CN105088274B - A kind of device for processing and reclaiming aluminium electroloysis solid waste - Google Patents

A kind of device for processing and reclaiming aluminium electroloysis solid waste Download PDF

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Publication number
CN105088274B
CN105088274B CN201510519831.4A CN201510519831A CN105088274B CN 105088274 B CN105088274 B CN 105088274B CN 201510519831 A CN201510519831 A CN 201510519831A CN 105088274 B CN105088274 B CN 105088274B
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refractory
furnace
alkali metal
resistance heater
liner
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CN105088274A (en
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冯乃祥
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Shenyang Beiye Metallurgical Technology Co Ltd
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Shenyang Beiye Metallurgical Technology Co Ltd
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Abstract

A kind of device for processing and reclaiming aluminium electroloysis solid waste, including the refractory material wall at middle part, alkali metal crystallizer, heat-insulated cover plate, metal cap, electrode and secondary material room, electrolyte crystallisation chamber and alkali metal crystallisation chamber in furnace shell, bell, inner lining of furnace, furnace wall refractory wall, bottom refractory liner body, resistance heater, stove;The fragment of waste cathode carbon block of the described resistance heater by particle diameter less than 10cm is constituted.Device of the invention can realize being completely separated for charcoal in waste cathode carbon block and charcoal liner, alkali metal and electrolyte, be a kind of aluminium electroloysis solid waste treatment device of energy-conserving and environment-protective, be especially suitable for industrially large-scale promotion application.

Description

A kind of device for processing and reclaiming aluminium electroloysis solid waste
Technical field
The invention belongs to metallurgy environment technical field, more particularly to a kind of dress for processing and reclaiming aluminium electroloysis solid waste Put.
Background technology
Aluminium is, using cryolite-alumina electrolyte system, life to be electrolysed under 950 ~ 980 DEG C of temperature conditionss in industry Produce, during aluminum electrolysis, produce following 4 kinds of solid wastes:
1st, waste cathode carbon block.Waste cathode of aluminum electrolytic cell carbon block refers to aluminium cell through electrolysis after a while, appearance After bottom land breakage, the bottom land cathode carbon pieces and side wall carbon block taken out from damaged electrolytic cell, wherein also include side wall carbon block with The carbon block formed by ramming paste between bottom cathode carbon block, and ramming paste between cathode carbon pieces is under the conditions of electrolysis temperature The carbon block of formation.During aluminum electrolysis, it is metallic sodium that small part sodium fluoride can also be reduced electrochemically.In electrolytic cell In whole usage cycles, electrolyte and metallic sodium can permeate in carbonaceous cathode material always.Therefore, going out from damaged plow Aluminium electroloysis waste cathode carbon block typically contains about 30% or so electrolyte and about 10% or so metallic sodium.Current China electrolytic aluminium factory The average life span of the electrolytic cell for being used by taking an electrolytic aluminium factory for producing 1000000 tons/year per year as an example, was produced every year at 5 years or so Raw waste cathode carbon block is about at 10,000 tons or so, that is to say, that electrolytic aluminium factory often produces 100 tons of electrolytic aluminiums it is necessary to produce 1 ton useless Cathode carbon pieces.
2nd, give up electrolytic cell refractory lining.Useless electrolytic cell refractory lining is that electrolyte passes through the moon in electrolytic process The crack that ramming paste between the hole of pole carbon block and the crack of cathode bottom block and cathode bottom block and sole piece is formed penetrates into In the refractory material of charcoal cathode bottom block bottom, and reacted with refractory material and formed.Therefore, give up electrolytic cell refractory lining The main compound by the reaction generation of electrolyte, electrolyte and refractory material, and unreacted refractory material composition, wherein electricity Solution matter is mainly by Na with the compound of refractory material reaction generation2O, Al2O3And SiO2The compound of formation.In aluminium cell It is this by silicon nitride bonded silicon also including a kind of Tercod liner by silicon nitride bonded silicon in waste refractory materials liner Tercod liner, only apply the sidepiece in large scale electrolytic cell.
3rd, anode breeze.The anode of cryolite-alumina electrolyte system is broken into difference using the petroleum coke after calcining Grade mix with coal tar pitch, kneading and compacting, then it is fired after be made.In the production process of aluminium electroloysis, carbon anode is constantly consumed, Need to consume 0.334 ton of carbon anode per one ton of metallic aluminium of electrolysis production in theory, and actually often produce one ton of metallic aluminium, charcoal sun Pole is consumed more than 0.4 ton, i.e., actual carbon anode consumption consumes many 70kg/t-Al or so than theoretical carbon anode, and what is had is up to 100 more than kg/t-Al, 70~100 kg/t-Al of this many consumption are mainly the CO in air and electrolytic cell2Carbon anode is entered Row oxidation and lose, also sizable part consumption is that part charcoal sheds into electrolytic cell from anode in electrolytic process In turn into breeze.This breeze has fine-powdered and a graininess, consolute in or can not only influence aluminium electrolyte in being suspended in electrolyte Physical and chemical performance, such as electrical conductivity, viscosity, the current efficiency of the also working condition to electrolytic cell and electrolytic cell causes shadow Ring.So that electrolysis workman periodically pulls these breezes out from electrolytic cell, and adhered in the breeze pulled out substantial amounts of Electrolyte, ratio accounts for 70%, and electrolytic aluminium factory gives it up this breeze, and what is also had is too high containing electrolyte ingredient by bulk Breeze carbon block smashing after, in returning to electrolytic cell, and tiny breeze is still discarded, and in turn results in the loss of charcoal and electrolyte And environment is polluted.1 ton of aluminium is often produced in usual industrial cell and about produces 3~5kg breezes, 500,000 tons of gold of an annual output Belong to the electrolytic aluminium factory of aluminium, the breeze amount of a year is about 1500~2000 tons.
