated with the leaching tower.
The method comprises the steps of removing moisture in the arsenic-containing material through a drying device, then sending the dried material and a carbonaceous reducing agent into a ball mill through a feeder to perform homogenization and mechanical activation of the material, controlling microwave power in a microwave generator to perform dearsenification, cooling flue gas produced by microwave dearsenification through a settling chamber, collecting dust through a cloth bag, and discharging the obtained tail gas through a chimney after the obtained tail gas enters a leaching tower to be purified.
According to the same inventive concept, the invention also provides a method for performing microwave dearsenification on arsenic-containing materials by adopting the system, which comprises the following steps:
a method for microwave dearsenification of arsenic-containing materials comprises the following steps:
(1) Drying the arsenic-containing material, mixing the arsenic-containing material with a carbonaceous reducing agent, and grinding to obtain a mixture;
(2) Sequentially performing microwave dearsenification and oxidation dearsenification on the mixture to obtain white arsenic and dearsenified flue gas; treating the arsenic-removed flue gas and then discharging;
the arsenic-containing material is black copper powder, lead anode mud or a mixture thereof; the black copper powder contains 15-30% of As, and the lead anode mud contains 5-15% of As.
Preferably, the black copper powder comprises As in parts by weight 2 O 3 (s) 20-30 parts of As 2 O 5 (s) 1-5 parts, cu 3 (AsO 4 ) 2 3-10 parts of Cu 3 3-10 parts of As(s), pb 3 (AsO 4 ) 2 1-5 parts of Cu, 40-60 parts of Cu, 1-10 parts of CuO and Bi 2 O 3 1-10 parts of Sb 2 O 3 1-10 parts.
Preferably, the lead anode mud comprises As in parts by weight 2 O 3 (s) 1-5 parts of As 2 O 5 (s) 1-5 parts, cu 3 (AsO 4 ) 2 0.1-5 parts of Cu 3 2-10 parts of As(s), pb 3 (AsO 4 ) 2 20-50 parts of Pb, 10-30 parts of CuO 2-10 parts of Bi 2 O 3 1-15 parts of Sb 2 O 3 10 to 30 portions of Pb x As y 5-20 parts.
The black copper powder and the lead anode mud mainly comprise copper, arsenic, lead, arsenic, copper and bismuth. Wherein the main phase of arsenic has As 2 O 3 (s)、As 2 O 5 (s)、Cu 3 As(s)、Pb x As y (s)、Cu 3 (AsO 4 ) 2 And Pb 3 (AsO 4 ) 2 And (4) forming.
As in the black copper powder is mainly arsenic copper alloy, namely Cu 3 As(s)，Cu 3 (AsO 4 ) 2 And As 2 O 3 (s) and As 2 O 5 (s) is present. As in lead anode slime, mainly Pb x As y (s)、Pb 3 (AsO 4 ) 2 And As 2 O 3 (s) and As 2 O 5 (s) is present. The occurrence of As is significantly different compared to the prior art. Therefore, the reaction principle of adding carbon is also different, and in addition to meeting the requirement of volatilization of arsenic oxide, cu is required to be added 3 As(s)，Cu 3 (AsO 4 ) 2 And Pb x As y (s)、Pb 3 (AsO 4 ) 2 As in the arsenic is in a solid phase in a simple substance arsenic form, and an arsenic oxide precise control technology is innovatively utilized, namely, the arsenic is volatilized and then enters a gas phase to be cooled at the rear end and is collected by a dust collecting system by being assisted with a weak oxidizing atmosphere, so that the technical effect of efficiently removing arsenic is realized.
Preferably, the carbonaceous reducing agent is one or more of coal powder, charcoal, lignite and graphite.
Preferably, the carbonaceous reducing agent is coal dust.
The carbonaceous reducing agent can reduce arsenic in arsenate and arsenic alloy into metallic arsenic, and the coal powder has the advantages of low price and moderate reducing capability.
Preferably, the proportion of the mixture with the particle size of 10-50 mu m in the mixture is more than 98%.
The grain size of the mixture with more than 98 percent is between 10 and 50 mu m, and under the grain size distribution, the arsenic-containing material of the invention is fully mixed, the material components are uniform, the wave absorption property is uniform, the local heating temperature rise is uniform, and the arsenic removal efficiency is obviously improved.
Through multiple tests, the inventor finds that the arsenic-containing material provided by the invention has insufficient homogenization of material components and local overheating and local supercooling due to the wave absorbing specificity of the material, and if the granularity of the material is controlled to be larger than the range.
