CN210420096U - Arsenic alkali residue resource utilization equipment - Google Patents

Arsenic alkali residue resource utilization equipment Download PDF

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CN210420096U
CN210420096U CN201921042504.4U CN201921042504U CN210420096U CN 210420096 U CN210420096 U CN 210420096U CN 201921042504 U CN201921042504 U CN 201921042504U CN 210420096 U CN210420096 U CN 210420096U
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arsenic
ammonia
reduction furnace
antimony
reduction
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尹小林
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Changsha Zichen Technology Development Co Ltd
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Changsha Zichen Technology Development Co Ltd
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    • 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

Abstract

An apparatus for resource utilization of arsenic alkali residue comprises an electric heating reduction furnace, a powder air lock meter feeding device, an ammonia spraying device, a heat exchanger, a residual ammonia finishing device, a centrifugal fan and an ammonia storage device. When the device is operated, preheated arsenic alkali residue powder materials are fed into an electrothermal reduction furnace, ammonia is directly blown into the materials in the furnace for reduction reaction, elemental antimony obtained by the reduction reaction is discharged from an outlet at the bottom of the reduction furnace to obtain crude antimony, residues are discharged from a slag discharge port at the edge of the reduction furnace to obtain alkali residues, elemental arsenic vapor obtained by blowing reduction sublimation enters a cooler along with hot waste gas flow drawn by an air inducing machine for condensation and solidification to obtain crude arsenic, and waste gas enters a residual ammonia finishing device for residual ammonia collection and recycling. The utility model discloses the result is simple, easily automated control, and the investment is less, and the handling capacity is big, safety ring protects.

Description

Arsenic alkali residue resource utilization equipment
Technical Field
The utility model relates to an arsenic alkali residue treatment facility, concretely relates to arsenic alkali residue utilization equipment.
Background
The arsenic alkali slag is a smelting waste slag containing sodium arsenate, sodium antimonate and sodium carbonate generated in the antimony refining arsenic removal process of antimony pyrometallurgy, and because the sodium arsenate is extremely toxic and easily soluble in water, the arsenic alkali slag is very easy to cause environmental pollution events, so that solid dangerous waste which is difficult to properly treat all the time is difficult to be treated, and the healthy development of the antimony smelting industry is restricted to a certain extent.
For arsenic alkali slag which is difficult to be properly treated, a great deal of research and practice is continuously carried out by domestic and foreign science and technology workers, and various technical methods for treating the arsenic alkali slag can be roughly summarized into three types of methods, namely solidification landfill, wet treatment and pyrogenic treatment.
The solidification landfill method of the arsenic-alkali slag comprises the steps of cement solidification, lime/calcium salt solidification, iron salt solidification, plastic solidification, asphalt solidification, melting/vitrification solidification and the like, and then landfill is carried out, although the solidification landfill can realize the fixation of arsenic to a certain extent within a certain time, the solidification landfill methods have the problems of large capacity increase ratio before and after solidification, large land landfill is needed in the later period, long-term pollution hidden danger and the like.
In conclusion, the existing treatment equipment for various arsenic-alkali residues has the defects that the separation of arsenic, antimony and alkali resources is difficult, particularly the treatment difficulty of arsenic is high, and the problems of environmental protection, economy and the like are prominent.
At present, the pyrometallurgical reduction treatment of arsenic-alkali residue and the production of metallic arsenic generally carry out reduction reaction on the arsenic-alkali residue, arsenic oxide or arsenic-containing ore by using carbon, hydrogen and the like as reducing agents, practice or research reports that ammonia is directly used as a high-efficiency reducing agent to directly blow reduction or blowing boiling reduction are not seen, and equipment which can efficiently separate three components of arsenic, antimony and alkali in the arsenic-alkali residue and recycle the arsenic-alkali residue with low production cost is unavailable.
SUMMERY OF THE UTILITY MODEL
The utility model aims to solve the technical problem that the above defects existing in the prior art are overcome, and the equipment which can efficiently separate three major components of arsenic, antimony and alkali in the arsenic alkali residue and can realize resource utilization of the arsenic alkali residue with low production cost is provided.
