CN109022801A - A kind of device and method of harmless treatment arsenic sulfide slag - Google Patents

A kind of device and method of harmless treatment arsenic sulfide slag Download PDF

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Publication number
CN109022801A
CN109022801A CN201811012984.XA CN201811012984A CN109022801A CN 109022801 A CN109022801 A CN 109022801A CN 201811012984 A CN201811012984 A CN 201811012984A CN 109022801 A CN109022801 A CN 109022801A
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arsenic
furnace
temperature
sulfide slag
condenser
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CN109022801B (en
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郭键柄
杨东伟
卢超
陈正
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Lanzhou Engineering and Research Institute of Nonferrous Metallurgy Co Ltd
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Lanzhou Engineering and Research Institute of Nonferrous Metallurgy Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/02Roasting processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/04Obtaining arsenic
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a kind of device and method of harmless treatment arsenic sulfide slag, belong to hazardous waste disposal field, at high cost existing for existing wet processing to solve, it is difficult to the problem of realizing industrial applications.A kind of device of harmless treatment arsenic sulfide slag, including roasting system, reduction furnace, reduction furnace dust collecting system, roasting system includes the roaster being sequentially connected, the first condenser, the first bagroom, lye absorption tower and the first air-introduced machine, and reduction furnace dust collecting system includes the second condenser, the second bagroom, the second air-introduced machine being sequentially connected.The entire production process of the present invention is completed under totally-enclosed and tiny structure environment, and treatment process is generated without dust, and operator is not directly contacted with noxious material, without secondary pollution compared to traditional arsenic removal method treatment process clean and environmental protection.High production efficiency.Realize the harmless treatment of arsenic sulfide slag.

Description

A kind of device and method of harmless treatment arsenic sulfide slag
Technical field
The invention belongs to hazardous waste disposal fields, and in particular to a kind of device of harmless treatment arsenic sulfide slag and side Method.
Background technique
China is non-ferrous metal big country, during non-ferrous metal metallurgy flue gas acid preparing, can generate largely containing arsenic, copper, The sour water of the elements such as lead, zinc.To reduce sewage discharge, water circulation use rate is improved, domestic smelting enterprise is mostly acid dirty The salt of sulfur-bearing, such as vulcanized sodium, NaHS, sodium thiosulfate are added in water, is reacted with arsenic, copper, the lead etc. in water Sulfide precipitation is generated, to achieve the purpose that arsenic removal and reduce heavy metal ion.Currently, vulcanization processing sour water is more next More is used by domestic large-scale smeltery, therefore, also produces a large amount of arsenic sulfide slag.
Valuable metal copper, lead, zinc, cadmium content are relatively low in arsenic sulfide slag, but arsenic content is up to 30%-40%, have recycling valence Value.Since the leachate of arsenic sulfide slag is highly acid, the leaching concentration of the heavy metal ion such as arsenic, copper, lead, cadmium in arsenic slag is super Cross national standard of landfill.Arsenic sulfide slag belongs to the hazardous waste for being not only corrosive but also having Leaching feature, both at home and abroad to vulcanization The processing approach of arsenic slag mainly send to dangerous waste disposition center and carries out stabilizing/solidifying two kinds of arsenic of landfill and recycling.
The stabilisation of arsenic slag/solidification landfill is mainly mixed by the additives such as lime, cement, pitch and arsenic sulfide slag The substance with low-solubility, hypotoxicity and low-flow is formed, is allowed to that chemical stability is presented or one kind of leakproofness is harmless Change processing method.The arsenic sulfide slag high for arsenic content, stabilisation/solidification landfill process need a large amount of additive to reduce arsenic Content, processing cost are expensive.In addition, the arsenic in slag does not recycle, there are the risks of the wasting of resources and secondary arsenic pollution.