If the granularity of the material is controlled to be smaller than the range, the dissociation of all phases in the material is too sufficient, but the wave absorption properties are obviously different, the temperature of the substance with strong wave absorption properties is preferentially increased, the temperature of the substance with weak wave absorption properties is lower, the reaction is insufficient, and the removal of arsenic is not facilitated.
Preferably, the addition amount of the coal dust is 0.5-3% of the mass of the material.
The content of arsenic alloy and arsenate in the material can influence the addition amount of carbonaceous reducing agent-coal powder.
In the invention, the addition amount of the coal dust can be controlled in such a low range, and at such a low temperature, the homogenizing and activating procedures of the carbonaceous reducing agent and the arsenic-containing material are added, so that the materials are contacted more uniformly and reacted more fully, the reaction temperature is further reduced, and the technical effect of energy conservation is achieved.
Preferably, the technological parameters of microwave dearsenification are as follows: regulating the microwave power to 3000W-20 kW, raising the temperature for 2-6 min, keeping the microwave temperature at 340-450 ℃, removing arsenic by microwave for 3-60 min, and introducing inert gas in the arsenic removing process.
Preferably, the inert gas is argon or nitrogen.
The technological parameters of microwave dearsenization are closely related to the characteristics of the materials. Under the power, temperature and time, the arsenic-containing material can reduce most of arsenic into metallic arsenic and accelerate the volatilization process of arsenic, thereby improving the efficiency of arsenic removal.
If the microwave heating temperature is lower than the range, the reduction of the temperature weakens the arsenic reduction and arsenic volatilization reaction processes, and the arsenic removal rate is lower.
On the contrary, if the microwave temperature rise is obviously higher than the range, the temperature rise is favorable for arsenic reduction and arsenic volatilization reaction processes, but due to the temperature rise and the rise of the flue gas temperature, part of As is still used As after the flue gas temperature is cooled and cooled 4 O 6 (g) The gas phase exists and therefore the arsenic capture rate will be significantly reduced.
Preferably, the technological parameters of the oxidation dearsenification are as follows: and introducing oxidizing gas to react for 3-60 min for oxidation dearsenification.
The purpose of the oxidation dearsenification is to weakly oxidize the reduced metallic arsenic into gaseous As 4 O 6 (g) Thereby performing arsenic removal.
Preferably, the oxidizing gas is oxygen or a mixture of ozone and an inert gas in a volume ratio of 1 to 3.
Preferably, the flow rate of the oxidizing gas is 10 to 100L/(min kg).
In the present invention, the reduced arsenic metal must be effectively treated only by a weak oxidation to obtain gaseous arsenic oxide.
The oxidizing power of the mixture is too weak to oxidize the arsenic simple substance obtained by reducing the coal powder into As 4 O 6 (g) Entering the gas phase, the arsenic removal efficiency is reduced.
If the oxidizing power of the mixed gas is too strong, part of As is oxidized to As 2 O 5 (s), which cannot be volatilized into the gas phase, also results in a decrease in the efficiency of arsenic removal.
Meanwhile, the flow of the weak oxidizing gas is controlled, the oxidizing atmosphere and the proper oxidizing degree are controlled, and the arsenic removal efficiency is improved. The oxidation state and the dearsenification efficiency of the metal arsenic can be obviously influenced by the over-large or over-small flow of the weak oxidizing gas. In the present invention, the optimum arsenic removal efficiency can be obtained only by controlling the flow rate within this range. Preferably, the arsenic-removed flue gas is directly discharged after being cooled, dust-collected and leached.
The main component of tail gas obtained by treating arsenic-removed flue gas is N 2 /Ar、CO 2 And H 2 O，Meets the requirement of environmental protection and can be directly discharged.
Preferably, the material after arsenic removal can be used as a raw material for valuable metal recovery and can enter a zinc recovery system, a lead recovery system and a copper recovery system.
The invention is further explained below:
the arsenic-containing material in the invention is arsenic-containing solid waste in the smelting process, and the occurrence form and arsenic removal characteristics of arsenic are as follows:
in the present invention, the form of arsenic is mainly arsenic alloy, i.e., cu 3 As(s)、Pb x As y (s), and arsenate and arsenic oxide compositions. One part of the arsenic oxide is volatilized at low temperature, and the other part is supplemented with a carbonaceous reducing agent to ensure that Cu is evaporated 3 As(s)，Cu 3 (AsO 4 ) 2 And Pb x As y (s)、Pb 3 (AsO 4 ) 2 As in the arsenic alloy exists in a solid phase in the form of simple substance arsenic, and the part of arsenic is volatilized through weak oxidizing atmosphere and then enters a gas phase to be captured by a rear-end cooling and dust collecting system, so that the technical effect of efficiently removing arsenic is realized. Compared with the prior art, the invention has higher dearsenization efficiency by simply volatilizing oxides at low temperature, and simultaneously, compared with the prior art, by volatilizing simple substance arsenic at high temperature, the invention not only saves energy, but also has better dearsenization efficiency.
