WO2017143697A1 - Aluminum industry solid waste recovery/petroleum coke high-temperature desulphurization device and using method therefor - Google Patents

Abstract

Provided are an aluminum industry solid waste recovery/petroleum coke high-temperature desulphurization device and a using method therefor. The device comprises a furnace body, a low-melting-point matter crystallizer (23) at the rear end of the furnace body, and a liquid low-melting-point matter collector (30) below the low-melting-point matter crystallizer. A main material chamber (14) inside the furnace body is used for placing broken waste cathode carbon blocks of an aluminum electrolysis cell or petroleum coke as a resistance heating body. A sleeve (21) is arranged at the rear end in communication with the low-melting-point matter crystallizer (23). The bottom of the low-melting-point matter crystallizer (23) is in communication with the liquid low-melting-point matter collector (30) through a discharge valve (31). The using method mainly comprises: placing the resistance heating body into the main material chamber; vacuumizing and introducing cooling water; heating the resistance heating body by energization; separating at a high-temperature by vacuumizing, stopping vacuumizing and heating, and charging argon; and heating to melt the material coagulated in the low-melting-point matter crystallizer and enter the liquid low-melting-point matter collector. The device and the method are simple in operation, save energy sources and reduce pollution.

Description

Aluminum industrial solid waste recycling / petroleum coke high temperature desulfurization device and using method thereof Technical field

The invention belongs to the technical field of metallurgical environmental protection, and particularly relates to an aluminum industrial solid waste recycling/ petroleum coke high temperature desulfurization device and a using method thereof.

Background technique

Metallic aluminum is produced by cryolite-alumina molten salt electrolysis. In the entire production process from primary aluminum to primary aluminum purification, into metal ingots and alloy materials, the following types of waste are produced:

1. The following solid waste generated during the overhaul of the aluminum electrolysis cell: (1) waste cathode carbon block containing sodium and electrolyte; (2) waste fireproof containing electrolyte, metal sodium and refractory material to form sodium aluminosilicate Material lining; (3) waste cathode lining of silicon nitride containing electrolyte combined with silicon carbide; (4) Fe-Al alloy formed by corrosion of aluminum alloy rod by aluminum;

2. An anode carbon residue containing an electrolyte produced during the production of aluminum electrolysis;

3. Aluminum ash slag produced during the production of primary aluminum, ingots and alloy materials.

The solid waste generated in these aluminum industries, if discarded, not only causes harm to the environment, but also wastes many valuable resources in these wastes. Therefore, many researchers have studied it and proposed many individual treatments. The method of these wastes. Recently, our previous patent "A device for treating and recovering aluminum electrolytic solid waste" (Application No. 2015105198314) invented a method for comprehensively treating and recovering aluminum electrolytic solid waste in the same furnace.

The patent technology can realize the above-mentioned solid waste from the original aluminum production to the purification, casting and alloying of aluminum, and the solid waste can be effectively separated and recycled. However, the method and the device also have the following disadvantages and disadvantages:

1. The inner wall and inner lining of the entire upper structure of the vacuum resistance furnace of the technical device have no heat preservation measures, so the heat loss is large and the thermal efficiency is low;

2. The metal sodium or sodium potassium alloy separated from the waste is not easily removed from the furnace, and it is difficult to remove it from the sodium crystallizer;

3. When the furnace is discharged, the alkali metal sodium or sodium potassium alloy is exposed to the air in a large area, and the alkali metal potassium sodium is very easily oxidized. If it is slightly inadvertent, it may cause oxidative fire and is not easily extinguished;

4. When the alkali metal separated from the solid waste is a Na-K alloy, the sodium-potassium alloy exists in a liquid form at normal temperature, and the liquid sodium-potassium alloy is difficult to peel off from the crystallizer, even if it is pure The sodium metal is often adhered to the crystallizer in a very soft state at normal temperature.

Petroleum coke is the basic raw material for the manufacture of aluminum electrolysis carbon anodes in the aluminum metallurgical industry and the basic raw materials for the manufacture of graphite electrodes in the metallurgical industry. That is to say, the graphite electrodes used in metallurgical industry steelmaking and the carbon anodes used in aluminum electrolysis are made of petroleum coke. Stone The consumption of oil coke is huge. Taking aluminum electrolysis as an example, the carbon anode consumed per ton of metal aluminum produced by electrolysis is about 420-500 kg, and the petroleum coke consumed is about 600 kg. An electrolytic aluminum plant with an annual output of 500,000 tons consumes about 300,000 tons of petroleum coke per year. Petroleum coke is produced by coking of residual oil after petroleum smelting. It is a by-product of the petroleum smelting industry, so it is called petroleum coke.

The sulfur content in petroleum coke varies widely, from less than 0.5% to more than 10%, depending on the sulfur content of the petroleum used in the production of petroleum coke. Petroleum coke can be divided into low sulfur coke and high sulfur coke according to its sulfur content. However, there is no uniform standard for the classification of high sulfur coke. Generally, petroleum coke with a sulfur content higher than 3% is considered to be high sulfur coke, which is low. The petroleum coke with a sulfur content of 1.5% is considered to be low sulfur coke, and the petroleum coke with a sulfur content of 1.5 to 3.0% is considered to be medium sulfur coke. However, the low sulfur coke content with a sulfur content of less than 1.5% is small, the market has low and low sulfur coke, and the price is also high. Therefore, in China, the electrolytic aluminum plant can only mix low sulfur coke with high sulfur coke. After use, the petroleum coke after mixing has a sulfur content of about 2 to 3% or less, and has an increasing tendency. In the current medium sulfur content range, it seems that the sulfur content does not have much influence on the quality of the aluminum electrolytic anode, but for electrolytic aluminum plants and electrode manufacturers, the impact of sulfur in the petroleum coke on the environment is enormous; For example, in an electrolytic aluminum plant with an annual output of 500,000 tons, if a carbon anode produced by using petroleum coke containing 2% sulfur is produced, the amount of SO ₂ produced by aluminum electrolysis per year is 10,000 tons. These SO ₂ emissions into the atmosphere react with the moisture in the air to produce 12,000 tons of sulfurous acid. It can be seen that the impact of sulfur in petroleum coke on the environment is enormous; however, it has not been found so far. An industrial scale petroleum coke desulfurization method and technique.

