CN109364659A - The purification of thallium and recovery method and device in a kind of flue gas during smelting - Google Patents
The purification of thallium and recovery method and device in a kind of flue gas during smelting Download PDFInfo
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- CN109364659A CN109364659A CN201811284857.5A CN201811284857A CN109364659A CN 109364659 A CN109364659 A CN 109364659A CN 201811284857 A CN201811284857 A CN 201811284857A CN 109364659 A CN109364659 A CN 109364659A
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- thallium
- flue gas
- pond
- catalyst
- active carbon
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- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 94
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 53
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003546 flue gas Substances 0.000 title claims abstract description 45
- 238000003723 Smelting Methods 0.000 title claims abstract description 20
- 238000000746 purification Methods 0.000 title claims abstract description 15
- 238000011084 recovery Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000007789 gas Substances 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 29
- 239000000428 dust Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000010521 absorption reaction Methods 0.000 claims description 40
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- 125000004122 cyclic group Chemical group 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 25
- 238000003795 desorption Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000012716 precipitator Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910018957 MClx Inorganic materials 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910008649 Tl2O3 Inorganic materials 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000003011 anion exchange membrane Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- QTQRFJQXXUPYDI-UHFFFAOYSA-N oxo(oxothallanyloxy)thallane Chemical compound O=[Tl]O[Tl]=O QTQRFJQXXUPYDI-UHFFFAOYSA-N 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract 1
- 231100000086 high toxicity Toxicity 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- 238000013508 migration Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000004094 preconcentration Methods 0.000 abstract 1
- 238000010301 surface-oxidation reaction Methods 0.000 abstract 1
- 229910003438 thallium oxide Inorganic materials 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009825 accumulation Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 239000012717 electrostatic precipitator Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000010903 husk Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling 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
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 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
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
- B01D47/02—Separating dispersed particles from gases, air or vapours by liquid as separating agent by passing the gas or air or vapour over or through a liquid bath
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/88—Handling or mounting catalysts
-
- 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
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
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- B01D2255/204—Alkaline earth metals
- B01D2255/2045—Calcium
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- B01D2255/00—Catalysts
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- B01D2255/2047—Magnesium
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Abstract
The invention discloses a kind of purification of thallium in flue gas during smelting and recovery methods and device, belong to atmosphere pollution technical field.The present invention adsorbs thallous compound hypertoxic in simultaneously catalysis oxidation flue gas during smelting using activated carbon supported metal chloride as catalyst；Flue gas during smelting after dust removal process, it is passed through the fixed bed reactors equipped with catalyst, by catalyst trap and in catalyst surface oxidation reaction occurs for the thallous compound in gas, wherein heavy metal thallium is by high toxicity, the monovalence compound of high migration is changed into the thallium oxide for being easier to remove, and is attached to catalyst surface；Catalyst after the reaction was completed is electrolysed after overpickling, thallium can be recycled, and medicine preparation, the preparation of electronic equipments original part, optical component preparation are used for.Present invention process is simple, easy to operate, and removing recycling thallium is high-efficient, at low cost, and energy Preconcentration of Thallium realizes the purification and recycling of thallium in flue gas, is suitable for industrial applications and popularization.
Description
Technical field
The present invention relates to a kind of purification of thallium in flue gas during smelting and recovery methods and device, belong to atmosphere pollution technology neck
Domain.
Background technique
Thallium is typical hypertoxic heavy metal element, to the toxicity of organism considerably beyond mercury, lead, cadmium, adult lethal agent
Amount is 12mg/kg, and as typical distributed element, thallium is not individually at mine, mainly in a variety of gold such as lead, zinc, arsenic, copper, antimony, mercury
In the mineral deposits such as category, coal be enriched with, formed associated mineral, and with Tl(I in high-temperature calcination process) form be released, institute
With lead-zinc smelting, the industries such as Copper making are the emphasis that thallium pollution is administered.