4th, aluminium ash.The aluminium slag that will generally be clawed from the aluminum holding furnace of electrolytic aluminium foundry, and aluminium ingot(Rod or plate)Casting The slag for coming is laid during making, and the slag charge of pouring aluminium ladle liner adhesion is referred to as aluminium slag.The main component of aluminium slag is alumina A small amount of reunion shape metallic aluminium that the powdery aluminum and powdery aluminum formed after change are coated.Aluminium slag is sieved after ball milling, The metallic aluminium of reunion shape can be sifted out, the powder under sieve is referred to as aluminium ash.Aluminium ash is by tiny granular metallic aluminium and aluminum oxide Composition, wherein also inevitable that micro electrolyte fluoride is present.Either electrolytic aluminium factory or aluminium slag are returned at present Workshop is zoomed in, it is all abandoned in this part " aluminium ash " as rubbish, environment is affected greatly.
In addition to the solid waste that above-mentioned 4 kinds of aluminum electrolysis are produced, by the damaged leakage aluminium fusing cathode steel of bottom of electrolytic tank Rod and the Al-Fe alloys that produce, although in principle and be not belonging to solid waste, but due to its amount less, alloying component is not again solid It is fixed, thus often the liner by electrolytic aluminium factory as rubbish companion electrolytic cell is abandoned.
At present, there is no one technically and economically all feasible method aluminium electroloysis solid waste is effectively treated and Reclaim.But the method explored treatment and reclaim the solid waste that aluminium cell production is produced, always people of being turned waste into wealth Hope and research topic.Among these, enjoy that people pay close attention to and most study is waste cathode of aluminum electrolytic cell carbon block and anode The treatment and recycling of breeze, because the chemical combination of the charcoal, electrolyte components and charcoal in waste cathode carbon block and anode breeze Thing component is the component with very big recovery value, and amount is big, if abandoning it, not only valuable component therein cannot Recycle, and fluoride components therein can cause very big influence to environment.Comparatively, to the useless fire resisting of electrolytic cell It is few that the recycling of material liner is then studied.Early in the fifties in last century, people begin to how research processes and reclaim The waste cathode carbon block and breeze produced using aluminium cell production, these methods are nothing more than three kinds:1 is as other Chemical Manufactures During additive, such as using waste cathode carbon block grinds as manufacture of cement additive, but this partial amounts seldom because Too many, the fluoride in its waste cathode carbon block can influence the quality of cement, therefore not welcome by cement producer;2 are As fuel, but secondary pollution problem is there is also as fuel;3 is to reclaim electrolyte therein, among these most study Be to be separated the charcoal in anode breeze and waste cathode carbon block and electrolyte components using the method for flotation, but be up to now Only, this method is not yet successfully applied to industrially, because can not fully by electrolyte from waste cathode carbon using floatation Separated in block, and the waste water that floatation process is produced also easily causes secondary pollution.1958, in the patent of US2858198 A kind of method that use way of distillation separates electrolyte components in waste cathode of aluminum electrolytic cell carbon block is proposed, but this method is used Device be tower structure, heating means are external heat, presumably due to device is complicated, operating difficulties, energy consumption are higher etc., and reason is straight Also fail to industrially be applied till now.
The content of the invention
Regarding to the issue above, the present invention provides a kind of device for processing and reclaiming aluminium electroloysis solid waste, using aluminium electroloysis The conduction property of groove waste cathode carbon block solid parts is made the high-temperature vacuum electricity using waste cathode carbon block fragment as resistance heater Resistance stove;Produce high temperature using the resistance heat of waste cathode carbon block fragment, make the chunky shape material of waste cathode carbon block under vacuum by 1000-1400 DEG C is heated to, in the electrolyte ingredient in waste cathode carbon block fragment is evaporated and is condensed in electrolyte crystallisation chamber, Alkali metal in waste cathode carbon block fragment(Na or Na-K alloys)Be evaporated the alkali metal knot being agglomerated in alkali metal crystallisation chamber On brilliant device, while the pair adjacent with resistance heater is expected into room using the heat of high temperature of this heated waste cathode carbon block fragment Interior anode breeze material or useless electrolytic cell refractory lining milling material are mixed with the levigate material of aluminium ash or Al-Fe alloys Briquetting material be heated to 900-1200 DEG C, the electrolyte components in anode breeze or waste refractory materials is evaporated, condense in In electrolyte crystallisation chamber, electrolytic cell waste refractory materials liner is milled and expect to be mixed with the levigate material of aluminium ash or Al-Fe alloys Briquetting material the alkali metal of generation is reacted under elevated temperature in vacuo(Sodium or Na-K alloy etc.)Alkali is agglomerated to after being evaporated On alkali metal crystallizer in metallic crystal room.