The utility model provides a technical scheme that its technical problem adopted as follows: the utility model provides an equipment of arsenic alkali sediment utilization, mainly includes: the device comprises an electrothermal reduction furnace, a powder air lock meter feeding device, an ammonia spraying device, a cooling (heat exchanging) device, a residual ammonia arrangement device, a centrifugal fan and an ammonia storage device, wherein a discharge port of the powder air lock meter feeding device is connected with a powder inlet of the electrothermal reduction furnace, the ammonia spraying device is respectively connected with the electrothermal reduction furnace and the cooling (heat exchanging) device through ammonia conveying pipelines, the cooling (heat exchanging) device is respectively connected with an exhaust outlet of the electrothermal reduction furnace and an inlet of the residual ammonia arrangement device through pipelines, a waste gas outlet of the residual ammonia arrangement device is connected with an air inlet of the centrifugal fan, and the ammonia storage device is connected with the cooling (heat exchanging) device through a liquid ammonia conveying pipeline.
Furthermore, the centrifugal fan is respectively connected with a waste gas outlet of the cooling (heat exchange) device and an air inlet of the residual ammonia finishing device.
The utility model discloses when operation: feeding the preheated arsenic alkali residue powder material into an electrothermal reduction furnace for thermochemical reduction reaction, directly blowing ammonia into the material in the furnace for reduction reaction, discharging elemental antimony obtained by reduction reaction from an outlet at the bottom of the reduction furnace to obtain crude antimony, discharging residues from a slag discharge port at the edge of the reduction furnace to obtain alkaline residues, discharging the elemental arsenic vapor subjected to blowing reduction sublimation from an exhaust outlet of the reduction furnace along with hot waste gas flow drawn by a centrifugal (induced) fan, allowing the elemental arsenic vapor to enter a cooler for condensation and solidification to obtain crude arsenic, and allowing the waste gas to enter a residual ammonia finishing device for residual ammonia collection and cyclic utilization.
Further, the ammonia refers to anhydrous ammonia, or a mixture of anhydrous ammonia and hydrazine or derivatives thereof; the ammonia injection amount is preferably controlled to be 1.0-10% of the ammonia content in the waste gas; the ammonia injected into the furnace is evaporated by a heat exchanger and heated to 40-400 ℃, and preferably preheated by a heat exchange device of an exhaust gas flow cooler, so as to save energy.
Further, the preheated arsenic alkali residue powder material refers to arsenic alkali residue powder material which is obtained by pre-grinding arsenic alkali residue into powder of 80-300 meshes (preferably 120-200 meshes) and is preheated to more than 120 ℃ (preferably preheated to 200-600 ℃), so that the power consumption of a reduction furnace is saved, and water is removed; the heat energy for preheating is preferably the residual heat in the process.
Furthermore, natural gas or coal gas with the mass ratio of 5-50% can be added into the ammonia for blowing.
Further, biomass powder and/or coal powder with the mass ratio of 0-20% can be added into the preheated arsenic-alkali residue powder material.
Further, the obtained crude antimony is sold or returned to antimony refining, or is made into high-quality ash arsenic, black arsenic or yellow arsenic products according to mature refining process for marketing; a small amount of inorganic substance residues generated in the refining process are returned to the arsenic alkali residue material for utilization.
Furthermore, the main components of the obtained alkaline slag are sodium carbonate, sodium hydroxide and part of aluminosilicate minerals, and the alkaline slag can be returned to be used for refining antimony, or used as a raw material for refining caustic soda or calcined soda.
Further, the caustic soda or the soda ash refined by taking the alkaline slag as the raw material is used for preparing sodium hydroxide or sodium carbonate by taking the alkaline slag as the raw material. The refined caustic soda is prepared by crushing alkaline residues, adding water, adding a proper amount of roasted magnesia powder or roasted dolomite powder, stirring and reacting at 30-60 ℃, filtering, washing and separating into magnesium residues or magnesium-calcium residues and filtrate, wherein the filtrate is sodium hydroxide solution, dropwise adding a proper amount of phytic acid solution, mixing and reacting divalent calcium magnesium and heavy metal ions in the precipitation solution, removing organic metal salt precipitate, dehydrating and concentrating under negative pressure to prepare caustic soda solution or solid, and detecting that the arsenic content is less than 0.5mg/L by TCLP experiment; the organic metal salt precipitate can be returned to the arsenic alkali residue material for utilization or used as a raw material for preparing phytic acid; the main components of the magnesium slag or the magnesium-calcium slag are magnesium-calcium carbonate and magnesium-calcium aluminosilicate minerals, the arsenic content is less than 0.5 percent, and the arsenic content in the leachate is detected to be less than 5mg/L by TCLP experiments, so that the magnesium slag or the magnesium-calcium slag can be directly used for making bricks or used as a sintering-aid raw material for cement production.