In coal containing thallium and the combustion process of ore containing thallium: most thalliums are by Tl(I) enter in the form of halogen compounds
Meteorology, small part is by Tl(III) and thallium element in the form of be dispersed in tail gas and slag.Tl(III) can pass through with the thallium of particulate form
Dedusting, wet scrubbing or dry adsorbent injection method removal, and Tl(I) due to its low melting point, high equilibrium vapour pressure and
It is water-soluble and in an atmosphere mean residence time be up to the several years, easily formed extensively by long range Atmospheric Transportation in an atmosphere
Thallium pollution be further enriched in vivo with food chain and as rainfall dustfall enters water body.Various countries and area are
Prevention and treatment thallium pollution is put into effect and is performed and its stringent standard: putting into effect discharge standard of air pollutants such as Shanghai City and requires
Flue gas thallium content is lower than 0.2mg/m3。
Thallium in flue gas has the characteristics that content is few and toxicity is very big, electrostatic precipitator (ESP) in traditional industrial process
The particulate matter in flue gas can effectively be trapped, but since only about 8% thallium is attached in flue dust, and Tl(I) partial size is minimum
Easily, so ESP (being lower than 7%) very low to its removal efficiency；Bag filter FF) there is uniqueness to other heavy metal removal performances
Effect, but thallium removal efficiency is also extremely low.And wet desulfurization system (WFGD) is to Tl(I not soluble in water) capture effect is unobvious,
To Tl(III) can removal efficiency it is low (be lower than 30%).According to the data of International Energy Agency, the average fire coal per ton of China contains thallium about
100g, an annual output other zinc smelting factory of 10 10,000 tons discharge more than 40 tons thalliums every year and enter atmosphere.Selective catalytic oxidation method
Using the boiling characteristics and Tl(I of thallium) medium reproducibility selectively and is efficiently oxidized and is converted into more stable Tl
(III) the catalysis oxidation efficiency reduces the activity of thallium up to 90% or more (this technique), and then effectively removes, and reaches deep purifying and incites somebody to action
The purpose of thallium resource utilization in exhaust gas.
Currently, there is no can be with economical and efficient, and environmental friendly regenerated smelts cigarette containing thallium in flue gas in the Controlling research of gaseous state thallium
Gas disposal method.Patent CN101255502 discloses the comprehensive recycling process and device of a kind of meteorological thallium, using sulfuric acid leaching,
The units operation such as extraction, back extraction, displacement, thallium is cemented out.But the complex technical process, solution absorption is repeatedly introduced, is set
It changes, the methods of extraction is with high costs, and is only applicable to lead smelting industry, Difficulty.Patent application CN106929683A is disclosed
The device of thallium is taken off for flue gas, mainly includes flue gas scrubber, multilevel circulating cleaning equipment, lye conditioning tank, filter press, guarantor
Pacify filter, reverse osmosis membrane apparatus, ion exchange column, photoelectrocatalysidevice device, clear water collecting box, solid-liquid point is carried out using filter press
From finally successively by cartridge filter, reverse osmosis membrane apparatus, ion exchange column and photoelectrocatalysidevice device multiple purifying, purification
It is high-efficient, wherein purified water serves as cleaning solution by clear water collecting box in being back to lye conditioning tank, realizes online resource
It utilizes.But this method fails to convert Tl(III for Tl(I)), and thallium is introduced into liquid phase, it is be easy to cause secondary pollution, no
Thallium can be recycled, the waste of resource is caused.
In recent years, with the continuous development of electronic technology, thallium is in semicon industry, pharmacy, space flight, military affairs etc. demand
It is increasing, a kind of purification tail gas containing thallium is researched and developed, and the technique for recycling thallium then becomes more and more important.Difficulty is removed in exhaust gas thallium
Greatly, demand is urgent and correlative study lacks under the situation of blank out, and the present invention can be efficient, safe and economically removes in exhaust gas
Thallium, and the recycling for completing thallium can bring huge economic interests to enterprise and society, have great promotional value.
Summary of the invention
It is an object of the invention to a kind of purification of thallium in flue gas during smelting and recovery method, the method for the invention is reaching
Environmental requirement while reducing energy and material loss, and has saved economic cost, specifically includes the following steps:
(1) flue gas containing thallium cools down by heat exchanger, through cyclone dust collectors, electric precipitator dedusting, subsequently into containing dilute acid soln
Cyclic absorption pond further remove foreign gas and soluble compound, removed by demister and dehumidifier contained in gas
Steam obtain pretreatment flue gas containing thallium；
(2) MCl will be usedxModified active carbon is put into packed tower as catalyst, at normal temperatures and pressures, is passed through pretreatment containing thallium
Flue gas makes Tl(I in flue gas containing thallium) transformation to Tl(III), flue gas is discharged through subsequent processing, to reach the mesh that flue gas removes thallium
's；
The MClxFor FeCl3、CuCl2、ZnCl2、CoCl2、MnCl2、MgCl2、CaCl2It is middle a kind of or arbitrarily ratio several；
(3) catalyst surface after adsorption reaction generates Tl2O3, by the catalyst soak after absorption in desorption liquid, desorption
Liquid is the HNO that mass percent concentration is 1-5%3With the mixed solution for the HCl that mass percent concentration is 1-5%, desorption is completed
It is afterwards 10-25kHz in frequency, the ultrasonic sound intensity is 100-250W/m-2Under conditions of be ultrasonically treated 0.5-2 hours；
(4) step (3) acquired solution is placed in electrolytic cell circular chamber, and circular chamber and cathode chamber are separated with cation-exchange membrane,
Circular chamber and anode chamber are separated with anion-exchange membrane, and anode chamber is packed into 1-5%NAOH solution, and cathode uses stainless steel plate, anode
Using insoluble electrode；Control voltage is that 1-5V is electrolysed afterwards；Thallium is slowly precipitated in cathode, and collection is placed on baking oven 40-80
It is DEG C dry and weigh, it is protected from light and seals up for safekeeping.