According to the invention, a proper amount of pulverized coal is added, and the arsenic-containing material and the pulverized coal are fully reacted through a fine grinding process, so that the components among particles of the arsenic-containing material are uniform, the uniform temperature rise is realized, the arsenic-removing efficiency is improved by synchronously heating to a set temperature.
The main reaction principle of the invention is as follows:
2As 2 O 3 (s)＝As 4 O 6 (g) (1)
2As 2 O 5 (s)+2C(s)＝As 4 O 6 (g)+2CO 2 (g) (2)
Cu 3 As(s)+C(s)+O 2 (g)＝Cu(s)+As(s)+CO 2 (3)
2Cu 3 (AsO 4 ) 2 +2C(s)＝6CuO+As 4 O 6 (g)+2CO 2 (g) (4)
Pb x As y (s)+C(s)+O 2 (g)＝xPb(s)+yAs(s)+CO 2 (5)
2Pb 3 (AsO 4 ) 2 +2C(s)＝6PbO+As 4 O 6 (g)+2CO 2 (g) (6)
4As(s)+3O 2 (g)＝As 4 O 6 (g) (7)
4As(s)+5O 2 (g)＝2As 2 O 5 (s) (8)
As 4 O 6 (g)＝2As 2 O 3 (s) (9)
the invention mixes a small amount of coal powder according to the content of arsenate and arsenic alloy in the material, can reduce arsenic in arsenate and arsenic alloy into metallic arsenic, and then generates gaseous As by weak oxidation 4 O 6 (g) Removing arsenic, and then collecting white arsenic products through a cooling process.
In order to solve the problem that local heating is not uniform due to inconsistent wave-absorbing characteristics of materials, the invention realizes uniform heating of the materials by adopting the working procedures of material pretreatment, material granularity control and material mixing, can better control the temperature and realizes high-efficiency static dearsenification of microwaves.
The invention has the beneficial technical effects that:
(1) The invention adopts a microwave dearsenification method and a microwave dearsenification system to realize the separation and recovery of arsenic and valuable metals in arsenic-containing materials. Microwave dearsenification process, heating acts on the material body, and energy utilization is high, and the process is clean environmental protection, except that As volatilizees, few machinery is mingled with, for this reason, white arsenic (As) of retrieving 2 O 3 ) The purity of the product is more than 95%. The arsenic removal rate of the material after arsenic removal reaches over 95 percent, and the material after arsenic removal can be used as a raw material and sent to a metal recovery system to recover valuable metals.
(2) In order to solve the problem of nonuniform local heating caused by inconsistent wave-absorbing characteristics of materials, the invention realizes the uniform heating of the materials by adopting the working procedures of material pretreatment, material granularity control and material uniform mixing, can better control the temperature and realize the high-efficiency static dearsenification of microwaves.
(3) The invention is suitable for treating single arsenic-containing material and can also treat a plurality of mixed materials containing arsenic simultaneously. Aiming at arsenic-containing materials which do not contain iron and have weak wave absorption, no wave absorption agent needs to be added, the dosage of the carbonaceous reducing agent is small, and the method is energy-saving and environment-friendly. The microwave dearsenification time is short, the arsenic removal rate is high, the white arsenic purity is high, and valuable metals are basically not lost. The invention organically integrates the procedures of fine grinding, dearsenization, tail gas treatment and the like, and realizes the purpose of efficiently removing arsenic from arsenic-containing materials.
Therefore, the method has the advantages of short reaction time, high arsenic removal rate, low dosage of the carbonaceous reducing agent, no wave absorbing agent addition, low microwave temperature, clean operation, environmental friendliness, high safety and great industrial application prospect.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic connection diagram of the microwave dearsenification system of the present invention.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1
As shown in figure 2, the system for removing arsenic from arsenic-containing materials by microwave comprises a drying kiln, a disc feeder, a ball mill, a microwave generator, a settling chamber, a bag-type dust remover, a leaching tower and a chimney which are sequentially communicated.