At present, all the desulfurization methods for petroleum coke are in the laboratory research stage. In these studies, it should be said that high temperature desulfurization is a more realistic desulfurization method; industrially, whether it is carbon anode of aluminum electrolysis or steel industry For the manufacture of graphite electrodes, the petroleum coke used is calcined at a temperature of 1200 to 1250 ° C. At such calcination temperature, not only the density, strength and performance of petroleum coke are improved, but also in petroleum coke. The sulfur content is reduced by 20 to 25%, but the higher sulfur content has not been effectively removed, and the temperature is further increased. If the temperature is raised to 1500 to 1700 ° C, more than 90% of the sulfur in the petroleum coke can be removed, but if the oil is The coke calcination temperature is increased to 1500 to 1700 ° C, which not only consumes a lot of energy, but also has a certain difficulty in device design. So far, no temperature has been developed in the industry at temperatures above 1500 ° C or above 1500 ° C. A method and apparatus for performing high temperature desulfurization.

Summary of the invention

In view of the above problems in the prior art aluminum industry solid waste recycling treatment and petroleum coke high temperature desulfurization, the present invention provides an aluminum industrial solid waste recycling/petrogon coke high temperature desulfurization device and a method for using the same, and an aluminum electrolytic cell among aluminum industrial solid waste. The scrap material or petroleum coke of the waste cathode carbon block is used as a resistance heating body, the furnace is made of refractory material, a high melting point crystallization chamber is arranged above the furnace, and a low melting point material crystallization chamber and a liquid low melting point material collecting device are arranged outside the furnace shell. The high-melting-point crystallization chamber and the low-melting-point crystallization chamber are respectively connected to the vacuum system, and the high-efficiency vacuum separation and recovery method is adopted to achieve high-efficiency separation of the aluminum industrial solid. The effect of body waste, or the effect of high-efficiency petroleum coke desulfurization.

The aluminum industrial solid waste recovery/peech coke high-temperature desulfurization device of the invention comprises a furnace body, a low melting point material crystallizer at the rear end of the furnace body and a liquid low melting point material collector under the low melting point material crystallizer; the furnace body is a furnace shell outside, The outer wall of the upper part of the furnace shell is provided with a cooling water jacket, and the top is provided with a furnace cover which is sealed and connected with the furnace shell, the furnace shell is provided with a heat insulating material layer, the heat insulating material layer is provided with a groove type refractory material wall, and the groove type refractory material The wall body is composed of four side wall panels and one bottom wall panel; the trough type refractory wall body is provided with a refractory concrete inner wall body; the refractory concrete inner wall body is composed of three inner wall wall panels perpendicular to the bottom wall panel. The height of the inner wall wall panel is lower than the height of the trough type refractory wall, and a part of the side wall panel of the refractory concrete inner wall body and the groove type refractory wall near the front end of the furnace body is formed into a rectangular parallelepiped auxiliary material chamber, and the groove type refractory material wall a space outside the auxiliary chamber inside the body serves as a main chamber; the main chamber is used for placing a scrap of a waste cathode carbon block of an aluminum electrolytic cell as a resistance heating body, or for placing petroleum coke as a resistance heating body, Said The petroleum coke is raw coke or calcined petroleum coke; the top of the main material chamber is provided with a top cover of the main material chamber; the inner wall of the refractory concrete is provided with a through hole, and the top of the inner wall of the refractory concrete is also provided with a slot type opening, a through hole and a trough type The opening connects the main chamber and the auxiliary chamber; the grooved refractory wall is provided with two graphite electrodes on the side wall plate near the front end of the furnace body, two graphite electrodes are located on both sides of the auxiliary chamber, and one end of the two graphite electrodes They are respectively assembled with a metal electrode, the metal electrode is sealed and fixed on the furnace shell, and the other ends of the two graphite electrodes are connected with the two ends of the resistance heating body; the top of the groove type refractory wall is provided with a prefabricated plate, a prefabricated plate and a furnace Between the cover is provided with a refractory insulation material plate; the upper part of the upper cover of the main material chamber and the upper part of the auxiliary material chamber and the space below the prefabricated plate serve as a crystallization chamber of high melting point material; the furnace shell is provided with a front end vacuum suction pipe with a valve, and the front end vacuum The suction pipe is located above the two graphite electrodes, and the vacuum suction pipe at the front end communicates with the vacuum passage on the insulation material layer and the grooved refractory wall, and the vacuum passage is connected with the high melting point material crystallization chamber; The rear end of the wall of the fire material is provided with a sleeve, the sleeve is connected with the crystallizer of the low melting point material, the bottom of the crystallizer of the low melting point material is connected with the liquid low melting point material collecting device through the valve, and the liquid low melting point material collecting device is provided with the lifting The low-melting substance crystallizer is provided with a rear end vacuum suction pipe with a valve and an argon gas inflation pipe.