Preferably, MCl of the present inventionxModified method for preparation of active carbon is as follows:
(1) weigh the active carbon that commercially available partial size is 20 ~ 120 mesh, it is washing, dry, then flow be 100mL/min ~
Under the inert gas shielding of 300mL/min, microwave modification 3min ~ 15min obtains pretreated active carbon；
(2) by MClxIt is dissolved in deionized water and is configured to MClxSolution, wherein MClxSolution concentration is the mol/ of 0.1mol/L ~ 0.3
L；
(3) active carbon is put into MCl in the ratio that solid-liquid volume ratio is 1:1 ~ 1:5xIn solution, sonication treatment time is that 1-2 is small
When, it is stirred continuously in treatment process；
(4) 3 ~ 5h is roasted under the conditions of 200 ~ 500 DEG C in Muffle furnace after drying the Immesion active carbon that step (3) processing obtains
Obtain MClxModified active carbon.
Preferably, the time of desorption process is 8-20 hours in step (2) of the present invention.
Active carbon of the present invention can select coal quality, in bamboo or coconut husk preparing active carbon any one or it is several
Mixing.
Another object of the present invention is to provide the purification of thallium in the flue gas during smelting and recovery method equipment therefors, including
Including heat exchanger 2, cyclone dust collectors 3, electric precipitator 4, cyclic absorption pond I 5, cyclic absorption pond II 6, demister 7, dehumidifier 8,
Packed tower I 9, packed tower II 10, circulation parsing pond I 11, circulation parsing pond II 12, electrolytic cell I 13, electrolytic cell II 14, metallurgical furnace
1, heat exchanger 2, cyclone dust collectors 3, electric precipitator 4 are sequentially communicated, electric precipitator 4 respectively with cyclic absorption pond I 5, cyclic absorption
Pond II 6 is connected to, and cyclic absorption pond I 5, cyclic absorption pond II 6 are connected to after converging with demister 7, and demister 7 is connected to dehumidifier 8,
Dehumidifier 8 is connected to packed tower I 9, packed tower II 10 respectively, packed tower I 9, packed tower II 10 discharge gate converge after respectively and
Circulation parsing pond I 11, circulation parsing pond II 12 be connected to, circulation parsing pond I 11, circulation parsing pond II 12 converge after respectively with electrolysis
Pond I 13, electrolytic cell II 14 are connected to, and valve is equipped between two containers.
The principle of the present invention
In the above process, related main chemical reactions are as follows:
4TlCl+2MnO2+O2=2MnCl2+2Tl2O3 (1)
4TlCl+2CuO+2O2=2CuCl2+2Tl2O3 (2)
4TlCl+2ZnO+2O2=2ZnCl2+2Tl2O3 (3)
4TlCl+2CoO+2O2=2CoCl2+2Tl2O3 (4)
4TlCl+2MgO+2O2=2MgCl2+2Tl2O3 (5)
4TlCl+2CaO+2O2=2CaCl2+2Tl2O3 (6)
The present invention is based on above-mentioned principle and proposes, by microwave, to impregnate modification using metal chloride modified activated carbon,
Improve the apparent structure and gap structure of active carbon, increases the type for being conducive to the chemical functional group of thallium absorption on activated carbon surface
And quantity, active carbon is significantly increased to the adsorption capacity of thallium, is reached efficiently, safety, and the thallium in flue gas is economically removed.Then exist
Under ultrasound condition, the modified activated carbon of adsorption saturation is desorbed in acid desorption liquid, thallium is transferred to desorption in the form of ion
In liquid；Finally by the method for electrolysis, simple substance thallium is obtained.