The refined soda is prepared by crushing alkaline residues, stirring and dissolving the crushed alkaline residues in hot water at 70-95 ℃, adding a polyaluminum ferric chloride flocculant, stirring and flocculating, filtering, washing and separating the mixture into solid residues and filtrate, wherein the filtrate is a mixture solution of sodium carbonate and sodium hydroxide, pressing the solid residues into carbon dioxide at 70-95 ℃ for reaction, completely converting the solid residues into a sodium carbonate solution, dropwise adding a proper amount of phytic acid solution, mixing the phytic acid solution for reaction, precipitating divalent calcium magnesium and heavy metal ions in the solution, removing organic metal salt precipitates, dehydrating, concentrating, spraying and drying under negative pressure to obtain a soda powder product, or dehydrating, concentrating, evaporating and drying under negative pressure to obtain solid soda, and grinding the solid soda to obtain a soda product, wherein the TCLP experiment detects that the arsenic content is less than 0.5; the organic metal salt precipitate can be returned to the arsenic alkali residue material for utilization or used as a raw material for preparing phytic acid; the main component of the solid slag is aluminosilicate mineral, the arsenic content is less than 1.0%, and the arsenic content in the leachate is less than 5mg/L by TCLP experiment detection, so that the solid slag can be directly used for making bricks or used as a raw material for cement production.
The technical principle and the beneficial effects of the utility model:
1) the simple powder material after being ground and pulverized is utilized to create the reaction condition of the raw materials for large-scale efficient reduction treatment; the 200-600 ℃ powder material preheated mainly by process waste heat is utilized, the processing capacity of the electric heating reduction furnace can be greatly improved, the power consumption is greatly saved, and the water content in the furnace is reduced;
2) selecting ' ammonia ' which can dissociate active hydrogen (ionic H +) under a certain condition and has strong reducing action as a reducing agent or a main reducing agent, injecting gasified and heated ammonia into materials in an electrothermal reducing furnace in a bottom injection or side injection or top injection or combined injection mode, rapidly reducing active hydrogen and ammonia which are activated and decomposed by ammonia into simple substance arsenic and simple substance antimony under the condition of 650-900 ℃ under the condition of blowing boiling of the efficient ' ammonia ' reducing agent, and rapidly reducing the reduced and generated simple substance arsenic into simple substance arsenic and simple substance antimony by ' ammonia ' and nitrogen (N) generated by decomposition of the ' ammonia2) The waste gas enters a residual ammonia finishing device, and residual ammonia is collected and recycled. Because the hot air flow is only limited by the negative pressure dragged by the centrifugal fan, the temperature is controlled to be not more than 900 ℃, the vapor pressure of antimony is very low, the antimony is difficult to escape along with the hot air flow, the high-efficiency and fast-reduced simple substance antimony (lead) is discharged from the outlet at the bottom of the reducing furnace in a clearance manner, the simple substance antimony (lead) is separated, the residue is discharged from the slag discharge port at the edge of the reducing furnace in a clearance manner,alkaline residue is separated. Thereby realizing the efficient and more thorough separation of arsenic, antimony and alkali in the arsenic-alkali residue; the main chemical reaction is as follows:
2NH3=N2+ 6H+/3H2
4NaAsO2+ 4NH3=As4↑+2N2↑+ 4NaOH + 4H2O↑
4Na3AsO4+ 8NH3=As4↑+ 4N2↑+ 12NaOH + 4H2O↑+2H2
4Na3AsO4+ 20H+/10H2=As4↑ + 12NaOH + 4H2O↑
2Na3AsO3+ 6H+/3H2=As4↑+ 6NaOH
2Na3SbO3+ 2NH3=2Sb + N2↑+6NaOH
2Na3SbO4+ 4NH3=2Sb + 2N2↑+ 6NaOH + 2H2O↑+ H2
2Na3SbO4+ 10H+/5H2=2Sb + 6NaOH+2H2O↑
2Na3SbO3+ 6H+/3H2=2Sb + 6NaOH
by using the ionic state H generated by decomposing ammonia at the temperature of 650-900 ℃ in the presence of arsenate, antimonate and the like+The catalyst shows extremely strong oxygen-deprivation reduction reaction activity and extremely high reduction efficiency; under the combined strong reduction action of active hydrogen and ammonia which are decomposition products of ammonia in a blowing state, the reduction separation efficiency of the arsenic-alkali residue is high, the reduction separation is high and thorough, no CO is generated, no pollution gas is generated, and no carbon is discharged;