The above-mentioned low melting point material crystallizer is of a horizontal structure or a vertical structure, and an externally wound electric wire heating device and a cooling water pipe are alternately wound; when the low melting point material crystallizer is of a horizontal structure, the lower portion thereof is an inverted conical shape. The bottom end of the inverted cone is connected to a collecting tube which communicates with the liquid low-melting substance collector through a valve, and the end of the low melting material crystallizer away from the furnace body is provided with an end cap and a low melting point material crystallizer Sealed connection; when the low melting point material crystallizer is of vertical structure, the low melting point material crystallizer consists of inclined section and vertical section, the inclined section is connected with the sleeve, and the lower part of the inclined section is connected with a collecting tube, the collecting tube The valve is connected to the interior of the liquid low-melting substance collector, and the top end of the vertical section is provided with an end cap and a low-melting substance crystallizer.

In the above device, the low melting point material crystallizer is provided with a baffle, the baffle is provided with a baffle through hole, and the rear end vacuum exhaust pipe and the argon gas inflation pipe are located between the end cover and the baffle.

In the above device, the top of the liquid low-melting substance collector is provided with a collector upper cover, and the collector upper cover is sealed and connected with the liquid low-melting substance collector; the collector upper cover and the collecting tube are fixed together. A resistance wire and a cooling water pipe are alternately wound around the pipe.

The method for using the aluminum industrial solid waste recycling/ petroleum coke high-temperature desulfurization device of the invention, wherein the aluminum industrial solid waste recycling method is carried out as follows:

1. The fragment material of the waste cathode carbon block of the aluminum electrolytic cell is placed in the main material chamber as a resistance heating body; the particle size of the scrap cathode material of the aluminum electrolytic cell waste cathode carbon block is ≤8 cm;

2. The anode carbon residue, or the waste refractory material with a particle size of ≤8cm, is lined with pieces, or the waste refractory material is lined with pieces, and then mixed with aluminum ash and pressed to form a compressed aggregate, or waste refractory lining. After crushing the pieces, the pressed aggregate formed by mixing with the Fe-Al alloy powder having a particle size of less than 100 mesh, or the silicon nitride block combined with the waste silicon nitride having a particle diameter of ≤ 8 cm is placed in the auxiliary material chamber;

3. Place or not place a grid plate in the crystallization chamber of the high melting point material, and the grid plate as an auxiliary crystallizer increases the crystal area;

4. Vacuuming the furnace body through the front end vacuum suction pipe to a pressure of ≤ 80 Pa;

5. Passing cooling water into the cooling water jacket, cooling the metal electrode through the cooling water system, and cooling the low melting material crystallizer through the cooling water system;

6. Applying DC power through two metal electrodes and a graphite electrode to electrically heat the resistance heating body; when the temperature of the resistance heating body reaches 500±10° C., the front end vacuum suction pipe is closed, and the rear end vacuum suction pipe is opened, and the furnace body is pumped. Vacuum to air pressure ≤ 80Pa; continue to heat the resistance heating body, and control the temperature in the auxiliary material chamber at 1100 ± 30 ° C;

7. After the alkali metal in the resistance heating body enters the crystallization chamber of the low melting point substance, the vacuuming and heating are stopped, and the argon gas is filled into the furnace body through the argon gas inflation tube;

8. Stop cooling the low melting point material crystallizer, heat the low melting point material crystallizer to melt the condensed material on the inner wall, and enter the lift bag in the liquid low melting point material collector.

In the above-mentioned aluminum industrial solid waste recycling method, in the step 7 and when the temperature in the furnace body falls below 700 ° C, the material condensed in the crystallization chamber of the high melting point substance is taken out.

In the above aluminum industrial solid waste recycling method, the material condensed in the crystallization chamber of the low melting point substance is an alkali metal or an alkali metal alloy, and the alkali metal alloy is a sodium potassium alloy, a sodium containing lithium metal or a sodium potassium alloy containing lithium, and a high melting point substance. The material condensed in the crystallization chamber is a fluoride salt electrolyte.

In the above aluminum industrial solid waste recycling method, in step 8, the low melting point material crystallizer is heated to melt the condensed material on the inner wall, and the temperature in the crystallizer of the low melting point substance is controlled to be higher than the melting point of the low melting point material by 30 to 100 ° C. The low melting point substance is an alkali metal or an alkali metal alloy.

In the above aluminum industrial solid waste recycling method, in step 2, the waste refractory lining pieces are ground and mixed with aluminum ash. Pressing the formed compact material, or the waste refractory material, the lining pieces are ground and mixed with the Fe-Al alloy powder having a particle size of less than 100 mesh, and the pressed aggregate is formed by pressing, and the waste refractory material is lined with the aluminum ash or Fe. - The chemical reaction formula of the Al alloy powder is based on:

3Na ₂ O+2Al=6Na+Al ₂ O ₃

3K ₂ O+2Al=6K+Al ₂ O ₃

Wherein Al is aluminum or an Al ash Fe-Al alloy powder of Al, Na ₂ O and K ₂ O in the waste pieces of the refractory lining Na ₂ O and K ₂ O.