Beneficial effects of the present invention:
The present invention can efficiently and rapidly remove thallium (the 0.05 μ g/ of thallium-containing quantity < in the tail gas after removing in industrial smelting exhaust
M3)；And the thallium being adsorbed can be recycled, the final simple substance thallium (purity >=99.99%) for obtaining high-purity, can sell or
It uses；While removing thallium, solid and liquid are recycled during realizing, and prevent secondary pollution.
Detailed description of the invention
Fig. 1 is the figure of technological process for flue gas purification containing thallium.
In figure: 1- metallurgical furnace；2- heat exchanger；3- cyclone dust collectors；4- electric precipitator；5- cyclic absorption pond I；6- circulation is inhaled
Receives pond II；7- demister；8- dehumidifier；9- packed tower I；10- packed tower II；11- circulation parsing pond I；12- circulation parsing pond
Ⅱ；13- electrolytic cell I；14- electrolytic cell II.
Specific embodiment
The present invention is described further below by specific embodiment, is carried out under premised on inventive technique scheme real
It applies, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following embodiments.
Equipment therefor of the embodiment of the present invention includes metallurgical furnace 1, heat exchanger 2, cyclone dust collectors 3, electric precipitator 4, circulation suction
Receives pond I 5, cyclic absorption pond II 6, demister 7, dehumidifier 8, packed tower I 9, packed tower II 10, circulation parsing pond I 11, circulant solution
Pond II 12, electrolytic cell I 13, electrolytic cell II 14 are analysed, metallurgical furnace 1, heat exchanger 2, cyclone dust collectors 3, electric precipitator 4 are sequentially communicated,
Electric precipitator 4 is connected to cyclic absorption pond I 5, cyclic absorption pond II 6 respectively, and cyclic absorption pond I 5, cyclic absorption pond II 6 are converged
It is connected to afterwards with demister 7, demister 7 is connected to dehumidifier 8, and dehumidifier 8 is connected to packed tower I 9, packed tower II 10 respectively, is filled out
Material tower I 9, packed tower II 10 discharge gate converge after respectively with circulation parsing pond I 11, circulation parsing pond II 12 be connected to, circulant solution
Analysis pond I 11, circulation parsing pond II 12 are connected to electrolytic cell I 13, electrolytic cell II 14 respectively after converging.
Detailed process are as follows: tail gas is generated from metallurgical furnace 1, is cooled down by heat exchanger 2, through cyclone dust collectors 3, electric precipitator
4 dedustings, subsequently into the dilute acid soln in cyclic absorption pond I 5, II 6 pond of cyclic absorption pond being 5% or so, tail gas passes through demister
7 with dehumidifier 8 it is dry after enter packed tower I 9 and packed tower II 10, be then discharged；Cyclic absorption pond I 5 and cyclic absorption pond
After solution in II 6 absorbs saturation, it is transferred to circulation parsing pond I 11, recycles parsing pond II 12, after the completion of desorption, will contain
The solution of thallium is passed into electrolytic cell I 13 and middle electrolytic cell II 14, obtains pure thallium simple substance in cathode, and the catalyst after desorption can be with
It is refilled with, reuses.
Embodiment 1
(1) preparation of modified active carbon catalyst: it is crushed dry coaly activated carbon, sieving, choosing partial size is about that 30 purposes are standby
With；It is that 30 DEG C of deionized waters wash 5 removal dusts with temperature, is put into baking oven and is dried 12 hours at 80 DEG C, weigh 20.00g
Active carbon is put into the microwave reactor of 500W, the microwave modification 15min in the case where flow is the nitrogen protection of 100mL/min, activity
Charcoal preprocessing process is completed；
Weigh the MnCl of 2.102g2Solid sample pours into beaker, after suitable distilled water is added, with glass bar stir to
MnCl3After solid is completely dissolved, which is made to the MnCl of 0.1mol/L into the volumetric flask of 100mL3It is spare；It weighs
10g, 30 mesh sieving microwave-modified activated-carbon, is put into prepared MnCl by the solid-liquid volume ratio of 1:13In solution, and use magnetic force
Blender stirs 26h, and supersonic frequency 28kH, ultrasonic sound intensity 300W/m is arranged-2 Processing sample 1 hour under ultrasonic conditions, very
Air filter removes clear liquid, and the solid matter filtered out is put into 100 DEG C of baking ovens and dries 12h, then roasts 3h at 500 DEG C of Muffle furnace,
After being cooled to room temperature, obtains modified coaly activated carbon and take off thallium adsorbent；
(2) flue gas during smelting treatment process:
Tail gas is generated from metallurgical furnace 1, is cooled to by heat exchanger 2 lower than 100 degrees Celsius, through cyclone dust collectors 3, electric precipitator
Dust and partial impurities compound in 99% flue gas are got rid of in 4 dedustings, are prevented it from entering follow up device, are made catalyst poisoning；