The device for the treatment of of the invention and recovery aluminium electroloysis solid waste includes furnace shell, bell, inner lining of furnace, furnace wall fire proofed wood Refractory material wall, alkali metal crystallizer, the insulation cover at middle part in material wall, bottom refractory liner body, resistance heater, stove Plate, metal cap, electrode and secondary material room, electrolyte crystallisation chamber and alkali metal crystallisation chamber;
Described furnace shell is a box metal shell, is made up of sheet metal material;The top outer of furnace shell has method Blue structure, the outer wall of the primary reformer shell under flange arrangement is provided with cooling jacket, and vacuum is welded with the furnace shell of flange arrangement bottom Exhaust tube;Also be welded with furnace shell top flange structure lower edge can be filled with stove argon gas or other inert gases gas tube and The pressure vacuum gauge of display furnace pressure and vacuum condition;
Described bell is made of steel metal material, and vacuum pad is provided between the flange arrangement and bell on edge on furnace shell Circle;
Described inner lining of furnace is made up of stove lateral lining and bottom lining, and the inwall of stove lateral lining is made up of refractory material Wall, referred to as furnace wall refractory wall, the internal layer of bottom lining is the liner body being made up of refractory material, referred to as furnace bottom fire resisting Material liner body, is the liner body being made up of insulation material between furnace wall refractory wall and side fireplace shell, referred to as furnace wall thermal insulating material Material liner body;It is the liner body being made up of insulation material, referred to as bottom heat insulation material between bottom refractory liner body and furnace bottom furnace shell Liner body;
Described furnace wall refractory wall is higher than furnace wall insulation material liner body, has groove at the top of furnace wall refractory wall Type opening, makes electrolyte crystallisation chamber be connected with alkali metal crystallisation chamber by this slot-type openings;
The refractory material wall at middle part is seated on bottom refractory liner body in described stove, with furnace bottom fire resisting Material liner body is vertical, and against the medial surface wall vertically upward of resistance heater;Middle part refractory material wall in stove Highly equal to or less than the height of furnace wall refractory wall, when the height of middle part refractory material wall in stove is equal to furnace wall fire resisting During the height of material wall, slot-type openings are provided with the top of the refractory material wall of middle part in stove, are expected pair by this slot-type openings The electrolyte crystallisation chamber on room top is connected with the electrolyte crystallisation chamber above resistance heater;
Described heat-insulated cover plate makes of refractory material, positioned at the top of furnace wall refractory wall;Outside heat-insulated cover plate Along the outer more than furnace wall refractory wall;
Described metal cap is one the rectangle bucket of bottom uncovered, and left-hand thread makes the bucket of metal cap on heat-insulated cover plate Wall is inserted into alkali metal crystallizer;On metal cap, bell is arranged with warming plate;
Described alkali metal crystallizer is made up of stainless steel plate, and alkali metal crystallizer outer wall is close to the stove with cooling jacket The inwall of shell, the bottom of alkali metal crystallizer is a groove-shaped design;Alkali metal crystalliser feet is served as a contrast positioned at furnace wall insulation material The upper surface of body;
The fragment of waste cathode carbon block of the described resistance heater by particle diameter less than 10cm is constituted;By the broken of waste cathode carbon block Block is placed between the refractory material wall and the graphite body of two electrodes by middle part in furnace wall refractory wall, stove and is surrounded Strip space in, formed resistance heater;Resistance heater is higher than 0 ~ 30cm of graphite body;
Described electrode is made up of two parts electric conductor, and the electric conductor of the part that is in contact with resistance heater on the inside of stove is stone Black electric conductor;The section configuration of graphite body is rectangle;The electric conductor being connected with graphite body is metallic conductor, referred to as Metal electrode, its section is circle;The cross-sectional area of metal electrode leads to less than the cross-sectional area of graphite body in metal electrode There is cooling water;There is insulation seal device between metal electrode and furnace shell;
Described secondary material room is to be located at the refractory material wall and two by middle part in stove on bottom refractory liner body Interelectrode furnace wall refractory wall surrounded its highly with resistance heater height identical space.
Described electrolyte crystallisation chamber has two kinds, and one kind is located on resistance heater, under heat-insulated cover plate by height The space that refractory material wall in middle part in the furnace wall refractory wall and stove of resistance heater is surrounded;Another kind electrolysis Matter crystallisation chamber is located on secondary material room charge level position, under heat-insulated cover plate by the stove higher than resistance heater middle part it is resistance to The space that furnace wall refractory wall between fiery material wall and two electrodes is formed;
Described alkali metal crystallisation chamber is located on the insulation material liner body of furnace wall, resistance to by the furnace wall higher than resistance heater The space surrounded between fiery material wall and alkali metal crystallizer;In alkali metal crystallisation chamber, left-hand thread is on heat-insulated cover plate The bucket wall of metal cap extend into from the top down in alkali metal crystallisation chamber.
In said apparatus, there is an electrode at the two ends of each individual resistors heater, and one of them is into electrode, separately One is electrode;When resistance heater is set for U-shaped design or П types, two electrodes of resistance heater are in furnace shell Same side;It is parallel to each other and when separate straight line body is designed when resistance heater is two, the heating of each individual resistors Two electrodes of body are located on two corresponding sides of furnace shell respectively, now, two electrodes and power supply of same side Connection, is connected between two electrodes of another side with metallic conductor, makes heated current same from a resistance heater inflow Another resistance heater in individual stove;After can also be by the two of opposite side electrode metallic conductor connections, by the device Heated current be input to in its structure identical another device;The resistance heater made by waste cathode of aluminum electrolytic cell carbon block It is the heat source body for making to be produced in stove resistance heat, is again aluminium cell solid waste that is a kind of processed and being reclaimed.
Above-mentioned secondary material room is used to load the anode breeze or the levigate material of electrolytic cell waste refractory materials to be processed and reclaimed The briquetting material being mixed with aluminium ash or the levigate material of Al-Fe alloys.
The distance of the bucket wall of above-mentioned metal cap and the bottom of alkali metal crystallizer is in 5 ~ 30cm.
A kind of application method of device for processing and reclaiming aluminium electroloysis solid waste of the invention is carried out according to the following steps:
(1)Fragment by waste cathode of aluminum electrolytic cell carbon block smashing into particle diameter less than 10cm, is placed in bottom refractory liner body On, the space formed by the refractory material wall and the graphite body of two electrodes in the middle part of furnace wall refractory wall, stove It is interior, form resistance heater;
(2)Briquetting material is placed in secondary material room;The height of briquetting material is highly identical with resistance heater;Described briquetting Expect to be formed by the compacting of anode breeze, or mix compacting with aluminium ash by the milling material of the waste refractory materials liner of electrolytic cell and form, Or formed with Al-Fe alloyed powder mixing compactings by the milling material of the waste refractory materials liner of electrolytic cell;
(3)Alkali metal crystallizer is placed into, heat-insulated cover plate is covered, metal cap is put, then puts warming plate, stove is covered afterwards Lid;
(4)Below 100Pa will be evacuated down in body of heater, to being passed through cooling water in cooling jacket, then be passed through to metal electrode Cooling water, is then electrified to, and the temperature of resistance heater is risen to 1000 ~ 1400 DEG C, reaches the temperature of the indoor briquetting material of secondary material 900~1200℃;In electrolyte components, the indoor anode breeze of secondary material in resistance heating body at this temperature and vacuum condition Electrolyte components in the milling material of the waste refractory materials liner of electrolyte components or electrolytic cell are evaporated, and condense in electricity In solution matter crystallisation chamber;And after the alkali metal in resistance heater is distilled off, through the groove profile at the top of furnace wall refractory wall Opening enters alkali metal crystallisation chamber, then in alkali metal crystallizer condensed on inner walls;And the waste refractory materials liner of electrolytic cell After the alkali metal of the reactive aluminum generation in milling material and aluminium ash or Al-Fe alloyed powders is distilled off, via middle part fire resisting in stove Gap and furnace wall in slot-type openings or stove at the top of material wall between middle part refractory material wall top and heat-insulated cover plate is resistance to Slot-type openings at the top of fiery material wall enter alkali metal crystallisation chamber, then in alkali metal crystallizer condensed on inner walls.