The method for using the aluminum industrial solid waste recycling/ petroleum coke high-temperature desulfurization device of the invention, wherein the method for high-temperature desulfurization of petroleum coke is carried out as follows:

1. The petroleum coke is placed in the main material chamber as a resistance heating body; the particle size of the petroleum coke is ≤8 cm;

2. When the raw coke is used as the resistance heating body, the furnace body is evacuated to the air pressure ≤ 80 Pa through the front end vacuum suction pipe; when the calcined petroleum coke is used as the resistance heating body, the furnace body is evacuated through the rear end vacuum suction pipe. To air pressure ≤ 80Pa;

3. Passing cooling water into the cooling water jacket, cooling the metal electrode through the cooling water system, and cooling the low melting material crystallizer through the cooling water system;

4. Applying direct current through two metal electrodes and a graphite electrode to electrically heat the resistance heating body; when the raw coke is used as the resistance heating body, and when the temperature of the resistance heating body reaches 700 to 900 ° C, the front end vacuum suction pipe is closed. Vacuuming the furnace body through the back end vacuum suction pipe to a pressure of ≤ 80 Pa;

5. When the temperature of the resistance heating body reaches 1500~1700 °C, stop vacuuming and heating, and fill the furnace body with argon gas through the argon gas inflation tube;

6. Stop cooling the crystallizer of the low melting point material, heat the crystallizer of the low melting point material to melt the condensed elemental sulfur on the inner wall, and enter the lifting bag in the liquid low melting point material collector.

In the above method for high-temperature desulfurization of petroleum coke, in step 6, the low-melting substance crystallizer is heated to melt the condensed material on the inner wall, and the temperature in the crystallizer of the low-melting substance is controlled to be higher than the melting point of the low-melting substance by 30 to 100 °C. The low melting point substance is elemental sulfur.

In the above two methods, the low melting point material crystallizer is cooled by a cooling water pipe outside the low melting point material crystallizer, and the low melting point material crystallizer is heated by a resistance wire heating device outside the low melting point material crystallizer.

When the method of the invention uses the fragment of the waste cathode carbon block of the aluminum electrolytic cell as the resistance heating body, the treated aluminum electrolytic cell waste cathode carbon block contains CaF ₂ , the melting point is 1402 ° C, and is separated from the waste cathode carbon block. CaF ₂ needs to be higher than the melting point of CaF ₂ ; if it is not necessary to separate CaF ₂ from the waste cathode carbon block, and the auxiliary material does not place other aluminum industrial solid wastes other than the waste cathode carbon block, the temperature of the resistance heating body is controlled at Between 1100 and 1200 ° C temperature.

In the above two methods, a cooling water chamber is provided in the metal electrode, and the metal electrode is cooled by passing cooling water into the cooling water chamber.

In the above method for high-temperature desulfurization of petroleum coke, the desulfurization rate of petroleum coke is ≥90%.

In the above method for high-temperature desulfurization of petroleum coke, when the temperature in the furnace body falls below 700 ° C, the argon gas is stopped, and the desulfurized petroleum coke is taken out from the main chamber.

In the above two methods, when the scrap material of the waste cathode carbon block of the aluminum electrolytic cell is used as the resistance heating body, the high melting point substance is condensed in the crystallization chamber of the high melting point substance, and the low melting point substance is condensed in the crystallization chamber of the low melting point substance; When the petroleum coke is used as the resistance heating element, the volatile matter is discharged from the front end vacuum pipe and collected, and the gaseous elemental sulfur enters the crystallization chamber of the low melting point substance and condenses on the low melting point material crystallizer.

The apparatus and method of the present invention can realize complete separation of carbon, alkali metal and electrolyte in the waste cathode carbon block of the industrial aluminum electrolytic cell, and complete separation of electrolyte, alkali metal and refractory components in the refractory material of the electrolytic cell lining, and The separation of electrolyte and carbon in the anode carbon residue also makes efficient use of aluminum in the Al-Fe alloy formed by the aluminum ash and the cathode steel rod melted by aluminum, and the separated alkali metal is well recovered; The process is free from waste residue, waste gas and waste water. It is an energy-saving and environmentally-friendly aluminum electrolytic solid waste treatment device, which is very suitable for large-scale application in industry.

The device and method of the invention can achieve the desulfurization rate of petroleum coke by more than 90%, not only can reduce the pollution of sulfur in the petroleum coke of the metallurgical industry, and can effectively recover sulfur in the petroleum coke; in addition, the petroleum coke can be desulfurized after high temperature. Reducing the swelling of the graphite electrode caused by sulfur during the graphitization process, which not only improves the heating rate during the graphitization of the electrode, but also improves the yield of the graphite electrode, thereby greatly reducing the power consumption during the graphitization of the graphite electrode. .

DRAWINGS

1 is a schematic view showing the structure of an aluminum industrial solid waste recovery/ petroleum coke high-temperature desulfurization device with a low-melting substance crystallizer in a horizontal structure according to an embodiment of the present invention;

Figure 2 is a cross-sectional view taken along line B-B of Figure 1;

Figure 3 is a cross-sectional view taken along line C-C of Figure 1;

Figure 4 is a cross-sectional view taken along line D-D of Figure 1;

5 is a schematic structural view of an aluminum industrial solid waste recovery/ petroleum coke high-temperature desulfurization device with a low-melting-point material crystallizer in a vertical structure according to an embodiment of the present invention;

In the figure, 1, furnace shell, 2, insulation material layer, 3, trough refractory wall, 4, furnace cover, 5, refractory insulation board, 6, prefabricated board, 7, refractory concrete inner wall, 8, Through hole, 9, slot type opening, 10, graphite electrode, 11, metal electrode, 12, cooling water chamber, 13, sealing device, 14, main material chamber, 15, main material chamber upper cover, 16, auxiliary material chamber, 17, front vacuum exhaust pipe, 18, front vacuum valve, 19, front vacuum gauge, 20, high melting point material crystallization chamber, 21, sleeve, 22, Baffle, 23, low melting point material crystallizer, 24, end cap, 25, rear vacuum evacuation tube, 26, rear vacuum valve, 27, argon gas tube, 28, cooling water tube, 29, resistance wire, 30, Liquid low melting point material collector, 31, discharge valve, 32, collector upper cover, 33, vacuum seal, 34, cooling water jacket, 35, lift bag, 36, upper flange of the furnace shell, 37, after End vacuum gauge.

detailed description

In the embodiment of the invention, the cooling water pipe is welded and fixed to the low melting point material crystallizer.