Subsequently into being 4% to obtain sulfuric acid solution in cyclic absorption pond I 5, II pond 6(of cyclic absorption pond), further remove foreign gas and
Soluble compound；Tail gas removes steam contained in gas by demister 7 and dehumidifier 8, prevents water from entering packed tower；So
Gas is passed through packed tower I 9 afterwards and packed tower II 10 is handled, and gaseous state thallium is oxidized or adsorbent is to adsorbent surface, after purification
Tail gas direct emission；Catalyst after reaction is passed into circulation parsing pond I 11, circulation parses in pond II 12, circulation parsing
(desorption liquid 3%HNO in pond3Mixed with 3%HCl), desorption process 9 hours, subsequent 10kHz, ultrasonic sound intensity 120W/m-2Condition
Lower ultrasonic treatment 1.5 hours；Solution is transferred to electrolytic cell I 13 and middle electrolytic cell II 14, the anode of electrolytic cell after absorbing saturation
Room is packed into 2%NaOH solution, and cathode uses stainless steel plate, and anode uses insoluble electrode；Control voltage is that 2V is electrolysed afterwards；
Thallium is slowly precipitated in cathode, and collection is placed on 40 DEG C of dryings of baking oven and weighs, and is protected from light and seals up for safekeeping；Catalyst after desorption can be again
Filling, recycling.
Test result is as follows: when using modified coaly activated carbon absorption flue gas thallium, the accumulation thallium of the active carbon of unit mass
Penetrating adsorbance is 0.53g/kg；In entire removal process, accumulation recycling simple substance thallium 1.62kg, the rate of recovery 91.70%；The catalysis
Agent shows well under the conditions of complicated gas component；The anti-toxicity of the catalyst, resistance to reduction and leach resistance are very high, no
Only stable in catalytic performance, and it is long using the time.
Embodiment 2
(1) preparation of modified active carbon catalyst: it is crushed dry coaly activated carbon, sieving, choosing partial size is about that 20 purposes are standby
With；It is that 30 DEG C of deionized waters wash 3 removal dusts with temperature, is put into baking oven and is dried 6 hours at 80 DEG C, it is living to weigh 20.00g
Property charcoal be put into the microwave reactor of 700W, the microwave modification 3min in the case where flow is the nitrogen protection of 100mL/min, active carbon is pre-
Treatment process is completed；
The zinc chloride solid sample for weighing 2.0445g, is poured into beaker, after suitable distilled water is added, with glass bar stir to
After zinc chloride solid is completely dissolved, it is spare which is made to 0.1mol/L liquor zinci chloridi into the volumetric flask of 100mL；
10g is weighed, 60 mesh sieving active carbon is put into prepared liquor zinci chloridi, and use magnetic agitation by the solid-liquid volume ratio of 1:1
Device stirs for 24 hours, and supersonic frequency 28kH, ultrasonic sound intensity 300W/m is arranged-2 It handles sample 1 hour under ultrasonic conditions, vacuum filter
Clear liquid is removed, the solid matter filtered out is put into 100 DEG C of baking ovens and dries 5h, 3h is roasted at 200 DEG C of Muffle furnace, is cooled to room temperature
Afterwards, it obtains modified coaly activated carbon and takes off thallium adsorbent.
(2) flue gas during smelting treatment process: tail gas is generated from metallurgical furnace 1, is cooled to by heat exchanger 2 Celsius lower than 100
Degree, through cyclone dust collectors 3,4 dedusting of electric precipitator, get rid of the dust and partial impurities compound in 99% flue gas, prevent its into
Enter follow up device, makes catalyst poisoning；It is molten subsequently into sulfuric acid is obtained in cyclic absorption pond I 5, II pond 6(of cyclic absorption pond for 4%
Liquid), further remove foreign gas and soluble compound；Tail gas is removed contained in gas by demister 7 and dehumidifier 8
Steam prevents water from entering packed tower；Then gas is passed through packed tower I 9 and packed tower II 10 is handled, and gaseous state thallium is oxidized or inhales
Attached dose is arrived adsorbent surface, purified tail gas direct emission；Catalyst after reaction is passed into circulation parsing pond I 11, is followed
Ring parses in pond II 12, (the desorption liquid 1%HNO in circulation parsing pond3Mixed with 1%HCl), desorption process 8 hours, then
10kHz, ultrasonic sound intensity 100W/m-2Under the conditions of be ultrasonically treated 0.5 hour；Solution is transferred to I 13 He of electrolytic cell after absorbing saturation
Middle electrolytic cell II 14, the anode chamber of electrolytic cell are packed into 1%NaOH solution, and cathode uses stainless steel plate, and anode uses insoluble electricity
Pole；Control voltage is that 1V is electrolysed afterwards；Thallium is slowly precipitated in cathode, and collection is placed on 40 DEG C of dryings of baking oven and weighs, and is protected from light
It seals up for safekeeping；Catalyst after desorption can be refilled with, recycling.