The approach of recycling arsenic has two kinds of techniques of pyrogenic process and wet process.Thermal process mostly uses roasting method, and arsenic is directly with three oxidations The recycling of two arsenic forms.This technology maturation, process is short, at low cost, but the arsenic trioxide for handling drying regime is violent in toxicity, difficult In ensuring good operating environment, secondary pollution is easily caused;Wet process uses acidleach, alkali leaching or salt leaching etc. to be handled, and first Arsenic is separated from slag, is then further recycled or is carried out harmless treatment, product mainly has arsenic trioxide, arsenate Deng.Wet processing does not generate dust, is able to satisfy environmental requirement, has many advantages, such as that low energy consumption, pollutes less, is high-efficient, but its process Complex, processing cost is higher.
Since arsenic content is high in arsenic sulfide slag, in recent years, the processing of arsenic sulfide slag is gradually from " Gu arsenic " to recycling arsenic transformation. Either thermal process or wet processing, product arsenic trioxide or arsenate are the compound of arsenic, have certain poison Property, and the market demand is limited.The production technology that the existing arsenic by arsenic sulfide slag is converted into the compound of arsenic cannot be from basic The recycling of the upper pollution for solving the problems, such as arsenic and arsenic resource.
Summary of the invention
The object of the present invention is to provide a kind of device of harmless treatment arsenic sulfide slag that the arsenic rate of recovery is high,
It is a further object to provide a kind of methods of harmless treatment arsenic sulfide slag, are deposited with solving existing wet processing It is at high cost, it is difficult to the problem of realizing industrial applications.
The technical solution adopted by the invention is as follows: a kind of device of harmless treatment arsenic sulfide slag, including roasting system, also Former furnace, reduction furnace dust collecting system, roasting system include the roaster being sequentially connected, the first condenser, the first bagroom, alkali Liquid absorption tower and the first air-introduced machine, reduction furnace dust collecting system include the second condenser being sequentially connected, the second bagroom, Two air-introduced machines, the first condenser, the first bagroom, the second bagroom are connected by Pneumatic conveying pipeline and storage bin It connects, it can be achieved that the closing of arsenic oxide, being continuously conveyed.Pass through pneumatic conveying between the bottom and storage bin of second bagroom Pipeline connection;The bottom of storage bin is equipped with screw below the bin device, and the end of screw below the bin device is located at the top of reduction furnace.
As a further improvement of the present invention, condenser and the first bagroom bottom are equipped with star-like discharging device, star It is connected between discharger bottom and storage bin by Pneumatic conveying pipeline.
As a further improvement of the present invention, the roaster and reduction furnace are sealed using refractory material;
As a further improvement of the present invention, the first air-introduced machine and the second air-introduced machine are respectively connected with chimney.
A method of processing harmless treatment arsenic sulfide slag, comprising the following steps:
(1) roaster feed inlet is added in arsenic sulfide slag to be processed, opens roaster heating system;
(2) when being increased to 150-200 DEG C wait roast in-furnace temperature, the first condenser, the first bagroom, lye is opened and is absorbed Tower, the first air-introduced machine make in roaster in micro-vacuum state, pressure limit 20-60 kPa;
(3) heating power is adjusted after the completion of the step (2), so that roasting in-furnace temperature is risen to 600-800 DEG C, is opened air feed system System, comes into full contact with material in furnace with oxygen;
(4) temperature range reached in the step (3) keeps the temperature 30-90 min, carries out the oxidizing roasting of arsenic in arsenic sulfide slag;
(5) roaster heating system is closed after the completion of the step (4);
(6) roaster cooling system, dust collecting system and vent gas treatment system are closed when roasting in-furnace temperature and being down to 200 DEG C or less System, until in-furnace temperature is down to room temperature;
(7) (6) open air-transport system after the completion of the step, and the oxide of the arsenic of collection is delivered to reduction furnace bin stock Storehouse;
(8) arsenic oxide is added in reduction furnace using screw below the bin, opens reduction furnace heating system, opens simultaneously the second condensation Device, the second bagroom, the second air-introduced machine make to restore furnace pressure range 50-90 kPa;
(9) heating power is adjusted after the completion of the step (8), so that reduction in-furnace temperature is risen to 600-800 DEG C, control second is cold 400-500 DEG C of condenser temperature;
(10) temperature range reached in the step (9) keeps the temperature 30-90 min, carries out the reduction melting of arsenic oxide,
(11) reduction furnace heating system is closed after the completion of the step (10);
(12) dust collecting system is closed when in-furnace temperature to be restored is down to 100 DEG C or less, until in-furnace temperature is down to room temperature;
(13) after the completion of the step (12), metallic arsenic is recycled from condenser pipe.