On one hand, the settling chamber has the function of cooling the flue gas by using the cavity and collecting dust in a subsequent cloth bag. On the other hand, partial white arsenic can be deposited to reduce the subsequent dust collecting load of a cloth bag, so that the method is more favorable for improving the recovery rate of the white arsenic.
The inlet of the bag-type dust collector is communicated with the settling chamber, and the outlet of the bag-type dust collector is communicated with the leaching tower.
The arsenic-containing material is dried in a kiln to remove water in the material, so that the material contains almost no water. And then, the dried material and the coal powder are sent into a ball mill through a disc feeder to be homogenized and mechanically activated, the microwave power is controlled in a microwave generator to carry out dearsenization, flue gas produced by microwave dearsenization is cooled by a settling chamber and is subjected to dust collection by a bag-type dust collector, and the obtained tail gas enters a leaching tower to be purified and is exhausted through a chimney.
The arsenic-containing materials in the examples and comparative examples of the present invention were black copper powder and lead anode slime, and the compositions thereof are shown in table 1. Is a high arsenic material, wherein the arsenic exists in the forms of oxides, arsenic alloys and arsenates.
TABLE 1 composition of arsenic-containing materials
Example 2
According to the flow shown in figure 1, 1000g of black copper powder is dried by blowing at 100 ℃ for 8h, then 2% of coal powder is added, and the discharged material is controlled to have the particle size of 10-50 microns by adopting the ball mill for homogenization and mechanical activation. And then flatly spreading the fine black copper powder into a tray in a microwave generator, controlling the microwave power to be 10kW, raising the temperature for 5min, keeping the temperature of the materials at 400 ℃, and performing microwave dearsenification for a period of 10min, wherein Ar protection is introduced in the process. Then, the power output is stopped and V (O) is introduced 2 ): v (Ar) =1, mixed gas flow rate 50L/min, reaction 10min. The flue gas generated by microwave dearsenification is cooled by a settling chamber and is subjected to dust collection by a cloth bag, and the arsenic concentration of the flue gas is 5mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has the purity of 95.3 percent and the arsenic trapping rate of 99.9 percent. The arsenic content of the material after microwave arsenic removal is 0.98%, and the arsenic removal rate reaches 96.2%. And (5) feeding the material subjected to arsenic removal into a copper system to recover copper.
Comparative example 1
1000g of black copper powder is dried for 8 hours by blowing at 100 ℃, then 2 percent of coal powder is added, and then the materials are homogenized by a ball mill and mechanically activated, and the grain diameter of the discharged materials is controlled to be more than 85 microns. And then flatly paving the fine black copper powder into a tray in a microwave generator, controlling the microwave power to be 10kW, raising the temperature for 5min, carrying out unbalanced material temperature, and detecting by a thermocouple to locally reach 500 ℃ and partially reach 200 ℃. And (3) performing microwave dearsenization for 10min, and introducing Ar for protection in the process. Subsequently, the power output is stopped and V (O) is introduced 2 ): v (Ar) =1, mixed gas flow 50L/min, reaction 10min. The flue gas generated by microwave dearsenification is cooled by a settling chamber and is subjected to dust collection by a cloth bag, and the arsenic concentration of the flue gas is 5mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has the purity of 93.4 percent and the arsenic trapping rate of 99.9 percent. The arsenic content of the material after microwave arsenic removal is 9.08 percent, and the arsenic removal rate reaches 64.6 percent. And (5) feeding the material subjected to arsenic removal into a copper system to recover copper.
Compared with the example 2, the arsenic-containing material has the advantages that the granularity of the material is controlled to be larger than the range in the homogenizing and mechanical activation procedures, so that the homogenization of the material components is insufficient, the local overheating and local undercooling are caused, the reactions (1) to (4) are not completely carried out, and the arsenic removal effect is obviously weaker than that of the example 2.
Comparative example 2
1000g of black copper powder is dried for 8 hours by blowing at 100 ℃, then 2 percent of coal powder is added, and then the materials are homogenized and mechanically activated by a ball mill, and the grain size of the discharged materials is controlled to be less than 10 mu m. And then flatly paving the fine black copper powder into a tray in a microwave generator, controlling the microwave power to be 10kW, raising the temperature for 5min, carrying out unbalanced material temperature, and detecting by a thermocouple until the local temperature reaches 600 ℃ and the partial temperature reaches 180 ℃. And (3) performing microwave dearsenization for 10min, and introducing Ar for protection in the process. Subsequently, the power output is stopped and V (O) is introduced 2 ): v (Ar) =1, mixed gas flow 50L/min, reaction 10min. Cooling the flue gas produced by microwave dearsenification by a settling chamber and collecting dust by a cloth bag, wherein the arsenic concentration of the flue gas is 5mg/m 3 . And tail gas enters lime milk, is sprayed and purified and is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has the purity of 96.2 percent and the arsenic trapping rate of 99.9 percent. The arsenic content of the material after microwave arsenic removal is 8.48 percent, and the arsenic removal rate reaches 66.9 percent. And (5) feeding the material subjected to arsenic removal into a copper system to recover copper.