In the embodiment of the invention, the groove type refractory wall and the refractory concrete inner wall are made of refractory material.

The sleeve, the low melting point material crystallizer, the liquid low melting point material collector, the baffle and the lift bag in the embodiment of the invention are made of stainless steel.

In the embodiment of the invention, the material of the metal electrode is copper.

In the embodiment of the invention, the material of the furnace shell and the furnace cover is a steel material.

The material of the main chamber upper cover and the prefabricated plate in the embodiment of the present invention is a refractory concrete prefabricated plate material.

Example 1

The aluminum industrial solid waste recovery / petroleum coke high temperature desulfurization device structure is shown in Figure 1, the BB surface is shown in Figure 2, the CC surface is shown in Figure 3, the DD surface is shown in Figure 4, including the furnace. The body, the low melting point material crystallizer 23 and the liquid low melting point material collector 30; the outside of the furnace body is a furnace shell 1, and the outer wall of the upper part of the furnace shell 1 is provided with a cooling water jacket 34, and the top portion is provided with a sealing connection with the furnace shell 1 The furnace cover 4, the furnace shell 1 is provided with a thermal insulation material layer 2, the thermal insulation material layer 2 is provided with a trough-type refractory material wall 3, and the trough-shaped refractory material wall 3 is composed of four side wall panels and a bottom wall panel; The refractory concrete wall 3 is provided with a refractory concrete inner wall 7; the refractory concrete inner wall 7 is composed of three inner wall panels perpendicular to the bottom wall panel, the refractory concrete inner wall 7 and the grooved refractory wall a part of the side wall of the body 3 near the front end of the furnace body is enclosed by a rectangular parallelepiped chamber 16, and a space other than the auxiliary material chamber 16 inside the grooved refractory wall 3 is used as the main chamber 14;

The main material chamber 14 is used for placing the scrap material of the aluminum cathode electrolytic cell waste cathode carbon block as a resistance heating body; the main material chamber 14 is provided with a main chamber upper cover 15; the refractory concrete inner wall body 7 is provided with a through hole 8 The top of the refractory concrete inner wall is further provided with a slot-shaped opening 9, and the through hole 8 and the slot-shaped opening 9 communicate the main chamber 14 and the auxiliary chamber 16;

The grid type refractory wall 3 is provided with two graphite electrodes 10 on the side wall plate near the front end of the furnace body, two graphite electrodes 10 are located on both sides of the auxiliary chamber 16, and one end of the two graphite electrodes 10 is respectively connected with a metal electrode 11 Assembled together, the metal electrode 11 is sealed and fixed on the furnace shell 1 by the sealing device 13, and the other ends of the two graphite electrodes 10 are connected to both ends of the resistance heating body; the top of the groove type refractory wall 3 is provided with a prefabricated plate 6, a refractory insulation material plate 5 is disposed between the prefabricated plate 6 and the furnace cover 4;

The upper chamber upper cover 15 and the upper chamber 16 and the space below the prefabricated plate 6 serve as a high melting point material crystallization chamber 20; the furnace shell 1 is provided with a front end vacuum suction pipe 17 with a valve (front end vacuum valve 18), front end vacuum The suction pipe 17 is located in two stones Above the ink electrode 10, the front end vacuum suction pipe 17 communicates with a vacuum passage provided on the heat insulating material layer 2 and the grooved refractory wall 3, and the vacuum passage communicates with the high melting point material crystallization chamber 20;

The sleeve refractory wall 3 has a sleeve 21 at the rear end thereof, the sleeve 21 is in communication with the low melting point material crystallizer 23, and the bottom of the low melting point material crystallizer 23 is communicated with the liquid low melting point substance collector 30 through the discharge valve 31. The liquid low-melting substance collecting device 30 is provided with a lifting bag 35; the low-melting substance crystallizer 23 is provided with a rear end vacuum suction pipe 25 with a valve (rear vacuum valve 26) and an argon gas inflation pipe 27;

The low-melting-point material crystallizer 23 is of a horizontal structure, and the external resistance is alternately wound with a resistance wire 29 and a cooling water pipe 28; the lower portion of the low-melting substance crystallizer 23 is an inverted tapered structure, and the bottom end of the inverted conical shape is connected to a collecting tube. The collecting pipe is connected to the inside of the liquid low-melting substance collecting device 30 through a valve (discharge valve 31), and the end of the low-melting substance crystallizer 23 away from the furnace body is provided with an end cover 24 and a low-melting substance crystallizer 23;

The low melting point material crystallizer 23 is provided with a baffle 22, the baffle 22 is provided with a baffle through hole, and the rear end vacuum exhaust pipe 25 and the argon gas inflating pipe 27 are located between the end cover 24 and the baffle 22;

The top of the liquid low-melting substance collector 30 is provided with a collector upper cover 32, and the collector upper cover 32 is sealingly connected with the liquid low-melting substance collector 30; the collector upper cover 32 is fixed with the collecting tube. An electric resistance wire 29 and a cooling water pipe 28 are alternately wound around the collecting pipe;

The method of use is:

Disposing a piece of the cathode carbon block of the aluminum electrolytic cell in the main material chamber as a resistance heating body; the particle size of the scrap material of the aluminum cathode electrolytic cell waste cathode carbon block is ≤ 8 cm;