As a further improvement of the present invention, arsenic sulfide slag material is mainly that non-ferrous metals smelting works are handled using vulcanization The solid slag generated when sour water.
As a further improvement of the present invention, the lye absorption tower (5) is equipped with NaOH solution circulating pump, and lye is made to get to alkali At the top of liquid absorption tower, lye circulated sprinkling is realized from top to bottom, the desulfuration efficiency of roaster (1) output sulfur-containing smoke gas can be improved.
In the product of all arsenic, metallic arsenic (elemental arsenic) toxicity is minimum, and price is high, and the market demand is big.Therefore, from sulphur Change in arsenic slag and arsenic is changed into metallic arsenic, can not only solve arsenic slag bring pollution problem, but also can turn waste into wealth, realize arsenic resource Secondary recovery utilizes.
For above situation, the present invention is made using thermal process processing arsenic sulfide slag using a set of roasting-reduction apparatus The final output in the form of metallic arsenic of arsenic in arsenic sulfide slag, and finally obtain the metallic arsenic product of nonhazardous.
Arsenic content reaches 30%-40%, and the tenors such as copper, lead, zinc < 1% in arsenic sulfide slag.In arsenic sulfide slag arsenic mainly with As2S3, As2S5Form exists, other metals are also with the presence of respective oxide morphology.
In the roasting of roaster internal oxidition, 600-800 DEG C of maturing temperature is controlled, the sulfide of arsenic occurs following main anti- It answers:
2As2S3+9O2 = 2As2O3 +6SO2
2As2S5+13O2 = 2As2O3 +10SO2
2CuS + 3O2= 2CuO + 2SO2
2ZnS + 3O2= 2ZnO + 2SO2
2PbS + 3O2= 2PbO + 2SO2
Different according to the oxyphie ability of element, the sequence that sulfide contacts generation oxidation reaction with oxygen is also different, As2S3With As2S5Preferential oxidation and generate As2O3.Due to As2O3With very strong volatility, start to distil when temperature is higher than 120 DEG C Into in furnace gas.When oxygen is abundant in furnace, a small amount of non-volatile As2O3It can be oxidized and generate the small As of volatility2O5.With Furnace temperature increases, As2O3And As2O5Cooling process condensation of gathering dust is discharged into from furnace roof with flue gas to collect.
When carrying out carbon reduction melting in reduction furnace, due to As2O3Boiling point be 461 DEG C.Therefore, as long as in carbon thermal reduction When control 600-800 DEG C of in-furnace temperature, carry out furnace sealing, then the reduction of arsenic oxide will be carried out soon.Occur such as in furnace Lower key reaction:
As2O5 + C = As2O3 + CO2
2As2O3 + 6C = 4As + 6CO
2As2O3 + 6CO = 4As + 6CO2
C + O2 = CO2
C + 1 /2O2 = CO
CO + 1 /2O2 = CO2
The sublimation point of arsenic is 612 DEG C, and the metallic arsenic generated in reduction furnace is discharged into condensation with flue gas in the form of arsenic steam Device controls 400-500 DEG C of condenser temperature, then metallic arsenic condenses output in condenser.
Therefore, the feature volatile using arsenic and arsenic oxide, controls suitable reaction temperature, under the conditions of tiny structure i.e. The innoxious recycling of arsenic in arsenic sulfide slag can be achieved.The resultant metal arsenic poison finally obtained is minimum, and economic value is high, avoids The secondary pollution of arsenic.The harmless treatment of the arsenic sulfide slag generated when handling sour water suitable for non-ferrous metals smelting works.