Compared with the example 2, the arsenic-containing material has the advantages that the granularity of the material is controlled to be smaller than the range in the homogenizing and mechanical activation procedures, so that all the phases in the material are fully dissociated, the wave absorption is obviously different, the temperature of the material with strong wave absorption is preferentially increased, but the temperature of the material with weak wave absorption is lower at the moment, the reaction is insufficient, the removal of arsenic is not facilitated, and the arsenic removal effect is obviously weaker than that of the example 2.
Comparative example 3
1000g of black copper powder is dried for 8 hours by blowing at 100 ℃, then 2 percent of coal powder is added, and the mixture is homogenized and mechanically activated by a ball mill, and the grain diameter of the discharged material is controlled to be 10-50 mu m. And then, flatly paving the fine black copper powder into a tray in a microwave generator, controlling the microwave power to be 10kW, raising the temperature for 5min, and controlling the material temperature to be 270 ℃, wherein the phenomenon that the fluctuation range is large and the control is difficult can occur when the temperature controlled by the microwave generator is lower than 300 ℃. The time of microwave dearsenification is 10min, and Ar protection is applied in the process. Subsequently, the power output is stopped and V (O) is introduced 2 ): v (Ar) =1, mixed gas flow 50L/min, reaction 10min. Cooling the flue gas produced by microwave dearsenification by a settling chamber and collecting dust by a cloth bag, wherein the arsenic concentration of the flue gas is 5mg/m 3 ，SO 2 The concentration is 23mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has purity up to 95.4% and arsenic trapping rate 99.9%. The arsenic content of the material after microwave arsenic removal is 6.36%, and the arsenic removal rate reaches 75.2%. And (5) feeding the material subjected to arsenic removal into a copper system to recover copper.
In this comparative example, the microwave heating temperature was significantly lower, and the arsenic reduction and arsenic volatilization reaction processes were weakened due to the temperature decrease, so the arsenic removal rate was lower than that in example 2.
Comparative example 4
Blast drying 1000g of black copper powder at 100 deg.C for 8h, adding 2% coal powder, homogenizing with ball mill, mechanically activating, and controlling particle size10-50 μm. And then flatly paving the fine black copper powder into a tray in a microwave generator, controlling the microwave power to be 10kW, raising the temperature for 5min, and keeping the material temperature at 620 ℃. And (3) performing microwave dearsenization for 10min, and introducing Ar for protection in the process. Then, the power output is stopped and V (O) is introduced 2 ): v (Ar) =1, mixed gas flow 50L/min, reaction 10min. Cooling the flue gas produced by microwave dearsenization by a settling chamber, collecting dust by a cloth bag, and burning the tail gas by an ignition device to obtain the flue gas with arsenic concentration of 50mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has purity up to 95.4% and arsenic trapping rate 75%. The arsenic content of the material after microwave arsenic removal is 1.28%, and the arsenic removal rate reaches 95%. And (5) feeding the material subjected to arsenic removal into a copper system to recover copper.
In this comparative example, the microwave heating temperature was significantly higher. The temperature rise is beneficial to the reduction of arsenic and the volatilization reaction process of arsenic, but the arsenic content of the material after the arsenic removal of the comparative example is slightly increased, and in addition, the temperature rise of the flue gas causes that after the temperature reduction and cooling process of the flue gas, part of As is still As 4 O 6 (g) The gas phase was present and therefore the arsenic capture rate was significantly lower than in example 2.