Test result is as follows: when using modified coaly activated carbon absorption flue gas thallium, the accumulation thallium of the active carbon of unit mass
Penetrating adsorbance is 0.23 g/kg；In entire removal process, accumulation recycling simple substance thallium 0.72kg, the rate of recovery 93.91%.The catalysis
Agent shows well under the conditions of complicated gas component；The anti-toxicity of the catalyst, resistance to reduction and leach resistance are very high, no
Only stable in catalytic performance, and it is long using the time.
Embodiment 3
(1) preparation of modified active carbon catalyst: being crushed dry coaly activated carbon, and the powder that partial size is about 120 mesh is chosen in sieving
End is spare；It is that 60 DEG C of deionized waters wash 4 removal dusts with temperature, is put into baking oven and is dried 9 hours at 100 DEG C, weighed
20.00g active carbon is put into the microwave reactor of 900W, the microwave modification 8min in the case where flow is the nitrogen protection of 200mL/min,
Activated Carbon Pretreatment process is completed；
The copper chloride solid sample for weighing 3.4096g, is poured into beaker, after suitable distilled water is added, with glass bar stir to
After copper chloride solid is completely dissolved, it is spare which is obtained to 0.2mol/L copper chloride solution into the volumetric flask of 100mL.Claim
10g is taken, 120 mesh sieving active carbon is put into prepared copper chloride solution, and use magnetic agitation by the solid-liquid volume ratio of 1:3
Device stirs 27h, and supersonic frequency 25kH, ultrasonic sound intensity 270W/m is arranged-2 Sample 40min, vacuum filter are handled under ultrasonic conditions
Clear liquid is removed, the solid matter filtered out is put into 110 DEG C of baking ovens and is dried, 4h is roasted at 300 DEG C of Muffle furnace, is cooled to room temperature
Afterwards, it obtains modified coaly activated carbon and takes off thallium adsorbent.
(2) flue gas during smelting treatment process: tail gas is generated from metallurgical furnace 1, is cooled to by heat exchanger 2 Celsius lower than 100
Degree, through cyclone dust collectors 3,4 dedusting of electric precipitator, get rid of the dust and partial impurities compound in 99% flue gas, prevent its into
Enter follow up device, makes catalyst poisoning；It is molten subsequently into sulfuric acid is obtained in cyclic absorption pond I 5, II pond 6(of cyclic absorption pond for 4%
Liquid), further remove foreign gas and soluble compound；Tail gas is removed contained in gas by demister 7 and dehumidifier 8
Steam prevents water from entering packed tower；Then gas is passed through packed tower I 9 and packed tower II 10 is handled, and gaseous state thallium is oxidized or inhales
Attached dose is arrived adsorbent surface, purified tail gas direct emission；Catalyst after reaction is passed into circulation parsing pond I 11, is followed
Ring parses in pond II 12, (the desorption liquid 2%HNO in circulation parsing pond3Mixed with 4%HCl), desorption process 11 hours, then
11kHz, ultrasonic sound intensity 110W/m-2Under the conditions of be ultrasonically treated 2.5 hours；Solution is transferred to I 13 He of electrolytic cell after absorbing saturation
Middle electrolytic cell II 14, the anode chamber of electrolytic cell are packed into 1%NaOH solution, and cathode uses stainless steel plate, and anode uses insoluble electricity
Pole；Control voltage is that 1V is electrolysed afterwards；Thallium is slowly precipitated in cathode, and collection is placed on 60 DEG C of dryings of baking oven and weighs, and is protected from light
It seals up for safekeeping；Catalyst after desorption can be refilled with, recycling.
Test result is as follows: when using modified coaly activated carbon absorption flue gas thallium, the accumulation thallium of the active carbon of unit mass
Penetrating adsorbance is 0.88 g/kg；In entire removal process, accumulation recycling simple substance thallium 1.59kg, the rate of recovery 90.34%.The catalysis
Agent shows well under the conditions of complicated gas component；The anti-toxicity of the catalyst, resistance to reduction and leach resistance are very high, no
Only stable in catalytic performance, and it is long using the time.