The present invention has the advantages that
(1) treatment process clean and environmental protection, it is without secondary pollution.Harmful element arsenic of the present invention is in roaster first with the shape of arsenic oxide Formula volatilization, arsenic oxide is delivered to storage bin by air-transport system after condensation, then is added in reduction furnace by screw below the bin, carbon Nontoxic metallic arsenic is condensed into after reduction to concentrate in condenser.The entire production process of the present invention is under totally-enclosed and tiny structure environment It completes, treatment process is generated without dust, and operator is not directly contacted with noxious material, compared to traditional arsenic removal method treatment process cleaning Environmental protection, it is without secondary pollution.High production efficiency.Realize the harmless treatment of arsenic sulfide slag.
(2) the arsenic rate of recovery is high.Roaster and reduction furnace of the present invention have been equipped with condensation and dust arrester installation, and treatment process is complete Sealing, the basic free of losses of metallic arsenic, the arsenic rate of recovery are high.
(3) product economy value is high.Arsenic output in the form of arsenic compound after traditional arsenic sulfide slag recycling arsenic, arsenic chemical combination Object is poisonous and harmful, and economic value is low.The product of arsenic of the present invention is metallic arsenic, small toxicity, economic value height.
(4) continuous production can be achieved.Roasting-reduction apparatus that the present invention uses is, it can be achieved that arsenic sulfide slag is fed to gold certainly Belong to the continuous production of arsenic output, full process automatization degree height is, it can be achieved that remote control, high production efficiency.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of the device of harmless treatment arsenic sulfide slag.
In figure: roaster (1), air blower (2), the first condenser (3), the first bagroom (4), lye absorption tower (5), the first air-introduced machine (6), air-transport system (7), storage bin (8), screw below the bin device (9), reduction furnace (10), the second condensation Device (11), the second bagroom (12), the second air-introduced machine (13), chimney (14).
Specific embodiment
It is the preferred embodiment of the present invention below, but is not limited to such an embodiment.
Roaster 1 is configured with air blower 2, and the heating method that apparatus of the present invention use is not limited to this kind and adds for electric heating Hot mode further includes the heating methods such as coal, natural gas.
As shown, a kind of device of harmless treatment arsenic sulfide slag, roasting system, reduction furnace 10, reduction furnace gather dust and are System, roasting system include the roaster 1 being sequentially connected, the first condenser 3, the first bagroom 4, lye absorption tower 5 and the One air-introduced machine 6, reduction furnace dust collecting system include the second condenser 11 being sequentially connected, the second bagroom 12, the second air inducing Machine 13, the first condenser 3, the first bagroom 4, the second bagroom 12 are connected by Pneumatic conveying pipeline and storage bin 8 It connectsIt is connected between the bottom and storage bin 8 of second bagroom 12 by Pneumatic conveying pipeline;The bottom of storage bin 8 is equipped with Screw below the bin device 9, the end of screw below the bin device 9 are located at the top of reduction furnace 10.
Condenser 3 and 4 bottom of the first bagroom are equipped with star-like discharging device, star-like discharging device bottom and storage bin 8 it Between pass through Pneumatic conveying pipeline connect.Roaster 1 and reduction furnace 10 are sealed using refractory material;First air-introduced machine 6 and second draws Blower 13 is respectively connected with chimney 14.The tail gas of output enters the emptying of chimney 14.
The raw materials used acid water for certain southwestern non-ferrous metals smelting works of embodiment uses the solid of sulfuration process output Waste, i.e., a kind of arsenic sulfide slag, main component As2S3, CuS, ZnS, PbS etc., each essential element content is shown in Table 1.
Embodiment 1
The raw materials used ingredient of embodiment 1 is shown in Table 1, important technological parameters: 600 DEG C of maturing temperature, calcining time 30min, reduction temperature 600 DEG C, recovery time 30min, 400 DEG C of condensation temperature of degree.