Comparative example 5
1000g of black copper powder is blown and dried for 8 hours at the temperature of 100 ℃, then 2 percent of coal powder is added, and then a ball mill is adopted for homogenization and mechanical activation, and the grain size of discharged materials is controlled to be 10-50 mu m. And then flatly spreading the fine black copper powder into a tray in a microwave generator, controlling the microwave power to be 10kW, raising the temperature for 5min, keeping the temperature of the material at 400 ℃, performing microwave dearsenization for a period of time to be 10min, and introducing Ar for protection in the process. Subsequently, the power output is stopped and V (O) is introduced 2 ): v (Ar) =1, mixed gas flow rate 50L/min, reaction 10min. Cooling the flue gas produced by microwave dearsenification by a settling chamber and collecting dust by a cloth bag, wherein the arsenic concentration of the flue gas is 5mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has the purity of 95.3 percent and the arsenic trapping rate of 99.9 percent. The material after microwave dearsenization contains 5% of arsenic, and the dearsenization rate reaches 80.5% at this time. Feeding the arsenic-removed material to copperAnd (5) recovering copper in the system.
Compared with example 2, the volume ratio of oxygen to nitrogen is lower than the range, which results in too weak oxidizing ability of the weak oxidizing atmosphere and insufficient reoxidation of the elemental arsenic obtained by reducing the pulverized coal to As 4 O 6 (g) Into the gas phase, thereby reducing the arsenic removal efficiency.
Comparative example 6
1000g of black copper powder is dried for 8 hours by blowing at 100 ℃, then 2 percent of coal powder is added, and the mixture is homogenized and mechanically activated by a ball mill, and the grain diameter of the discharged material is controlled to be 10-50 mu m. And then flatly spreading the fine black copper powder into a tray in a microwave generator, controlling the microwave power to be 10kW, raising the temperature for 5min, keeping the temperature of the materials at 400 ℃, and performing microwave dearsenification for a period of 10min, wherein Ar protection is introduced in the process. Then, the power output is stopped and V (O) is introduced 2 ): v (Ar) =1 mixed gas, mixed gas flow 50L/min, reaction 10min. Cooling the flue gas produced by microwave dearsenification by a settling chamber and collecting dust by a cloth bag, wherein the arsenic concentration of the flue gas is 5mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has purity up to 95.3% and arsenic trapping rate 99.9%. The arsenic content of the material after microwave arsenic removal is 5.67%, and the arsenic removal rate reaches 77.9%. And (5) feeding the material subjected to arsenic removal into a copper system to recover copper.
In this comparative example, the volume ratio of oxygen to nitrogen is higher than the range in comparison with example 2, so that the oxidizing ability of the weakly oxidizing atmosphere is too strong and part of As is peroxidized to As 2 O 5 (s), which cannot be volatilized into a gas phase, leads to a decrease in the efficiency of arsenic removal.
Comparative example 7
1000g of black copper powder is dried for 8 hours by blowing at 100 ℃, then 2 percent of coal powder is added, and the mixture is homogenized and mechanically activated by a ball mill, and the grain diameter of the discharged material is controlled to be 10-50 mu m. And then flatly spreading the fine black copper powder into a tray in a microwave generator, controlling the microwave power to be 10kW, raising the temperature for 5min, keeping the temperature of the material at 400 ℃, performing microwave dearsenization for a period of time to be 10min, and introducing Ar for protection in the process. Subsequently, the power output is stopped and V (O) is introduced 2 ): v (Ar) =1, mixed gas flow 2L/min, reaction 10min. Cigarette produced by microwave dearsenicationCooling the gas in a settling chamber, collecting dust in a cloth bag, and obtaining the arsenic concentration of the flue gas of 5mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has purity up to 95.2% and arsenic trapping rate up to 99.9%. The arsenic content of the material after microwave arsenic removal is 2.88 percent, and the arsenic removal rate reaches 88.7 percent. And (5) feeding the material subjected to arsenic removal into a copper system to recover copper.
The flow rate of the mixed gas of this comparative example is lower than the range of the example, so that the oxidizing ability is weakened and thus the volatilization rate of arsenic is reduced lower than that of example 2.
Comparative example 8
1000g of black copper powder is dried for 8 hours by blowing at 100 ℃, then 2 percent of coal powder is added, and the mixture is homogenized and mechanically activated by a ball mill, and the grain diameter of the discharged material is controlled to be 10-50 mu m. And then flatly spreading the fine black copper powder into a tray in a microwave generator, controlling the microwave power to be 10kW, raising the temperature for 5min, keeping the temperature of the materials at 400 ℃, and performing microwave dearsenification for a period of 10min, wherein Ar protection is introduced in the process. Subsequently, the power output is stopped and V (O) is introduced 2 ): v (Ar) =1, mixed gas flow 120L/min, reaction 10min. Cooling the flue gas produced by microwave dearsenification by a settling chamber and collecting dust by a cloth bag, wherein the arsenic concentration of the flue gas is 5mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has purity up to 95.3% and arsenic trapping rate 99.9%. The arsenic content of the material after microwave arsenic removal is 0.97%, and the arsenic removal rate reaches 96.3%. And (5) feeding the material subjected to arsenic removal into a copper system to recover copper.