3) the cooling heat exchanger is used for evaporating and heating ammonia, so that energy is saved, efficiency is high, complete condensation and separation of simple substance arsenic vapor in the cooler are facilitated, arrangement and collection of residual ammonia are facilitated, and smooth operation of the system is facilitated; and the energy-saving centrifugal fan is adopted to guide the simple substance arsenic vapor and the nitrogen-containing arsenic vapor2The mixture airflow of waste gases such as ammonia and the like has good energy-saving effect and operatesSafety;
4) by controlling the ammonia content in the waste gas to be 1.0-10%, not only can full reduction be ensured, but also the problem of oxidation of simple substance arsenic can be avoided, and NO NO can be ensured in the waste gasx、SO2The emission of the waste gas is avoided, and the environmental protection problems such as waste gas pollution and the like are avoided;
5) the method has simple process flow, easy automatic control in production, less investment, large handling capacity and no environmental protection problem of the common smelting process;
6) as the arsenic alkali residue which is extremely difficult to be properly treated is used as a raw material for producing arsenic, antimony and alkali, high-quality products which are suitable for market demands are produced by an energy-saving environment-friendly process, the arsenic alkali residue is thoroughly treated and separated, the problems of the existing method are well solved, and no secondary pollution hidden trouble exists.
Drawings
FIG. 1 is a schematic diagram showing the results of an arsenic alkali residue resource utilization apparatus in example 1 of the present invention;
FIG. 2 is a schematic diagram showing the results of the arsenic-alkali residue resource utilization equipment in embodiment 2 of the present invention.
Detailed Description
The invention is further illustrated by the following examples and figures.
The chemical reagents used in the embodiments of the present invention, if not specifically described, are commercially available in a conventional manner.
Example 1
As shown in fig. 1, the apparatus for recycling arsenic-alkali residue in this embodiment mainly includes: the device comprises an electrothermal reduction furnace (1), a powder air lock meter feeding device (2), an ammonia spraying device (3), a cooling (heat exchange) device (4), a residual ammonia finishing device (5), a centrifugal fan (6) and an ammonia storage device (7), wherein a discharge hole of the powder air lock meter feeding device (2) is connected with a powder inlet of the electrothermal reduction furnace (1), the ammonia spraying device (3) is respectively connected with the electrothermal reduction furnace (1) and the cooling (heat exchange) device (4) through an ammonia conveying pipeline, the cooling (heat exchange) device (4) is respectively connected with an exhaust outlet of the electrothermal reduction furnace (1) and an inlet of the residual ammonia finishing device (5) through a pipeline, a waste gas outlet of the residual ammonia finishing device (5) is connected with an air inlet of the centrifugal fan (6), and the ammonia storage device (7) is connected with the cooling (heat exchange) device (4) through a liquid ammonia conveying pipeline.
The working process of the device for resource utilization of arsenic alkali slag comprises the following steps: the powder material air-lock meter feeding device (2) continuously or intermittently feeds the preheated arsenic alkali residue powder material into the electrothermal reduction furnace (1), the liquid ammonia in the ammonia storage device (7) is pumped into the cooling (heat exchange) device (4) for heating and gasification, the gasified and heated ammonia is injected into the material in the electrothermal reduction furnace (1) by the ammonia injection device (3) in a bottom injection or side injection or top injection or combined injection mode, and under the condition of blowing boiling of the high-efficiency ammonia reducing agent, active hydrogen (H) such as arsenate, antimonate and the like which are activated and decomposed by ammonia under the temperature condition of 650-900 DEG C+) And ammonia is rapidly reduced into elemental arsenic and elemental antimony, the ammonia content of the waste gas is controlled to be 1.0-10%, the reduced elemental antimony (containing lead) is discharged from an outlet at the bottom of the reduction furnace (1) to obtain crude antimony, residues are discharged from a slag discharge port at the edge of the reduction furnace (1) to obtain alkaline slag, the elemental arsenic which is blown to boil and sublimate in a reducing mode is discharged from an exhaust port of the reduction furnace (1) along with waste gas flow drawn by a centrifugal fan (6) to enter a cooler (4) for cooling and solidification to obtain crude arsenic, and the waste gas enters a residual ammonia finishing device (5) for residual ammonia collection and recycling.