(5)This temperature and vacuum condition are maintained more than 0.5 hour, make to be powered off after the completion of metallurgical processes whole in device, Vacuum is closed, then to argon gas is passed through in device, normal pressure in holding meanss after temperature is down to room temperature, opens bell, from stove Interior taking-up electrolyte, condensation has the alkali metal crystallizer of alkali metal, and the waste cathode carbon block for having isolated electrolyte, alkali metal Fragment, has isolated electrolyte or has removed the briquetting material of alkali metal and electrolyte.
Described alkali metal is sodium or Na-K alloy, or is sodium or Na-K alloy containing lithium.
The milling material of the waste refractory materials of electrolytic cell regards aluminium content and useless electrolytic cell in aluminium ash with the mixed proportion of aluminium ash Waste refractory materials milling material in alkali metal oxide content depending on, the aluminium that allow in principle in allocated into aluminium ash is by electricity Alkali metal oxide in the milling material of the waste refractory materials for solving groove is completely reduced into alkali metal for dispensing criterion;Electrolytic cell gives up The proportioning of refractory material pulverized powder and Al-Fe alloyed powders also carries out dispensing by this criterion, wherein the waste refractory materials of electrolytic cell The granularity of milling material, aluminium ash and Al-Fe alloyed powders is respectively less than 100 mesh.
When pair material interior does not load briquetting material or other materials, step(4)The heating-up temperature of middle resistance heater is 1000~1300℃。
A kind of device for processing and reclaiming aluminium electroloysis solid waste of the invention, is capable of achieving in waste cathode carbon block and charcoal liner Charcoal, alkali metal and electrolyte be completely separated, and electrolyte, alkali metal and refractory material in useless cathode inner lining refractory material Component is completely separated, and in anode breeze electrolyte and charcoal separation, also make aluminium ash and the cathode steel bar institute melted by aluminium The Al-Fe alloys of formation are utilized effectively.Whole process is produced without waste residue, waste gas, waste water, is a kind of aluminium electricity of energy-conserving and environment-protective Solution solid waste treatment device, is especially suitable for industrially large-scale promotion application.
Brief description of the drawings
Fig. 1 is A-A faces sectional view when resistance heater is the design of П types in present example 1;
Fig. 2 is B-B faces sectional view when resistance heater is the design of П types in present example 1;
Fig. 3 is the resistance heater and the C- C of electrode structure when resistance heater is the design of П types in present example 1 Face sectional view;
Fig. 4 is the U-shaped resistance heater and the C-C of electrode structure when resistance heater is U-shaped design in present example 2 Face sectional view;
Fig. 5 is that resistance heater is that C-C faces are cutd open when two independent and parallel to each other straight line bodies are designed in present example 3 View;
Fig. 6 is A-A faces profile when only single resistance heater is designed in present example 4;
Fig. 7 is B-B faces profile when only single resistance heater is designed in present example 4;
Fig. 8 is C-C faces profile when only single resistance heater is designed in present example 4;
In figure, 1- furnace shells, 2- bells, 3- resistance heaters, 4- furnace wall refractory walls, the fire proofed wood at middle part in 5- stoves Material wall, 6- furnace walls insulation material liner body, the slot-type openings at the top of 7- furnace wall refractory walls, the heat-insulated cover plates of 8-, 9- metals Cover, 10- warming plates, 11- alkali metal crystallizers, the secondary material rooms of 12-, 13- alkali metal crystallisation chambers, the electricity on 14- resistance heaters top Solution matter crystallisation chamber, the electrolyte crystallisation chamber on the secondary material room tops of 15-, 16- vacuum exhaust pipes, 17- gas tubes, 18- pressure vacuum gauges, 19- graphite bodies, 20- metal electrodes, 21- insulation seal devices, 22- cooling of electrode water water inlet pipes, 23- cooling of electrode water goes out Slot-type openings in water pipe, 24- stoves at the top of the refractory material wall at middle part, 25- vacuum packing rings, 26- metallic conductors, 27- coolings Water jacket, 28- bottom refractory liner bodies, 29- bottom heat insulation material liner bodies.
Specific embodiment
The device embodiments of a kind for the treatment of of the invention and recovery aluminium electroloysis solid waste are with following example explanation.
Furnace shell of the invention is a box metal shell, is made up of sheet metal material;Bell steel metal material It is made.
Heat-insulated cover plate of the invention makes of refractory material.
Refractory material of the invention selects refractory concrete.
Alkali metal crystallizer of the invention is made up of stainless steel plate.