This comparative example has a higher flow rate of the mixed gas than the example, so that the oxidation capacity is enhanced, and arsenic cannot be overoxidized to arsenic pentoxide due to the limitation of the mixed gas ratio, so that the arsenic volatilization rate is still higher and slightly higher than that of example 2.
Example 3
1000g of lead anode mud is dried for 12 hours by air blast at 80 ℃, then 3 percent of coal powder is added, and the materials are homogenized and mechanically activated by a ball mill, and the grain diameter of the discharged materials is controlled to be 10-50 mu m. Then, the fine lead anode slime powder is fed into a microwave generator, the microwave power is controlled to be 15kW, the temperature rise time is 5min, and the temperature is kept at 3 DEGRemoving arsenic for 50min at 50 deg.C by microwave, introducing N during arsenic removal process 2 And (4) protecting. Then, the power output is stopped and V (O) is introduced 3 )：V(N 2 ) Mixed gas of =1 and 5, mixed gas 50L/min, and reaction time 20min. Cooling the flue gas produced by microwave dearsenification by a settling chamber and collecting dust by a cloth bag, wherein the arsenic concentration of the flue gas is 5mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has the purity of 95.6 percent and the cloth bag trapping rate of 99.9 percent. The arsenic content of the material after microwave arsenic removal is 0.59 percent, and the arsenic removal rate reaches 95.2 percent. And (5) feeding the material subjected to arsenic removal to a lead bismuth recovery system.
Comparative example 9
1000g of lead anode mud is dried for 12 hours by air blast at 80 ℃, then 3 percent of coal powder is added, and the materials are homogenized and mechanically activated by a ball mill, and the grain diameter of the discharged materials is controlled to be 10-50 mu m. Then feeding the lead anode mud fine powder into a microwave generator, controlling the microwave power to be 15kW, raising the temperature for 5min, keeping the temperature at 260 ℃ for 50min for microwave dearsenization, and introducing N in the dearsenization process 2 And (4) protecting. Then, the power output is stopped and V (O) is introduced 3 )：V(N 2 ) Mixed gas of =1 and 5, mixed gas 50L/min, and reaction time 20min. Cooling the flue gas produced by microwave dearsenification by a settling chamber and collecting dust by a cloth bag, wherein the arsenic concentration of the flue gas is 5mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The product has the purity of 95.7 percent and the cloth bag trapping rate of 99.9 percent. The arsenic content of the material after microwave arsenic removal is 2.18 percent, and the arsenic removal rate reaches 82.3 percent. And (4) feeding the material subjected to arsenic removal into a lead bismuth recovery system.
This comparative example, compared to example 3, where the temperature for microwave dearsenification was below the range, the dearsenification efficiency was reduced because the temperature reduction decreased the arsenic reduction process.
Comparative example 10
1000g of lead anode mud is dried for 12 hours by air blast at 80 ℃, then 3 percent of coal powder is added, and the materials are homogenized and mechanically activated by a ball mill, and the grain diameter of the discharged materials is controlled to be 10-50 mu m. Then feeding the fine powder of the lead anode mud into a microwave generator, controlling the microwave power to be 15kW, raising the temperature for 5min, keeping the temperature to be 550 ℃, and performing microwave dearsenification for a period of timeIn 50min, dearsenization process is performed by introducing N 2 And (4) protecting. Subsequently, the power output is stopped and V (O) is introduced 3 )：V(N 2 ) Mixed gas of =1 and 5, mixed gas 50L/min, and reaction time 20min. Cooling the flue gas produced by microwave dearsenification by a settling chamber and collecting dust by a cloth bag, wherein the arsenic concentration of the flue gas is 30mg/m 3 . And tail gas enters lime milk to be sprayed and purified and then is exhausted through a chimney. As recovered from settling chamber and cloth bag 2 O 3 The purity of the product reaches 95.2 percent, and the cloth bag trapping rate reaches 82 percent. The arsenic content of the material after microwave arsenic removal is 6.66%, and the arsenic removal rate reaches 45.8%. And (4) feeding the material subjected to arsenic removal into a lead bismuth recovery system.