In the embodiment, arsenic alkali slag produced by an antimony smelting plant is used as a raw material, and the raw material comprises the following chemical components (average value): as9.34%, Sb 26.37%, Pb 4.95%, Na 24.46%, and arsenic alkali residue pre-grinding into powder with the residual content of 7% of a 180-mesh sieve; selecting commercially available liquid ammonia as a reducing agent; the test was conducted on a test apparatus.
The method for recycling arsenic alkali residue comprises the following steps: gasifying liquid ammonia by a heat exchange device, heating to 200 ℃, continuously feeding the arsenic alkali residue powder material preheated to 300 +/-10 ℃ into an electrothermal reduction furnace at 680 +/-10 ℃, directly blowing ammonia into the material in the furnace in a bottom spraying mode for rapid reduction, controlling the content of ammonia in the waste gas to be 4-6% by on-line detection, and discharging reduced elemental antimony from an outlet at the bottom of the reduction furnace to obtain crude antimony; discharging the residue from a slag discharge port at the edge of the reducing furnace to obtain alkaline slag; the simple substance arsenic vapor which is blown to boil and sublimated by reduction is discharged from the exhaust port of the reduction furnace along with the hot waste gas flow which is dragged by a centrifugal (draught) fan, enters a cooler for condensation and solidification, and is taken out to obtain crude arsenic; and the waste gas enters a residual ammonia finishing device, and residual ammonia is collected and recycled.
After the crude arsenic is crushed and dedusted, the purity is average 99 percent and the recovery rate of the arsenic is 99.3 percent.
The antimony and lead recovery rate is 98.5% and 98.1% through detection.
Refining crude arsenic by a mature process, namely crystallizing arsenic vapor at 450 ℃ to obtain gray α -arsenic, evaporating at 270 ℃ to obtain black glassy β -arsenic, and quenching the arsenic vapor by liquid nitrogen to obtain yellow gamma-arsenic.
The method takes alkaline slag as a raw material and comprises the following steps: crushing alkaline residues, adding 7.5 times of water, stirring, adding roasted magnesia powder according to the molar weight of 1.18 times of soda, stirring and reacting for 1 hour at 40 ℃, filtering, washing and separating into magnesium residues and filtrate, wherein the filtrate is sodium hydroxide solution, dropwise adding a proper amount of phytic acid solution for reaction, precipitating divalent calcium and magnesium and all heavy metal ions in the solution, filtering to remove organic metal salt precipitate, dehydrating and concentrating under negative pressure to prepare caustic soda solid, wherein the content of sodium hydroxide is 99.2%, and the content of arsenic is detected by TCLP experiment to be 0.08 mg/L. The magnesium slag detection mineral components are magnesium carbonate and magnesium calcium aluminosilicate, the arsenic content is 0.13%, and the TCLP experiment detection leachate has the arsenic content of 0.09mg/L, and is common fixed waste.
Example 2
As shown in fig. 2, the apparatus for recycling arsenic-alkali residue in this embodiment mainly includes: the device comprises an electrothermal reduction furnace (1), a powder air lock meter feeding device (2), an ammonia spraying device (3), a cooling (heat exchange) device (4), a residual ammonia finishing device (5), a centrifugal fan (6) and an ammonia storage device (7), wherein a discharge hole of the powder air lock meter feeding device (2) is connected with a powder inlet of the electrothermal reduction furnace (1), the ammonia spraying device (3) is respectively connected with the electrothermal reduction furnace (1) and the cooling (heat exchange) device (4) through an ammonia conveying pipeline, an inlet of the cooling (heat exchange) device (4) is connected with an exhaust outlet of the electrothermal reduction furnace (1), the centrifugal fan (6) is respectively connected with a waste gas outlet of the cooling (heat exchange) device (4) and an inlet of the residual ammonia finishing device (5) through pipelines, and the ammonia storage device (7) is connected with the cooling (heat exchange) device (4) through a liquid ammonia conveying pipeline.
Arsenic alkali slag produced by certain antimony smelting plant is selected as a raw material, and the raw material comprises the following chemical components (average value): as: 17.28%, Sb: 22.49%, Pb 4.35%, Na: 27.38 percent of arsenic alkali slag, and is pre-ground into powder with the residue of 1.7 percent of 200 meshes; selecting mixed ammonia of commercial liquid ammonia and hydrazine according to the mass ratio of 4:1 as a combined reducing agent; the test was conducted on a test apparatus.