Placing the anode carbon residue in the auxiliary material chamber;

The grid plate is placed or not placed in the crystallization chamber of the high melting point substance, and the grid plate is used as an auxiliary crystallizer to increase the crystal area;

Vacuuming the furnace body through the front end vacuum suction pipe to a pressure of ≤ 80 Pa;

Cooling water is introduced into the cooling water jacket, and the metal electrode is cooled by the cooling water system, and the low melting material crystallizer is cooled by the cooling water system;

The direct current is applied by two metal electrodes and the graphite electrode to electrically heat the resistance heating body; when the temperature of the resistance heating body reaches 500±10° C., the rear end vacuum suction pipe is closed, and the front end vacuum suction pipe is opened, and the furnace body is evacuated to Air pressure ≤ 80Pa; continue to heat the resistance heating body, and control the temperature in the auxiliary material chamber at 1100 ± 30 ° C;

After all the alkali metals in the resistance heating body enter the crystallization chamber of the low melting point substance, the vacuuming and heating are stopped, and the argon gas is filled into the furnace body through the argon gas inflation tube;

Stop cooling the low melting point material crystallizer, heat the low melting point material crystallizer to melt the condensed material on the inner wall, and enter the lifting bag in the liquid low melting point material collector;

When the temperature in the furnace body falls below 700 ° C, the material condensed in the crystallization chamber of the high melting point material is taken out;

The material condensed in the crystallization chamber of the low-melting substance is an alkali metal or an alkali metal alloy, and the alkali metal alloy is a sodium-potassium alloy, a sodium containing metal lithium or a sodium-potassium alloy containing lithium, and the condensed material in the crystallization chamber of the high-melting substance is a fluoride salt electrolyte. .

Example 2

The structure of the device is shown in Fig. 5. The furnace body and the liquid low-melting substance crystallizer are the same as those in the first embodiment, and the difference lies in:

The main chamber is used for placing the raw coke;

The low melting point material crystallizer 23 is a vertical structure composed of a slanted section and a vertical section, and the low melting point material crystallizer 23 is composed of a slanted section and a vertical section, the sloping section is connected to the sleeve, and the lower part of the slant section is connected to a collecting tube. The collecting pipe is connected to the inside of the liquid low-melting substance collecting device 30 through a valve (discharge valve 31), and the end of the vertical section is provided with an end cover 24 and a low-melting substance crystallizer 23;

The method is the same as that in Embodiment 1, except that:

(1) placing the raw coke in the main material chamber as a resistance heating body; the particle size of the raw coke is ≤ 8 cm;

(2) No material is placed in the auxiliary material room;

(3) no grid plate is placed in the crystallization chamber of the high melting point material;

(4) vacuuming the furnace body through the front end vacuum suction pipe to a pressure of ≤ 80 Pa;

(5) When the temperature of the resistance heating body reaches 700 to 900 ° C, the vacuum suction pipe at the front end is closed, and the vacuum is drawn through the rear end vacuum suction pipe to a pressure of ≤ 80 Pa;

(6) When the temperature of the resistance heating body reaches 1500~1700 °C, stop vacuuming and heating, and fill the furnace body with argon gas through the argon gas inflation tube; when the temperature in the furnace body falls below 700 °C, stop the argon introduction. Gas, remove the desulfurized petroleum coke from the main chamber;

(7) The low melting point material crystallizer is heated to melt the condensed material (single sulfur) on the inner wall, and the temperature in the crystallizer of the low melting point substance is controlled to be higher than the melting point of elemental sulfur by 30 to 100 ° C; the desulfurization rate of petroleum coke is 92.5. %.

Example 3

The structure of the device is the same as that in Embodiment 1, wherein the main chamber is used for placing the calcined petroleum coke;

The method is the same as that of Embodiment 2, and the difference lies in:

(1) placing the calcined petroleum coke in the main material chamber as a resistance heating body; the particle size of the calcined petroleum coke is ≤8 cm;

(2) The front end vacuum suction pipe is not opened, and the furnace body is evacuated to the air pressure ≤ 80 Pa through the rear end vacuum suction pipe; the desulfurization rate of the petroleum coke is 91.4%.

Example 4

The device structure is the same as Embodiment 1;

The method is the same as that in Embodiment 1, except that:

When a fragment of the waste cathode carbon block of the aluminum electrolytic cell is used as the resistance heating element, the waste refractory lining pieces having a particle diameter of ≤ 8 cm are placed in the auxiliary material chamber.

Example 5

The device structure is the same as in the embodiment 1:

The method is the same as that of Embodiment 4, and the difference lies in:

When the scrap material of the waste cathode carbon block of the aluminum electrolytic cell is used as the electric resistance heating body, the crushed aggregate of the waste refractory material is ground and then mixed with the aluminum ash and pressed to form the compressed aggregate placed in the auxiliary material; the waste refractory material The chemical reaction formula of the lining pieces and the aluminum ash ingredients is:

3Na ₂ O+2Al=6Na+Al ₂ O ₃

3K ₂ O+2Al=6K+Al ₂ O ₃

Wherein Al is aluminum in an Al ash Al, Na ₂ O and K ₂ O in the waste pieces of the refractory lining Na ₂ O and K ₂ O.