Embodiment 4
(1) preparation of modified active carbon catalyst: it is crushed dry coconut husk activated carbon, sieving, choosing partial size is about 120 purposes
It is spare；It is that 80 DEG C of deionized waters wash 5 removal dusts with temperature, is put into baking oven and is dried 12 hours at 120 DEG C, weighed
20.00g active carbon is put into the microwave reactor of 600W, the microwave modification in the case where flow is the nitrogen protection of 300mL/min
15min, Activated Carbon Pretreatment process are completed；
The cobalt chloride of 3.57g and the manganese chloride sample of 2.2096g are weighed, is poured into beaker, after suitable distilled water is added, uses glass
Glass stick stirs to manganese chloride solid and cobalt chloride solid be completely dissolved after, by the solution constant volume into the volumetric flask of 100mL
0.3mol/L chloride solution is spare.10g is weighed, 80 mesh sieving active carbon is put into prepared by the solid-liquid volume ratio of 1:5
MClxIn solution, after continuously stirring 30h, supersonic frequency 30kH, ultrasonic sound intensity 320W/m are set-2 It handles under ultrasonic conditions
Sample 3 hours, clear liquid is filtered off, the solid matter filtered out is put into 120 DEG C of baking ovens and dries 12h, is roasted at 500 DEG C of Muffle furnace
5h after being cooled to room temperature, obtains modified coconut husk activated carbon and takes off thallium adsorbent.
(2) flue gas during smelting treatment process: tail gas is generated from metallurgical furnace 1, is cooled to by heat exchanger 2 Celsius lower than 100
Degree, through cyclone dust collectors 3,4 dedusting of electric precipitator, get rid of the dust and partial impurities compound in 99% flue gas, prevent its into
Enter follow up device, makes catalyst poisoning；It is molten subsequently into sulfuric acid is obtained in cyclic absorption pond I 5, II pond 6(of cyclic absorption pond for 3%
Liquid), further remove foreign gas and soluble compound；Tail gas is removed contained in gas by demister 7 and dehumidifier 8
Steam prevents water from entering packed tower；Then gas is passed through packed tower I 9 and packed tower II 10 is handled, and gaseous state thallium is oxidized or inhales
Attached dose is arrived adsorbent surface, purified tail gas direct emission；Catalyst after reaction is passed into circulation parsing pond I 11, is followed
Ring parses in pond II 12, (the desorption liquid 5%HNO in circulation parsing pond3Mixed with 5%HCl), desorption process 20 hours, then
25kHz, ultrasonic sound intensity 120W/m-2Under the conditions of be ultrasonically treated 2 hours；Solution is transferred to electrolytic cell I 13 in after absorbing saturation
Electrolytic cell II 14, the anode chamber of electrolytic cell are packed into 5%NaOH solution, and cathode uses stainless steel plate, and anode uses insoluble electrode；
Control voltage is that 5V is electrolysed afterwards；Thallium is slowly precipitated in cathode, and collection is placed on 80 DEG C of dryings of baking oven and weighs, and is protected from light envelope
It deposits；Catalyst after desorption can be refilled with, recycling.
Test result is as follows: when using modified coaly activated carbon absorption flue gas thallium, the accumulation thallium of the active carbon of unit mass
Penetrating adsorbance is 1.65 g/kg；In entire removal process, accumulation recycling simple substance thallium 31.9g, the rate of recovery 96.67%.The catalysis
Agent shows well under the conditions of complicated gas component；The anti-toxicity of the catalyst, resistance to reduction and leach resistance are very high, no
Only stable in catalytic performance, and it is long using the time.