The method for recycling arsenic alkali residue comprises the following steps: the mixed ammonia is gasified by a heat exchange device and heated to 100 ℃. The method comprises the steps of continuously feeding arsenic alkali residue powder materials preheated to 350 +/-10 ℃ into an electrothermal reduction furnace at 750 +/-10 ℃, directly blowing mixed ammonia into the materials in the furnace in a side-spraying and top-spraying mode for rapid reduction, controlling the content of ammonia detected on line in waste gas to be 1.5-3%, discharging reduced elemental antimony from an outlet at the bottom of the reduction furnace to obtain crude antimony, discharging residues from a slag discharge port at the edge of the reduction furnace to obtain alkaline residues, feeding reduced and blown sublimated elemental arsenic vapor into a cooler along with hot waste gas flow drawn by a centrifugal (induced) fan for condensation and solidification, taking out crude arsenic, and feeding the waste gas into a residual ammonia sorting device for residual ammonia collection and recycling.
After the crude arsenic is crushed and dedusted, the purity is average 99.1 percent and the recovery rate of the arsenic is 99.4 percent.
The antimony and lead recovery rate is 98.2% and 98.6% through detection.
Refining crude arsenic by a mature process, namely crystallizing arsenic vapor at 480 ℃ to obtain gray α -arsenic, evaporating at 250 ℃ to obtain black glassy β -arsenic, and quenching the arsenic vapor by liquid nitrogen to obtain yellow gamma arsenic.
Refining soda ash by taking alkaline slag as a raw material: crushing alkaline residues, adding hot water of 5.5 times and 90 ℃ for stirring and dissolving, then dropwise adding a polyaluminum ferric chloride flocculant for stirring and flocculating, filtering, washing and separating into solid residues and filtrate, wherein the filtrate is a mixture solution of sodium carbonate and sodium hydroxide, pressing carbon dioxide at the temperature of 90 ℃ for reaction, completely converting into a sodium carbonate solution, dropwise adding a proper amount of phytic acid solution for mixing and reacting, precipitating divalent calcium and magnesium and all heavy metal ions in the solution, filtering to remove organic metal salt precipitate, dehydrating, concentrating, evaporating and drying under negative pressure to obtain solid soda, grinding to prepare a soda product, detecting the soda content of 99.51%, and detecting the arsenic content of 0.06mg/L by a TCLP experiment. The main mineral of the solid slag is aluminosilicate mineral, the arsenic content is 0.24 percent, and the TCLP experiment detects that the arsenic content in the leaching solution is 0.11mg/L, which is common solid waste.
Example 3
The device for recycling arsenic alkali residue in this embodiment is the same as that in embodiment 1.
Arsenic alkali slag produced by certain antimony smelting plant is selected as a raw material, and the raw material comprises the following chemical components (average value): as: 22.92%,
Sb: 34.85%, Pb 3.27%, Na: 27.78 percent of arsenic-alkali residue, 15 percent of chaff by mass ratio are pre-ground into powder with a sieve of 160 meshes and 5 percent of residual; selecting commercially available liquid ammonia as a reducing agent; the test was conducted on a test apparatus.
The method for recycling arsenic alkali residue comprises the following steps: the liquid ammonia is gasified by a heat exchange device and heated to 250 ℃. The method comprises the steps of continuously feeding arsenic alkali residue powder materials preheated to 350 +/-10 ℃ into an electrothermal reduction furnace at 800 +/-10 ℃, directly blowing ammonia into the materials in the furnace in a bottom spraying mode for rapid reduction, controlling the content of ammonia detected on line in waste gas to be 2-4%, discharging reduced elemental antimony from an outlet at the bottom of the reduction furnace to obtain crude antimony, discharging residues from a slag discharge port at the edge of the reduction furnace to obtain alkaline residues, feeding the reduced and blown sublimated elemental arsenic vapor into a cooler along with hot waste gas flow drawn by a centrifugal fan for condensation and solidification, taking out the solidified arsenic to obtain crude arsenic, and feeding the waste gas into an ammonia residue finishing device for collecting and recycling residual ammonia.
After the crude arsenic is crushed and dedusted, the average purity is 98.7 percent and the recovery rate of the arsenic is 99.5 percent.
The antimony and lead recovery rate is 98.2% and 98.0% through detection.
Refining crude arsenic by a mature process, namely crystallizing arsenic vapor at 400 ℃ to obtain gray α -arsenic, evaporating at 240 ℃ to obtain black glassy β -arsenic, and quenching the arsenic vapor by liquid nitrogen to obtain yellow gamma-arsenic.