Example 6

The structure of the device is the same as that in Embodiment 2, wherein the main material chamber is used for placing the scrap material of the aluminum cathode electrolytic cell waste cathode carbon block;

The method is the same as that of Embodiment 4, and the difference lies in:

When the scrap material of the waste cathode carbon block of the aluminum electrolytic cell is used as the electric resistance heating body, the waste refractory lining pieces are ground and mixed with the Fe-Al alloy powder having a particle size of less than 100 mesh, and the pressed aggregate is formed by pressing. In the auxiliary material chamber; the chemical reaction formula of the waste refractory lining fragments and the Fe-Al alloy powder is based on:

3Na ₂ O+2Al=6Na+Al ₂ O ₃

3K ₂ O+2Al=6K+Al ₂ O ₃

Wherein Al, Fe-Al alloy powder of Al, Na ₂ O and K ₂ O in the waste pieces of the refractory lining Na ₂ O and K ₂ O.

Example 7

The device structure is the same as in the embodiment 1:

The method is the same as that of Embodiment 4, and the difference lies in:

When a piece of the waste cathode carbon block of the aluminum electrolytic cell is used as the resistance heating element, the silicon nitride block bonded with the electrolyte having a particle diameter of ≤ 8 cm is placed in the auxiliary material chamber.

Claims (13)