Claims (5)
1. the purification of thallium and recovery method in a kind of flue gas during smelting, which is characterized in that specifically includes the following steps:
(1) flue gas containing thallium cools down by heat exchanger, through cyclone dust collectors, electric precipitator dedusting, subsequently into containing dilute acid soln
Cyclic absorption pond further remove foreign gas and soluble compound, removed by demister and dehumidifier contained in gas
Steam obtain pretreatment flue gas containing thallium；
(2) MCl will be usedxModified active carbon is put into packed tower as catalyst, at normal temperatures and pressures, is passed through pretreatment containing thallium
Flue gas makes Tl(I in flue gas containing thallium) transformation to Tl(III), flue gas is discharged through subsequent processing, to reach the mesh that flue gas removes thallium
's；
The MClxFor FeCl3、CuCl2、ZnCl2、CoCl2、MnCl2、MgCl2、CaCl2It is middle a kind of or arbitrarily ratio several；
(3) catalyst surface after adsorption reaction generates Tl2O3, by the catalyst soak after absorption in desorption liquid, desorption liquid
The HNO for being 1-5% for mass percent concentration3With the mixed solution for the HCl that mass percent concentration is 1-5%, after the completion of desorption
It is 10-25kHz in frequency, the ultrasonic sound intensity is 100-250W/m-2Under conditions of be ultrasonically treated 0.5-2 hours；
(4) step (3) acquired solution is placed in electrolytic cell circular chamber, and circular chamber and cathode chamber are separated with cation-exchange membrane,
Circular chamber and anode chamber are separated with anion-exchange membrane, and anode chamber is packed into 1-5%NAOH solution, and cathode uses stainless steel plate, anode
Using insoluble electrode；Control voltage is that 1-5V is electrolysed afterwards；Thallium is slowly precipitated in cathode, and collection is placed on baking oven 40-80
It is DEG C dry and weigh, it is protected from light and seals up for safekeeping.
2. the purification of thallium and recovery method in flue gas during smelting according to claim 1, it is characterised in that: the MClxModified
Method for preparation of active carbon is as follows:
(1) weigh the active carbon that commercially available partial size is 20 ~ 120 mesh, it is washing, dry, then flow be 100mL/min ~
Under the inert gas shielding of 300mL/min, microwave modification 3min ~ 15min obtains pretreated active carbon；
(2) by MClxIt is dissolved in deionized water and is configured to MClxSolution, wherein MClxSolution concentration is the mol/ of 0.1mol/L ~ 0.3
L；
(3) active carbon is put into MCl in the ratio that solid-liquid volume ratio is 1:1 ~ 1:5xIn solution, sonication treatment time is that 1-2 is small
When, it is stirred continuously in treatment process；
(4) 3 ~ 5h is roasted under the conditions of 200 ~ 500 DEG C in Muffle furnace after drying the Immesion active carbon that step (3) processing obtains
Obtain MClxModified active carbon.
3. the purification of thallium and recovery method in flue gas during smelting according to claim 1, it is characterised in that: desorption in step (2)
The time of process is 8-20 hours.
4. the purification of thallium and recovery method equipment therefor in flue gas during smelting described in claim 1, it is characterised in that: including including changing
Hot device (2), electric precipitator (4), cyclic absorption pond I (5), cyclic absorption pond II (6), demister (7), is removed cyclone dust collectors (3)
Wet device (8), packed tower I (9), packed tower II (10), circulation parsing pond I (11), circulation parsing pond II (12), electrolytic cell I (13),
Electrolytic cell II (14), metallurgical furnace (1), heat exchanger (2), cyclone dust collectors (3), electric precipitator (4) are sequentially communicated, electric precipitator
(4) it is connected to respectively with cyclic absorption pond I (5), cyclic absorption pond II (6), cyclic absorption pond I (5), cyclic absorption pond II (6) are converged
Be connected to after conjunction with demister (7), demister (7) is connected to dehumidifier (8), dehumidifier (8) respectively with packed tower I (9), packed tower
II (10) connection, packed tower I (9), packed tower II (10) discharge gate converge after respectively with circulation parse pond I (11), circulant solution
Analyse pond II (12) connection, circulation parsing pond I (11), circulation parsing pond II (12) converge after respectively with electrolytic cell I (13), electrolytic cell
II (14) connection.
5. device according to claim 4, it is characterised in that: be equipped with valve between two containers being connected.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876585A (en) * | 2019-04-26 | 2019-06-14 | 国药集团重庆医药设计院有限公司 | A kind of traditional Chinese medicine plaster production exhaust treatment system |
| CN112481507A (en) * | 2020-12-15 | 2021-03-12 | 江苏龙源催化剂有限公司 | Method for recovering metallic lead and thallium components from waste denitration catalyst |
| CN113289473A (en) * | 2021-06-11 | 2021-08-24 | 封云 | Method for treating heavy metal before smelting flue gas desulfurization |
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| CN109876585A (en) * | 2019-04-26 | 2019-06-14 | 国药集团重庆医药设计院有限公司 | A kind of traditional Chinese medicine plaster production exhaust treatment system |
| CN112481507A (en) * | 2020-12-15 | 2021-03-12 | 江苏龙源催化剂有限公司 | Method for recovering metallic lead and thallium components from waste denitration catalyst |
| CN113289473A (en) * | 2021-06-11 | 2021-08-24 | 封云 | Method for treating heavy metal before smelting flue gas desulfurization |
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| CN109364659B (en) | 2023-06-02 |
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