Compared with the example 3, the temperature of the first stage of microwave dearsenification is higher than the range, the arsenic reduction process can be enhanced due to the temperature rise, but the coal powder can reduce lead to generate metallic lead, the melting point of the metallic lead is low, the metallic lead is in a liquid state at the temperature, the material is partially melted, the arsenic is difficult to volatilize into a gas phase, and the dearsenification efficiency is further reduced. In addition, as the microwave temperature rises, the flue gas temperature also rises, so that after the flue gas temperature is cooled, part of As is still As 4 O 6 (g) The gas phase was present and therefore the arsenic capture rate was significantly lower than in example 3.
The above description is only for the preferred embodiment of the present invention, and the embodiment of the present invention should not be construed as limited to the above description, and any other embodiments that can be derived by those skilled in the art without departing from the technical scope of the present invention should be included in the present invention.
Claims (10)
1. A system for microwave dearsenification of arsenic-containing materials is characterized by comprising: comprises a drying device, a feeding device, a microwave generator and a post-processing device which are communicated in sequence;
the feeding device comprises a feeding machine and a ball mill;
the post-treatment device comprises cooling equipment and a tail gas treatment device;
and the inlet and the outlet of the cooling equipment are respectively communicated with the microwave generator and the tail gas treatment device.
2. The system of claim 1, wherein the temperature reduction device comprises a settling chamber.
3. The system according to claim 1, wherein the tail gas treatment device comprises a bag-type dust remover, a leaching tower and a chimney which are communicated in sequence; the inlet of the bag-type dust collector is communicated with the settling chamber, and the outlet of the bag-type dust collector is communicated with the leaching tower.
4. A method for microwave dearsenification of an arsenic bearing material using the system of any of claims 1-3, comprising the steps of:
(1) Drying the arsenic-containing material, mixing the arsenic-containing material with a carbonaceous reducing agent, and grinding to obtain a mixture;
(2) Sequentially performing microwave dearsenification and oxidation dearsenification on the mixture to obtain white arsenic and dearsenified flue gas; treating the arsenic-removed flue gas and then discharging;
the arsenic-containing material is black copper powder, lead anode mud or a mixture thereof; the black copper powder contains 15-30% of As, and the lead anode mud contains 5-15% of As.
5. The method of claim 4, wherein the black copper powder comprises As in parts by weight 2 O 3 (s) 20-30 parts of As 2 O 5 (s) 1-5 parts, cu 3 (AsO 4 ) 2 3-10 parts of Cu 3 3-10 portions of As(s) and Pb 3 (AsO 4 ) 2 1-5 parts of Cu, 40-60 parts of Cu, 1-10 parts of CuO and Bi 2 O 3 1 to 10 portions of Sb 2 O 3 1-10 parts; preferably, the lead anode slime comprises As in parts by weight 2 O 3 (s) 1-5 parts of As 2 O 5 (s) 1-5 parts of Cu 3 (AsO 4 ) 2 0.1-5 parts of Cu 3 2-10 parts of As(s), pb 3 (AsO 4 ) 2 20-50 parts of Pb, 10-30 parts of CuO 2-10 parts of Bi 2 O 3 1-15 parts of Sb 2 O 3 10 to 30 portions of Pb x As y 5-20 parts.
6. The method according to claim 4, wherein the carbonaceous reducing agent is one or more of coal powder, charcoal, lignite and graphite; preferably, the carbonaceous reducing agent is coal dust.
7. The method according to claim 4, wherein the proportion of the mixture with the grain size of 10-50 μm in the mixture is more than 98%.
8. The method according to claim 4, characterized in that the carbonaceous reducing agent is added in an amount of 0.5-3% by mass of the material.
9. The method according to claim 4, wherein the process parameters of microwave dearsenification are as follows: regulating the microwave power to 3000W-20 kW, raising the temperature for 2-6 min, keeping the microwave temperature at 340-450 ℃, removing arsenic for 3-60 min by microwave, and introducing inert gas in the arsenic removal process.
10. The method according to claim 4, wherein the process parameters for oxidative dearsenification are: introducing oxidizing gas to react for 3-60 min for oxidation dearsenification; preferably, the oxidizing gas is oxygen or a mixture of ozone and an inert gas in a volume ratio of 1 to 3.
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| US20080069746A1 (en) * | 2006-09-20 | 2008-03-20 | Hw Advanced Technologies, Inc. | Method and apparatus for microwave induced pyrolysis of arsenical ores and ore concentrates |
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| US20080069746A1 (en) * | 2006-09-20 | 2008-03-20 | Hw Advanced Technologies, Inc. | Method and apparatus for microwave induced pyrolysis of arsenical ores and ore concentrates |
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