Specific implementation step is as follows:
(1) above-mentioned arsenic sulfide slag material 3000g is added in roaster, covers bell, seal furnace body, open roasting stove heating system System;
(2) when being increased to 150 DEG C wait roast in-furnace temperature, open the first condenser, the first bagroom, lye absorption tower, First air-introduced machine makes in roaster in micro-vacuum state, 20 kPa of pressure;
(3) heating power is adjusted after the completion of the step (2), so that roasting in-furnace temperature is risen to 600 DEG C, is opened air blower, make Material comes into full contact with oxygen in furnace;
(4) temperature range reached in the step (3) keeps the temperature 30 min, carries out the oxidizing roasting of arsenic in arsenic sulfide slag;Sulphur with The form output of sulfur dioxide gas, arsenic output and cold in the first condenser and the first bagroom in the form of the oxide Retrogradation drop.
(5) roaster heating system is closed after the completion of the step (4);
(6) closed when roasting in-furnace temperature and being down to 200 DEG C or less the first condenser, the first bagroom, lye absorption tower, First air-introduced machine, until in-furnace temperature is down to room temperature;
(7) air-transport system is opened after the completion of the step (6), and the first condenser, the first bagroom are collected The oxide of arsenic is delivered to reduction furnace storage bin;
(8) arsenic oxide is added in reduction furnace using screw below the bin, opens reduction furnace heating system, opens simultaneously the second condensation Device, the second bagroom, the second air-introduced machine make to restore furnace pressure range 50kPa;
(9) heating power is adjusted after the completion of the step (8), so that reduction in-furnace temperature is risen to 600 DEG C, condenser temperature 400 ℃;
(10) temperature range reached in the step (9) keeps the temperature 30min, carries out the reduction melting of arsenic oxide, golden after reaction Belong to arsenic output in a gaseous form, condenses and settle in the second condenser.
(11) reduction furnace heating system is closed after the completion of the step (10);
(12) the second condenser, the second bagroom, the second air inducing are closed when in-furnace temperature to be restored is down to 100 DEG C or less Machine recycles metallic arsenic from condenser until in-furnace temperature is cooled to room temperature.
Because purpose product is metallic arsenic, embodiment 1 only weighs the metallic arsenic collected in condenser, is chemically examined, as a result It is shown in Table 2.As can be seen from the results, an open circuit operation arsenic rate of recovery is up to 81.62%, metallic arsenic product purity 95.52%.
Embodiment 2
The raw materials used same embodiment 1 of embodiment 2, is shown in Table 1.Important technological parameters: 700 DEG C of maturing temperature, calcining time 60min, 700 DEG C of reduction temperature, recovery time 60min, 450 DEG C of condensation temperature.
Specific implementation step is as follows:
(1) above-mentioned arsenic sulfide slag material 3000g is added in roaster, covers bell, seal furnace body, open roasting stove heating system System.
(2) when being increased to 150 DEG C wait roast in-furnace temperature, the first condenser, the first bagroom, lye is opened and is absorbed Tower, the first air-introduced machine make in roaster in micro-vacuum state, 40 kPa of pressure.
(3) heating power is adjusted after the completion of the step (2), so that roasting in-furnace temperature is risen to 700 DEG C, is opened air feed system System, comes into full contact with material in furnace with oxygen.
(4) temperature range reached in the step (3) keeps the temperature 60 min, carries out the oxidizing roasting of arsenic in arsenic sulfide slag.
(5) roaster heating system is closed after the completion of the step (4).
(6) cooling system, dust collecting system and exhaust treatment system are closed when roasting in-furnace temperature and being down to 200 DEG C or less, Until in-furnace temperature is down to room temperature.
(7) air-transport system is opened after the completion of the step (6), the arsenic that cooling system and dust collecting system are collected Oxide is delivered to reduction furnace storage bin.
(8) arsenic oxide is added in reduction furnace using screw below the bin, opens reduction furnace heating system, opens simultaneously second Condenser, the second bagroom, the second air-introduced machine make to restore furnace pressure range 70kPa.
(9) heating power is adjusted after the completion of the step (8), so that reduction in-furnace temperature is risen to 700 DEG C, condenser temperature 450℃。
(10) temperature range reached in the step (9) keeps the temperature 60min, carries out the reduction melting of arsenic oxide.