Refining caustic soda by taking alkaline slag as a raw material: crushing alkaline slag, adding 8 times of water, stirring, adding roasted magnesia powder according to the molar weight of 1.21 times of soda, stirring and reacting for 2.0 hours at 30 ℃, filtering, washing and separating into magnesium slag and filtrate, wherein the filtrate is sodium hydroxide solution, dropwise adding a proper amount of phytic acid solution for reaction, precipitating divalent calcium and magnesium and all heavy metal ions in the solution, filtering to remove organic metal salt precipitate, dehydrating and concentrating under negative pressure to prepare liquid alkali with the concentration of 60%, wherein the impurity content is less than 0.8%, and the TCLP experiment detects that the arsenic content is 0.09 mg/L. The magnesium slag detection mineral components are magnesium carbonate and magnesium calcium aluminosilicate, the arsenic content is 0.15%, and the TCLP experiment detection leachate has the arsenic content of 0.05mg/L, and is common fixed waste.
Example 4
The device for recycling arsenic alkali residue in this embodiment is the same as that in embodiment 1.
Arsenic alkali slag produced by certain antimony smelting plant is selected as a raw material, and the raw material comprises the following chemical components (average value): as: 13.87 percent,
Sb: 22.07%, Pb 2.97%, Na: 29.36 percent, arsenic-alkali residue and 5 percent of raw coal are pre-ground into powder with 200 meshes and 6 percent of residue; selecting mixed ammonia of commercial liquid ammonia and hydrazine according to the mass ratio of 2:1 as a combined reducing agent; the test was conducted on a test apparatus.
The method for recycling arsenic alkali residue comprises the following steps: the mixed ammonia is gasified by a heat exchange device and heated to 150 ℃. The method comprises the steps of continuously feeding arsenic alkali residue powder materials preheated to 300 +/-10 ℃ into an electrothermal reduction furnace at 780 +/-10 ℃, directly blowing mixed ammonia into the materials in the furnace in a side-spraying and top-spraying mode for rapid reduction, controlling the content of ammonia detected on line in waste gas to be 1.0-3.0%, discharging reduced elemental antimony from an outlet at the bottom of the reduction furnace to obtain crude antimony, discharging residues from a slag discharge port at the edge of the reduction furnace to obtain alkaline slag, feeding the reduced and blown sublimated elemental arsenic vapor into a cooler along with hot waste gas flow drawn by a centrifugal fan for condensation and solidification, taking out the cooled elemental arsenic vapor to obtain crude arsenic, and feeding the waste gas into a residual ammonia finishing device for residual ammonia collection and recycling.
After the crude arsenic is crushed and dedusted, the purity is average 99.3 percent and the recovery rate of the arsenic is 99.5 percent.
The antimony and lead recovery rate is 98.0% and 98.2% through detection.
Refining crude arsenic by a mature process, namely crystallizing arsenic vapor at 430 ℃ to obtain gray α -arsenic, evaporating at 250 ℃ to obtain black glassy β -arsenic, and quenching the arsenic vapor by liquid nitrogen to obtain yellow gamma-arsenic.
Refining soda ash by taking alkaline slag as a raw material: crushing alkaline residues, adding 6.5 times of hot water at 85 ℃, stirring and dissolving, then, dropwise adding a polyaluminum ferric chloride flocculant, stirring and flocculating, filtering, washing and separating into solid residues and filtrate, wherein the filtrate is a mixture solution of sodium carbonate and sodium hydroxide, pressing carbon dioxide at 85 ℃ for reaction, completely converting into a sodium carbonate solution, dropwise adding a proper amount of phytic acid solution for mixing and reacting, precipitating divalent calcium and magnesium and all heavy metal ions in the solution, filtering to remove organic metal salt precipitate, dehydrating under negative pressure, concentrating, spraying and drying to obtain a soda powder product, detecting the soda content to be 99.47%, and detecting the arsenic content to be 0.07mg/L by a TCLP experiment. The main mineral of the solid slag is aluminosilicate mineral, the arsenic content is 0.27 percent, and the TCLP experiment detects that the arsenic content in the leaching solution is 0.09mg/L, which is common solid waste.
Example 5
The device for recycling arsenic alkali residue in this embodiment is the same as that in embodiment 1.