Embodiment 1
Treatment and reclaim aluminium cell solid waste apparatus structure as shown in Figure 1, Figure 2 and Figure 3;Resistance heater is П Type is designed;
Fire proofed wood including middle part in furnace shell 1, bell 2, inner lining of furnace, furnace wall refractory wall 4, resistance heater 3, stove Material wall 5, alkali metal crystallizer 11, heat-insulated cover plate 8, metal cap 9, electrode, secondary material room 12, electrolyte crystallisation chamber and alkali metal knot Brilliant room 13;
Furnace shell 1 is a box metal shell, is made up of sheet metal material;The top outer of furnace shell 1 has flange knot Structure, the outer wall of the primary reformer shell 1 under flange arrangement is provided with cooling jacket 27, and vacuum is welded with the furnace shell 1 of flange arrangement bottom Exhaust tube 16;Also being welded with the top flange structure lower edge of furnace shell 1 can be to the inflation that argon gas or other inert gases are filled with stove The pressure vacuum gauge 18 of pipe 17 and display furnace pressure and vacuum condition;
Bell 2 is made of steel metal material, is provided with vacuum packing ring 25 on furnace shell 1 between the flange arrangement on edge and bell 2;
Described inner lining of furnace is made up of stove lateral lining and bottom lining, and the inwall of stove lateral lining is furnace wall refractory Wall 4, the internal layer of bottom lining is bottom refractory liner body 28, is stove between furnace wall refractory wall 4 and furnace wall furnace shell 1 Wall insulation material liner body 6, is bottom heat insulation material liner body 29 between bottom refractory liner body 28 and furnace bottom furnace shell;
Described furnace wall refractory wall 4 is higher than furnace wall insulation material liner body 6, the top of furnace wall refractory wall 4 There are slot-type openings 7, electrolyte crystallisation chamber 14 is connected with alkali metal crystallisation chamber 13 by this slot-type openings;
The refractory material wall 5 at middle part is seated on bottom refractory liner body in described stove, resistance to furnace bottom Fiery material liner body is vertical, and against the medial surface wall vertically upward of resistance heater 3;The refractory material wall at middle part in stove Slot-type openings 24 are also arranged at the top of body 5, and with the identical of furnace wall refractory wall 4 highly;The fire proofed wood at middle part in stove The slot-type openings 24 at material wall 5 top are by the electricity above the electrolyte crystallizer room 15 on the pair material top of room 12 and resistance heater 3 Solution matter crystallisation chamber 14 is connected;
Described heat-insulated cover plate 8 makes of refractory material, the fire proofed wood at middle part in furnace wall refractory wall 4 and stove Expect the top of wall 5;Outer of the outer of heat-insulated cover plate 8 more than furnace wall refractory wall 4;
The metal cap 9 is one the rectangle bucket of bottom uncovered, and left-hand thread makes the bucket of metal cap 9 on heat-insulated cover plate 8 Wall is inserted into alkali metal crystallizer 11;On metal cap 9, bell 2 is arranged with warming plate 10;
Described alkali metal crystallizer 11 is made up of stainless steel plate, and the outer wall of alkali metal crystallizer 11 is close to cooling jacket The inwall of 27 furnace shell 1, the bottom of alkali metal crystallizer 11 is a groove-shaped design;The groove position of the bottom of alkali metal crystallizer 11 In the upper surface of furnace wall insulation material liner body 6;
The fragment of waste cathode carbon block of the described resistance heater 3 by particle diameter less than 10cm is constituted;By waste cathode carbon block Fragment is placed in and is enclosed by the graphite body 19 of the electrode of refractory material wall 5 and two at middle part in furnace wall refractory wall 4, stove Into space in, formed resistance heater 3;Resistance heater 3 is higher by 10cm than graphite body 19;
Described electrode is made up of two parts electric conductor, and the electric conductor of the part that is in contact with resistance heater 3 on the inside of stove is Graphite body 19, the section of graphite body is rectangle;The electric conductor being connected with graphite body 19 is metallic conductor, is claimed It is metal electrode 20, its section is circle;The cross-sectional area of metal electrode 20 is less than the cross-sectional area of graphite body 19, metal Cooling water is connected with electrode 20;There is insulation seal device 21 between metal electrode 20 and furnace shell 1;
Described secondary material room 12 be located on bottom refractory liner body by the refractory material wall 5 at middle part in stove with Its spatial altitude that two interelectrode furnace wall refractory walls 4 are surrounded and the height identical space of resistance heater 3;
Described electrolyte crystallisation chamber has two kinds, and a kind of electrolyte crystallisation chamber 14 is located on resistance heater, heat-insulated The refractory material wall 5 by middle part in the furnace wall refractory wall 4 and stove higher than resistance heater 3 under cover plate is surrounded Space;Another electrolyte crystallisation chamber 15 is located on secondary material room charge level position, under heat-insulated cover plate by higher than resistance The space that furnace wall refractory wall 4 in the stove of heater between middle part refractory material wall 5 and two electrodes is formed;
Described alkali metal crystallisation chamber 13 is located on furnace wall insulation material liner body 6, by the furnace wall higher than resistance heater 3 The space surrounded between refractory material wall 4 and alkali metal crystallizer 11;In alkali metal crystallisation chamber 13, left-hand thread is in insulation cover The bucket wall of the metal cap 9 above plate 8 extend into alkali metal crystallisation chamber 13 from the top down;
There is an electrode at the two ends of resistance heater 3, and one of them is that, into electrode, another is electric electrode;Electricity Resistance heater 3 is set for П types, and two electrodes are in the same side of furnace shell 1;
The distance of the bucket wall of metal cap 9 and the bottom of alkali metal crystallizer 11 is in 15cm;
Application method is:
(1)Fragment by waste cathode of aluminum electrolytic cell carbon block smashing into particle diameter less than 10cm, is placed in bottom refractory liner body On, the space formed by the refractory material wall and the graphite body of two electrodes in the middle part of furnace wall refractory wall, stove It is interior, form resistance heater;
(2)Briquetting material is placed in secondary material room;The height of briquetting material is highly identical with resistance heater;Described briquetting Material is formed by the compacting of anode breeze;
(3)Alkali metal crystallizer is placed into, heat-insulated cover plate is covered, metal cap is put, then puts warming plate, stove is covered afterwards Lid;
(4)Below 100Pa will be evacuated down in body of heater, to being passed through cooling water in cooling jacket, then be passed through to metal electrode Cooling water, is then electrified to, and the temperature of resistance heater is risen to 1350 DEG C, the temperature of the indoor briquetting material of secondary material is reached 1100 ℃;The electrolyte group in electrolyte components, the indoor anode breeze of secondary material in resistance heating body at this temperature and vacuum condition Divide and be evaporated, and condense in electrolyte crystallisation chamber;And after the alkali metal in resistance heater is distilled off, through furnace wall Slot-type openings at the top of refractory material wall enter alkali metal crystallisation chamber, in alkali metal crystallizer condensed on inner walls;
(5)This temperature and vacuum condition are maintained more than 0.5 hour, make to be powered off after the completion of metallurgical processes whole in device, Vacuum is closed, then to argon gas is passed through in device, normal pressure in holding meanss after temperature is down to room temperature, opens bell, from stove Interior taking-up electrolyte, condensation has the alkali metal crystallizer of alkali metal, and the waste cathode carbon block for having isolated electrolyte, alkali metal Fragment, has isolated the briquetting material of electrolyte;
The XRD analysis of the waste cathode carbon block reclaimed after being distilled using the present embodiment device and operating method have not been found The rate of recovery of electrolyte components and metallic sodium, a remaining pure charcoal, sodium and electrolyte reaches 100%;Electrolyte in anode breeze All it is separated, the rate of recovery of electrolyte reaches 100% in anode breeze.