(11) reduction furnace heating system is closed after the completion of the step (10).
(12) dust collecting system is closed when in-furnace temperature to be restored is down to 100 DEG C or less, until in-furnace temperature is cooled to room temperature, Metallic arsenic is recycled from condenser.
Because purpose product is metallic arsenic, embodiment 2 only weighs the metallic arsenic collected in condenser, is chemically examined, as a result It is shown in Table 3.As can be seen from the results, an open circuit operation arsenic rate of recovery is up to 86.52%, metallic arsenic product purity 97.48%.
Embodiment 3
The raw materials used same embodiment 1 of embodiment 3, is shown in Table 1.Important technological parameters: 800 DEG C of maturing temperature, calcining time 90min, 800 DEG C of reduction temperature, recovery time 90min, 500 DEG C of condensation temperature.
Specific implementation step is as follows:
(1) above-mentioned arsenic sulfide slag material 3000g is added in roaster, covers bell, seal furnace body, open roasting stove heating system System.
(2) when being increased to 200 DEG C wait roast in-furnace temperature, the first condenser, the first bagroom, lye is opened and is absorbed Tower, the first air-introduced machine make in roaster in micro-vacuum state, 60 kPa of pressure.
(3) heating power is adjusted after the completion of the step (2), so that roasting in-furnace temperature is risen to 800 DEG C, is opened air feed system System, comes into full contact with material in furnace with oxygen.
(4) temperature range reached in the step (3) keeps the temperature 90 min, carries out the oxidizing roasting of arsenic in arsenic sulfide slag.
(5) roaster heating system is closed after the completion of the step (4).
(6) cooling system, dust collecting system and exhaust treatment system are closed when roasting in-furnace temperature and being down to 200 DEG C or less, Until in-furnace temperature is down to room temperature.
(7) air-transport system is opened after the completion of the step (6), the arsenic that cooling system and dust collecting system are collected Oxide is delivered to reduction furnace storage bin.
(8) arsenic oxide is added in reduction furnace using screw below the bin, opens reduction furnace heating system, opens simultaneously second Condenser, the second bagroom, the second air-introduced machine make to restore furnace pressure range 90kPa.
(9) heating power is adjusted after the completion of the step (8), so that reduction in-furnace temperature is risen to 800 DEG C, condenser temperature 500℃。
(10) temperature range reached in the step (9) keeps the temperature 90min, carries out the reduction melting of arsenic oxide.
(11) reduction furnace heating system is closed after the completion of the step (10).
(12) dust collecting system is closed when in-furnace temperature to be restored is down to 100 DEG C or less, until in-furnace temperature is cooled to room temperature, Metallic arsenic is recycled from condenser.
Because purpose product is metallic arsenic, embodiment 3 only weighs the metallic arsenic collected in condenser, is chemically examined, as a result It is shown in Table 4.As can be seen from the results, an open circuit operation arsenic rate of recovery is up to 87.57%, metallic arsenic product purity 96.28%.
Embodiment 4: difference from Example 1 is, completes step (1)-step (6), between being suitable on a small scale Medium well produces.
Embodiment 5: difference from Example 1 is, step (7)-step is directly carried out after the completion of step (4) (13), and continuous production situation big suitable for treating capacity.
The slag of step (4) roaster output in embodiment, Gu can by sent after water quenching to dangerous waste treatment plant stabilize/ Change landfill;The sulfur dioxide of output is then absorbed in the lye absorption tower of exhaust treatment system.
Wherein a small amount of black powder of step (12) reduction furnace the second bagroom output, can return to reduction furnace and continues with.
Open circuit operation of device of processing arsenic sulfide slag provided by the invention can reach 95% or more metallic arsenic purity, 80% or more the arsenic rate of recovery.Through the invention, valuable element arsenic in arsenic slag, and the metallic arsenic product of output high added value have been recycled, The secondary pollution of arsenic slag is avoided, realizing turns waste into wealth.