Arsenic alkali slag produced by certain antimony smelting plant is selected as a raw material, and the raw material comprises the following chemical components (average value): as: 9.74%, Sb: 27.45%, Pb4.18%, Na: 29.12 percent of arsenic-alkali residue and 8 percent of raw coal by mass are added and pre-ground into powder with the particle size of 120 meshes and the particle size of 0.7 percent; mixing commercially available liquid ammonia and natural gas according to the mass ratio of 2:1 to serve as a combined reducing agent; the test was conducted on a test apparatus.
The method for recycling arsenic alkali residue comprises the following steps: gasifying and heating mixed ammonia to 180 ℃ by a heat exchange device, continuously feeding arsenic alkali slag powder materials preheated to 210 +/-10 ℃ into an electrothermal reduction furnace at 850 +/-10 ℃, directly blowing the mixed ammonia into the materials in the furnace in a side-spraying and top-spraying mode for rapid reduction, controlling the content of ammonia in waste gas to be 2-3% in an on-line detection mode, discharging reduced elemental antimony from an outlet at the bottom of the reduction furnace to obtain crude antimony, discharging residues from a slag discharge port at the edge of the reduction furnace to obtain alkaline residues, feeding reduced and blown sublimated elemental arsenic vapor into a cooler along with hot waste gas flow drawn by a centrifugal fan for condensation and solidification, taking out the crude arsenic, and feeding waste gas into a residual ammonia finishing device for residual ammonia collection and recycling.
After the crude arsenic is crushed and dedusted, the average purity is 98.9 percent and the recovery rate of the arsenic is 99.1 percent.
The antimony and lead recovery rate is 98.1% and 98.6% through detection.
Refining crude arsenic by a mature process, namely crystallizing arsenic vapor at 480 ℃ to obtain gray α -arsenic, evaporating at 250 ℃ to obtain black glassy β -arsenic, and quenching the arsenic vapor by liquid nitrogen to obtain yellow gamma arsenic.
Refining soda ash by taking alkaline slag as a raw material: crushing alkaline residues, adding hot water of 8 times of the alkaline residues and stirring and dissolving the alkaline residues, then adding a polyaluminum ferric chloride flocculating agent dropwise, stirring and flocculating, filtering, washing and separating the solid residues and filtrate, wherein the filtrate is a mixture solution of sodium carbonate and sodium hydroxide, pressing carbon dioxide at the temperature of 80 ℃ for reaction, completely converting the mixture solution into a sodium carbonate solution, adding a proper amount of phytic acid solution for mixing and reacting, precipitating divalent calcium magnesium and all heavy metal ions in the solution, filtering to remove organic metal salt precipitates, dehydrating the organic metal salt precipitates under negative pressure, concentrating the organic metal salt precipitates under the proper amount of negative pressure, performing spray drying to obtain a soda powder product, detecting the soda content to be 99.53 percent, and detecting the arsenic content to be 0.07 mg. The main mineral of the solid slag is aluminosilicate mineral, the arsenic content is 0.37 percent, and the TCLP experiment detects that the arsenic content in the leaching solution is 0.16mg/L, which is common solid waste.

Claims (2)

1. An arsenic alkali residue resource utilization device is characterized by comprising an electrothermal reduction furnace (1), a powder air lock meter feeding device (2), an ammonia spraying device (3), a cooling heat exchanger (4), a residual ammonia finishing device (5), a centrifugal fan (6) and an ammonia storage device (7), the device is characterized in that a discharge hole of the powder air lock meter feeding device (2) is connected with a powder inlet of the electrothermal reduction furnace (1), the ammonia spraying device (3) is respectively connected with the electrothermal reduction furnace (1), the cooling heat exchanger (4) is connected with an ammonia conveying pipeline, the cooling heat exchanger (4) is respectively connected with an exhaust outlet of the electrothermal reduction furnace (1), an inlet of the residual ammonia sorting device (5) is connected with a pipeline, a waste gas outlet of the residual ammonia sorting device (5) is connected with an air inlet of the centrifugal fan (6), and the ammonia storage device (7) is connected with the cooling heat exchanger (4) through a liquid ammonia conveying pipeline.
2. The arsenic alkali residue resource utilization equipment as claimed in claim 1, wherein the centrifugal fan (6) is respectively connected with the waste gas outlet of the cooling heat exchanger (4) and the air inlet of the residual ammonia finishing device (5).
CN201921042504.4U 2019-07-05 2019-07-05 Arsenic alkali residue resource utilization equipment Active CN210420096U (en)

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