Embodiment 2
Fig. 4 is the U-shaped resistance heater and electrode structure C-C profiles when resistance heater of the invention is U-shaped design;
Apparatus structure is with the difference of embodiment 1:
(1)Resistance heater is designed for U-shape structure;
(2)Resistance heater is higher by 10cm than graphite body;
Method is with the difference of embodiment 1:
(1)Briquetting material mixes compacting and forms by the milling material of the waste refractory materials liner of electrolytic cell with aluminium ash;Electrolytic cell Na in the milling material of waste refractory materials liner2O components are 5%, and electrolyte components are 10%;Pure aluminum is 15% in aluminium ash, and dispensing is pressed Added aluminium ash can be by the Na in waste refractory materials liner with the aluminium in aluminium ash2O is reduced to dispensing criterion completely;Electrolytic cell it is useless The milling material of refractory lining and the granularity of aluminium ash are less than 100 mesh;
(2)The temperature of resistance heater rises to 1400 DEG C, 1200 DEG C of the temperature of the indoor reaction material of pair material;Electrolytic cell it is useless resistance to Na in the milling material and aluminium ash of fiery material liner2O components are metallic sodium by the aluminium reducing in aluminium ash, and are distilled off through stove Enter alkali metal after the slot-type openings at the top of slot-type openings and furnace wall refractory wall at the top of the refractory material wall at middle part In alkali metal crystallizer condensed on inner walls after crystallisation chamber;
(3)This temperature and vacuum condition is maintained to be more than 2 hours;
The XRD analysis of the waste cathode carbon block reclaimed after being distilled using the present embodiment device and operating method have not been found The rate of recovery of electrolyte components and metallic sodium, a remaining pure charcoal, sodium and electrolyte reaches 100%;The waste refractory materials of electrolytic cell The electrolyte and alkali metal of the milling material of liner are all separated, and the rate of recovery of sodium and electrolyte reaches 100%.
Embodiment 3
Fig. 5 be the present embodiment resistance heater be two independences and be parallel to each other straight line Dam Configuration Design when C-C sections Figure;
It is with the difference of embodiment 2:
(1)Resistance heater is two independences and the straight line three-dimensional-structure design being parallel to each other, each independent resistance hair Two electrodes of hot body are respectively on two sides of electric furnace;Now two electrodes of same side, are connected with power supply, Two electrodes of another side are connected with metallic conductor;
(2)Resistance heater is higher by 20cm than graphite body;
Method is with the difference of embodiment 2:
(1)Briquetting material is formed by the milling material of the waste refractory materials liner of electrolytic cell with Al-Fe alloyed powder mixing compactings, its Metal aluminum content is 67% in middle Al-Fe alloys, and granularity is below 100 mesh, in the milling material of the waste refractory materials liner of electrolytic cell Na2O components are 5%, and fluoride is 8%, add the Al-Fe alloys amount can be by useless fire proofed wood with the aluminium in Al-Fe alloys in dispensing Na in material liner2O is reduced to dispensing criterion completely;
(2)The temperature of resistance heater rises to 1400 DEG C, 1250 DEG C of the temperature of the indoor reaction material of pair material;Electrolytic cell it is useless resistance to Na in the milling material of fiery material liner2O components are metallic sodium by the aluminium reducing in Al-Fe alloys;
The XRD analysis of the waste cathode carbon block reclaimed after being distilled using the present embodiment device and operating method have not been found The rate of recovery of electrolyte components and metallic sodium, a remaining pure charcoal, sodium and electrolyte reaches 100%;The waste refractory materials of electrolytic cell Electrolyte and alkali metal in the milling material of liner are all separated, and the rate of recovery of sodium and electrolyte has reached 100%.
Embodiment 4
A-A sectional views, B-B profiles when Fig. 6, Fig. 7, Fig. 8 are the only single resistance heater designs of the present embodiment With C-C profiles;
Apparatus structure is with the difference of embodiment 1:
(1)Resistance heater is designed for single resistance heater, without secondary material room, two electrodes of resistance heater in stove It is arranged on two corresponding surfaces of body of heater length direction;
(2)Electrolysis of fluorides matter of the waste cathode carbon block containing sodium, potassium metal and sodium potassium;
(3)Resistance heater is highly identical with graphite body;
(4)The distance of the bucket wall of metal cap and the bottom of alkali metal crystallizer is in 20cm;
Method is with the difference of embodiment 1:
(1)Briquetting material is not used;
(2)The temperature of resistance heater rises to 1200 DEG C;
The XRD analysis of the waste cathode carbon block reclaimed after being distilled using the present embodiment device and operating method have not been found Electrolyte components, metallic sodium and potassium, the charcoal after distillation in cathode carbon pieces are pure charcoal, and the alkali metal for distilling is Na-K alloys, The electrolyte rate of recovery of the fluoride of potassium containing sodium is 100%.