Claims (7)

1. a kind of device of harmless treatment arsenic sulfide slag, it is characterised in that: including roasting system, reduction furnace (10), reduction furnace Dust collecting system, roasting system include the roaster (1), the first condenser (3), the first bagroom (4), lye being sequentially connected Absorption tower (5) and the first air-introduced machine (6), reduction furnace dust collecting system include the second condenser (11), the second cloth bag being sequentially connected Dust-precipitator (12), the second air-introduced machine (13), the first condenser (3), the first bagroom (4), the second bagroom (12) It is connect by Pneumatic conveying pipeline with storage bin (8), passes through gas between the bottom and storage bin (8) of the second bagroom (12) The connection of power conveyance conduit;The bottom of storage bin (8) is equipped with screw below the bin device (9), and the end of screw below the bin device (9) is located at reduction furnace (10) top.
2. a kind of device of harmless treatment arsenic sulfide slag as described in claim 1, it is characterised in that: condenser (3) and the One bagroom (4) bottom is equipped with star-like discharging device, passes through pneumatic carrier between star-like discharging device bottom and storage bin (8) Road connection.
3. a kind of device of harmless treatment arsenic sulfide slag as claimed in claim 1 or 2, it is characterised in that: the roaster (1) it is sealed with reduction furnace (10) using refractory material.
4. a kind of device of harmless treatment arsenic sulfide slag as claimed in claim 3, it is characterised in that: the first air-introduced machine (6) Chimney (14) are respectively connected with the second air-introduced machine (13).
5. a kind of method for handling harmless treatment arsenic sulfide slag, it is characterised in that the following steps are included:
(1) roaster feed inlet is added in arsenic sulfide slag to be processed, opens roaster heating system;
(2) when being increased to 150-200 DEG C wait roast in-furnace temperature, the first condenser, the first bagroom, lye is opened and is absorbed Tower, the first air-introduced machine make in roaster in micro-vacuum state, pressure limit 20-60 kPa;
(3) heating power is adjusted after the completion of the step (2), so that roasting in-furnace temperature is risen to 600-800 DEG C, is opened air feed system System, comes into full contact with material in furnace with oxygen;
(4) temperature range reached in the step (3) keeps the temperature 30-90 min, carries out the oxidizing roasting of arsenic in arsenic sulfide slag;
(5) roaster heating system is closed after the completion of the step (4);
(6) roaster cooling system, dust collecting system and vent gas treatment system are closed when roasting in-furnace temperature and being down to 200 DEG C or less System, until in-furnace temperature is down to room temperature;
(7) (6) open air-transport system after the completion of the step, and the oxide of the arsenic of collection is delivered to reduction furnace bin stock Storehouse;
(8) arsenic oxide is added in reduction furnace using screw below the bin, opens reduction furnace heating system, opens simultaneously the second condensation Device, the second bagroom, the second air-introduced machine make to restore furnace pressure range 50-90 kPa;
(9) heating power is adjusted after the completion of the step (8), so that reduction in-furnace temperature is risen to 600-800 DEG C, control second is cold 400-500 DEG C of condenser temperature;
(10) temperature range reached in the step (9) keeps the temperature 30-90 min, carries out the reduction melting of arsenic oxide,
(11) reduction furnace heating system is closed after the completion of the step (10);
(12) dust collecting system is closed when in-furnace temperature to be restored is down to 100 DEG C or less, until in-furnace temperature is down to room temperature;
(13) after the completion of the step (12), metallic arsenic is recycled from condenser pipe.
6. the method for processing harmless treatment arsenic sulfide slag according to claim 5, it is characterised in that: arsenic sulfide slag material The solid slag generated when predominantly non-ferrous metals smelting works handle sour water using vulcanization.
7. the method for processing harmless treatment arsenic sulfide slag according to claim 6, it is characterised in that:
The lye absorption tower (5) is equipped with NaOH solution circulating pump, gets to lye at the top of lye absorption tower, realizes alkali from top to bottom Liquid circulated sprinkling.
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