Embodiment 5
A kind for the treatment of of the present embodiment and the device and operating method and the basic phase of embodiment 1 of recovery aluminium electroloysis solid waste Together, except that:
(1)The top of the refractory material wall at middle part does not have slot-type openings in stove, and it is highly less than furnace wall refractory wall The height 10cm of body;
(2)In operation, pair material room does not load briquetting material or other any reaction masses;
Method is with the difference with embodiment 1:
(1)It it is 1200 DEG C using waste cathode carbon block as the warming temperature of resistance heater;
Found through XRD material phase analysis, the waste cathode carbon block reclaimed using the apparatus and method of the present embodiment except charcoal it Outward, a small amount of CaF is comprised only2

Claims (8)

1. it is a kind of process and reclaim aluminium electroloysis solid waste device, it is characterised in that including furnace shell, bell, inner lining of furnace, furnace wall The refractory material wall at middle part in refractory material wall, bottom refractory liner body, resistance heater, stove, alkali metal crystallizer, Heat-insulated cover plate, metal cap, electrode and secondary material room, electrolyte crystallisation chamber and alkali metal crystallisation chamber;
Described furnace shell is a box metal shell, is made up of sheet metal material;The top outer of furnace shell has flange knot Structure, the outer wall of the primary reformer shell under flange arrangement is provided with cooling jacket, and vacuum suction is welded with the furnace shell of flange arrangement bottom Pipe;Also being welded with furnace shell top flange structure lower edge can be to the gas tube and display that argon gas or other inert gases are filled with stove The pressure vacuum gauge of furnace pressure and vacuum condition;
Described bell is made of steel metal material, and vacuum packing ring is provided between the flange arrangement and bell on edge on furnace shell;
Described inner lining of furnace is made up of stove lateral lining and bottom lining, the wall that the inwall of stove lateral lining is made for refractory material Body, referred to as furnace wall refractory wall, the internal layer of bottom lining are the liner body being made up of refractory material, referred to as bottom refractory Liner body, is the liner body being made up of insulation material between furnace wall refractory wall and side fireplace shell, referred to as furnace wall insulation material lining Body;It is the liner body being made up of insulation material, referred to as bottom heat insulation material liner body between bottom refractory liner body and furnace bottom furnace shell;
Described furnace wall refractory wall is higher than furnace wall insulation material liner body, has groove profile to open at the top of furnace wall refractory wall Mouthful, electrolyte crystallisation chamber is connected with alkali metal crystallisation chamber by this slot-type openings;
The refractory material wall at middle part is seated on bottom refractory liner body in described stove, with bottom refractory Liner body is vertical, and against the medial surface wall vertically upward of resistance heater;The height of middle part refractory material wall in stove Equal to or less than the height of furnace wall refractory wall, when the height of middle part refractory material wall in stove is equal to furnace wall refractory During the height of wall, middle part refractory material wall top is provided with slot-type openings in stove, and pair is expected into room top by this slot-type openings Electrolyte crystallisation chamber connected with the electrolyte crystallisation chamber above resistance heater;
Described heat-insulated cover plate makes of refractory material, positioned at the top of furnace wall refractory wall;The outer of heat-insulated cover plate is big In the outer of furnace wall refractory wall;
Described metal cap is one the rectangle bucket of bottom uncovered, and left-hand thread plugs in the bucket wall of metal cap on heat-insulated cover plate Enter in alkali metal crystallizer;On metal cap, bell is arranged with warming plate;
Described alkali metal crystallizer is made up of stainless steel plate, and alkali metal crystallizer outer wall is close to the furnace shell with cooling jacket Inwall, the bottom of alkali metal crystallizer is a groove-shaped design;Alkali metal crystalliser feet is located at furnace wall insulation material liner body Upper surface;
The fragment of waste cathode carbon block of the described resistance heater by particle diameter less than 10cm is constituted;The fragment of waste cathode carbon block is put In the length by being surrounded between the refractory material wall and the graphite body of two electrodes at middle part in furnace wall refractory wall, stove In the space of bar shaped, resistance heater is formed;Resistance heater is higher than 0 ~ 30cm of graphite body;
Described electrode is made up of two parts electric conductor, and the electric conductor of the part that is in contact with resistance heater on the inside of stove is graphite guide Electric body;The section configuration of graphite body is rectangle;The electric conductor being connected with graphite body is metallic conductor, referred to as metal Electrode, its section is circle;The cross-sectional area of metal electrode is connected with cold less than the cross-sectional area of graphite body in metal electrode But water;There is insulation seal device between metal electrode and furnace shell;
Described pair expects room on bottom refractory liner body, by the refractory material wall and two electrodes at middle part in stove Between furnace wall refractory wall surrounded, its highly with resistance heater height identical space;
Described electrolyte crystallisation chamber has two kinds, and one kind is located on resistance heater, under heat-insulated cover plate by higher than electricity Hinder the space that the refractory material wall at middle part in the furnace wall refractory wall and stove of heater is surrounded;Another electrolyte knot Brilliant room is located on secondary material room charge level position, the fire proofed wood by middle part in the stove higher than resistance heater under heat-insulated cover plate The space that furnace wall refractory wall between material wall and two electrodes is formed;
Described alkali metal crystallisation chamber is located on the insulation material liner body of furnace wall, by the furnace wall fire proofed wood higher than resistance heater The space surrounded between material wall and alkali metal crystallizer;In alkali metal crystallisation chamber, gold of the left-hand thread on heat-insulated cover plate The bucket wall for belonging to cover extend into alkali metal crystallisation chamber from the top down.
2. it is according to claim 1 it is a kind of process and reclaim aluminium electroloysis solid waste device, it is characterised in that each is only There is an electrode at the two ends of vertical resistance heater, and one of them is that, into electrode, another is electric electrode;Work as resistance heating When body is for U-shaped design or the setting of П types, two electrodes of resistance heater are in the same side of furnace shell;When resistance heater is two Individual to be parallel to each other and when separate straight line body is designed, two electrodes of each individual resistors heater are respectively positioned at furnace shell On two corresponding sides, now, two electrodes of same side are connected with power supply, between two electrodes of another side Connected with metallic conductor, make another resistance heater of heated current from a resistance heater same stove of inflow.
3. it is according to claim 1 it is a kind of process and reclaim aluminium electroloysis solid waste device, it is characterised in that it is described Pair material room is used to load the briquetting material that anode breeze is made, or the levigate material of electrolytic cell waste refractory materials and aluminium ash or Al-Fe alloys The briquetting material that levigate material is mixed.
4. it is according to claim 1 it is a kind of process and reclaim aluminium electroloysis solid waste device, it is characterised in that it is described The distance of the bucket wall of metal cap and the bottom of alkali metal crystallizer is in 5 ~ 30cm.
5. a kind for the treatment of described in claim 1 and the application method of the device of recovery aluminium electroloysis solid waste, it is characterised in that Carry out according to the following steps:
(1)Fragment by waste cathode of aluminum electrolytic cell carbon block smashing into particle diameter less than 10cm, is placed on bottom refractory liner body, By in the space that is formed between furnace wall refractory wall, stove middle part refractory material wall and the graphite body of two electrodes, Form resistance heater;
(2)Briquetting material is placed in secondary material room;The height of briquetting material is highly identical with resistance heater;Described briquetting material by The compacting of anode breeze is formed, or by the waste refractory materials liner of electrolytic cell milling material and aluminium it is grey mix compacting and form, or Formed with Al-Fe alloyed powder mixing compactings by the milling material of the waste refractory materials liner of electrolytic cell;
(3)Alkali metal crystallizer is placed into, heat-insulated cover plate is covered, metal cap is put, then puts warming plate, bell is covered afterwards;
(4)Below 100Pa will be evacuated down in body of heater, to being passed through cooling water in cooling jacket, then cooling be passed through to metal electrode Water, is then electrified to, and the temperature of resistance heater is risen to 1000 ~ 1400 DEG C, and the temperature for making the indoor briquetting material of secondary material reaches 900 ~ 1200℃;The electrolysis in electrolyte components, the indoor anode breeze of secondary material in resistance heating body at this temperature and vacuum condition Electrolyte components in the milling material of the waste refractory materials liner of matter component or electrolytic cell are evaporated, and condense in electrolyte In crystallisation chamber;And after the alkali metal in resistance heater is distilled off, through the slot-type openings at the top of furnace wall refractory wall Into alkali metal crystallisation chamber, then in alkali metal crystallizer condensed on inner walls;And the milling of the waste refractory materials liner of electrolytic cell After the alkali metal of the reactive aluminum generation in material and aluminium ash or Al-Fe alloyed powders is distilled off, via middle part refractory material in stove Gap between middle part refractory material wall top and heat-insulated cover plate and furnace wall fire proofed wood in slot-type openings or stove at the top of wall Slot-type openings at the top of material wall enter alkali metal crystallisation chamber, then in alkali metal crystallizer condensed on inner walls;
(5)This temperature and vacuum condition are maintained more than 0.5 hour, makes to be powered off after the completion of metallurgical processes whole in device, closed Vacuum, then to argon gas is passed through in device, normal pressure in holding meanss after temperature is down to room temperature, opens bell, is taken from stove Go out electrolyte, condensation has the alkali metal crystallizer of alkali metal, and isolated electrolyte, alkali metal waste cathode carbon block it is broken Block, has isolated electrolyte or has removed the briquetting material of alkali metal and electrolyte.
6. it is according to claim 5 it is a kind of process and reclaim aluminium electroloysis solid waste device application method, its feature It is that described alkali metal is sodium or Na-K alloy, or is sodium or Na-K alloy containing lithium.
7. it is according to claim 5 it is a kind of process and reclaim aluminium electroloysis solid waste device application method, its feature Aluminium content and useless electrolysis of the milling material of the waste refractory materials of the electrolytic cell described in being with the mixed proportion of aluminium ash in aluminium ash In the milling material of the waste refractory materials of groove depending on the content of alkali metal oxide, the aluminium in allowing allocated into aluminium grey in principle will Alkali metal oxide in the milling material of the waste refractory materials of electrolytic cell is completely reduced into alkali metal for dispensing criterion;Electrolytic cell Waste refractory materials pulverized powder also carries out dispensing, the wherein waste refractory materials of electrolytic cell with the proportioning of Al-Fe alloyed powders by this criterion Milling material, aluminium ash and the granularity of Al-Fe alloyed powders be respectively less than 100 mesh.
8. it is according to claim 5 it is a kind of process and reclaim aluminium electroloysis solid waste device application method, its feature It is the step when pair material interior does not load briquetting material or other materials(4)The heating-up temperature of middle resistance heater be 1000 ~ 1300℃。
CN201510519831.4A 2015-08-24 2015-08-24 A kind of device for processing and reclaiming aluminium electroloysis solid waste Expired - Fee Related CN105088274B (en)

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CN106643120B (en) * 2016-11-03 2018-10-02 沈阳北冶冶金科技有限公司 Separate and recover the resistance furnace of internal lining of aluminium electrolytic bath solid waste and desulfurizing petrol coke
CN106756139A (en) * 2016-12-06 2017-05-31 沈阳化工大学 A kind of method that utilization aluminium electrolytic graphite cathode prepares graphite rotator
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