An aluminum industrial solid waste recovery/ petroleum coke high temperature desulfurization device, characterized in that the device comprises a furnace body, a low melting point material crystallizer at the rear end of the furnace body and a liquid low melting point material collector under the low melting point material crystallizer; the furnace body The outer part is a furnace shell, the outer wall of the upper part of the furnace shell is provided with a cooling water jacket, and the top is provided with a furnace cover which is sealed and connected with the furnace shell, the furnace shell is provided with a heat insulating material layer, and the heat insulating material layer is provided with a groove type refractory material wall. The trough type refractory wall body is composed of four side wall panels and one bottom wall panel; the trough type refractory wall body is provided with a refractory concrete inner wall body; the refractory concrete inner wall body is composed of three inner walls perpendicular to the bottom wall panel The wall panel is composed of a wall panel having a height lower than that of the trough refractory wall, and a portion of the refractory concrete inner wall and the trough refractory wall adjacent to the front wall of the furnace body is surrounded by a rectangular parallelepiped chamber. A space other than the auxiliary chamber inside the groove type refractory wall is used as a main material chamber; the main material chamber is used for placing a scrap material of the aluminum cathode electrolytic cell waste cathode carbon block as a resistance heating body, or is used for placing as a resistance heating body of Petroleum coke, the petroleum coke is raw coke or calcined petroleum coke; the top of the main material chamber is provided with a top cover of the main material; the inner wall of the refractory concrete is provided with a through hole, and the top of the inner wall of the refractory concrete is also provided with a slot opening The through hole and the slot type opening communicate the main material chamber and the auxiliary material chamber; the side wall plate of the groove type refractory material wall near the front end of the furnace body is provided with two graphite electrodes, and the two graphite electrodes are located on both sides of the auxiliary material chamber. One end of the two graphite electrodes is respectively assembled with a metal electrode, the metal electrode is sealed and fixed on the furnace shell, and the other ends of the two graphite electrodes are connected to the two ends of the resistance heating body; the top of the groove type refractory wall is prefabricated a plate, a refractory insulation material plate is arranged between the prefabricated plate and the furnace cover; a top of the upper cover of the main material chamber and a space above the auxiliary material chamber and a space below the prefabricated plate serve as a crystallization chamber of a high melting point material; the furnace shell is provided with a front end vacuum with a valve An air suction pipe, the front end vacuum suction pipe is located above the two graphite electrodes, and the front end vacuum suction pipe is connected with the vacuum material channel on the insulating material layer and the groove type refractory wall, and the vacuum channel and the high melting point material are crystallized. Connected; the grooved refractory wall has a sleeve at the rear end of the wall, the sleeve is connected with the low melting point material crystallizer, and the bottom of the low melting point material crystallizer is connected with the liquid low melting point material collector through the valve, and the liquid low melting point material collector There is a lifting bag inside; the low melting point material crystallizer is provided with a rear end vacuum suction pipe with a valve and an argon gas inflation pipe. The aluminum industrial solid waste recovery/ petroleum coke high temperature desulfurization apparatus according to claim 1, wherein the low melting point material crystallizer is of a horizontal structure or a vertical structure, and an externally wound electric wire heating device is alternately wound Cooling water pipe; when the low melting point material crystallizer is of horizontal structure, the lower part is an inverted cone, and the bottom end of the inverted cone is connected to a collecting pipe, and the collecting pipe passes through the valve and the liquid low melting point substance collecting device Internally connected, the end of the low melting point material crystallizer away from the furnace body is provided with an end cap sealed with a low melting point material crystallizer; when the low melting point material crystallizer is a vertical structure, the low melting point material crystallizer consists of a sloped section and a vertical section The upper part of the inclined section is connected with the sleeve, the lower part of the inclined section is connected with the lower part of the vertical section, and the lower part of the inclined section is connected with a collecting tube which communicates with the inside of the liquid low-melting substance collector through the valve, the top of the vertical section An end cap is provided in sealing connection with the low melting material crystallizer. The aluminum industrial solid waste recycling/ petroleum coke high temperature desulfurization device according to claim 1, wherein the low melting point material crystallizer is provided with a baffle, the baffle is provided with a baffle through hole, and the rear end is vacuum pumped. Trachea and argon gas tubes are located Between the end cap and the baffle. The aluminum industrial solid waste recovery/peech coke high-temperature desulfurization device according to claim 2, wherein the liquid low-melting substance collection collector is provided with a collector upper cover, a collector upper cover and a liquid low melting point. The material collecting device is sealed and connected; the upper cover of the collecting device is fixed together with the collecting tube, and the electric resistance wire and the cooling water pipe are alternately wound around the collecting tube. A method for using an aluminum industrial solid waste recovery/ petroleum coke high temperature desulfurization apparatus according to claim 1, wherein the aluminum industrial solid waste recovery method is carried out as follows: (1) placing the scrap material of the waste cathode carbon block of the aluminum electrolytic cell in the main material chamber as a resistance heating body; the particle size of the scrap material of the aluminum cathode electrolytic cell waste cathode carbon block is ≤ 8 cm; (2) The anode carbon residue, or the waste refractory material with a particle size of ≤8 cm, or the waste refractory material, the lining pieces are ground and then mixed with aluminum ash and pressed to form a compact mass, or waste refractory material. After the lining block is ground and mixed with the Fe-Al alloy powder having a particle size of less than 100 mesh, the compressed compact formed by pressing, or the waste silicon nitride bonded silicon carbide block having a particle diameter of ≤ 8 cm is placed in the auxiliary material chamber; (3) placing or not placing a grid plate in the crystallization chamber of the high melting point substance, and the grid plate as an auxiliary crystallizer increases the crystal area; (4) vacuuming the furnace body through the front end vacuum suction pipe to a pressure of ≤ 80 Pa; (5) introducing cooling water into the cooling water jacket, cooling the metal electrode through the cooling water system, and cooling the low melting material crystallizer through the cooling water system; (6) Applying direct current through two metal electrodes and a graphite electrode to electrically heat the resistance heating body; when the temperature of the resistance heating body reaches 500±10° C., the front end vacuum suction pipe is closed, and the rear end vacuum suction pipe is opened at the same time. Vacuuming to air pressure ≤ 80Pa; continue to heat the resistance heating body, and control the temperature in the auxiliary material chamber at 1100 ± 30 ° C; (7) after the alkali metal in the resistance heating body enters the crystallization chamber of the low melting point substance, the vacuuming and heating are stopped, and the argon gas is filled into the furnace body through the argon gas inflation tube; (8) Stop cooling the low melting point material crystallizer, heat the low melting point material crystallizer to melt the condensed material on the inner wall, and enter the lift bag in the liquid low melting point material collector. A method for using an aluminum industrial solid waste recovery/ petroleum coke high temperature desulfurization apparatus according to claim 1, characterized in that the method for high temperature desulfurization of petroleum coke is carried out as follows: (1) placing petroleum coke in the main material chamber as a resistance heating body; the particle size of the petroleum coke is ≤ 8 cm; (2) When the raw coke is used as the resistance heating body, the furnace body is evacuated to the air pressure ≤ 80 Pa through the front end vacuum suction pipe; when the calcined petroleum coke is used as the resistance heating body, the furnace body is pumped through the rear end vacuum suction pipe. Vacuum to air pressure ≤ 80Pa; (3) introducing cooling water into the cooling water jacket, cooling the metal electrode through the cooling water system, and cooling the low melting material crystallizer through the cooling water system; (4) Applying direct current through two metal electrodes and a graphite electrode to electrically heat the resistance heating body; when raw coke is used as the resistance heating body, and when the temperature of the resistance heating body reaches 700 to 900 ° C, the front end vacuum exhaust pipe is closed. , vacuuming the furnace body through the back end vacuum suction pipe, to the air pressure ≤ 80Pa; (5) When the temperature of the resistance heating body reaches 1500 ~ 1700 ° C, stop vacuuming and heating, and fill the furnace body with argon gas through an argon gas inflation tube; (6) Stop cooling the crystallizer of the low melting point material, heat the crystallizer of the low melting point material to melt the condensed elemental sulfur on the inner wall, and enter the lift bag in the liquid low melting point material collector. The method for using the aluminum industrial solid waste recovery/ petroleum coke high-temperature desulfurization device according to claim 5, characterized in that in the step (7) and when the temperature in the furnace body falls below 700 ° C, the high melting point substance crystallizing chamber is condensed. The material is taken out. The method for using the aluminum industrial solid waste recovery/ petroleum coke high-temperature desulfurization device according to claim 5, characterized in that the material condensed in the crystallization chamber of the low-melting substance is an alkali metal or an alkali metal alloy, and the alkali metal alloy is a sodium-potassium alloy, containing The sodium of metallic lithium or the sodium-potassium alloy containing lithium, and the material condensed in the crystallization chamber of the high melting point substance is a fluoride salt electrolyte. The method for using the aluminum industrial solid waste recovery/ petroleum coke high temperature desulfurization device according to claim 5 or 6, wherein the low melting point material crystallizer is cooled by a cooling water pipe outside the low melting point material crystallizer, and the low melting point substance is passed through. A wire heater outside the crystallizer heats the low melting material crystallizer. The method for using the aluminum industrial solid waste recovery/ petroleum coke high-temperature desulfurization device according to claim 5, characterized in that in the step (2), the waste refractory material is lined with a crushed piece and then mixed with aluminum ash and pressed to form a pressure group. Material, or waste refractory lining pieces are ground and mixed with Fe-Al alloy powder with a particle size of less than 100 mesh, and pressed to form a compacted material, wherein the waste refractory lining pieces and aluminum ash or Fe-Al alloy powder ingredients The chemical reaction formula is based on: 3Na ₂ O+2Al=6Na+Al ₂ O ₃ 3K ₂ O+2Al=6K+Al ₂ O ₃ Wherein Al is aluminum or an Al ash Fe-Al alloy powder of Al, Na ₂ O and K ₂ O in the waste pieces of the refractory lining Na ₂ O and K ₂ O. The method for using the aluminum industrial solid waste recovery/ petroleum coke high temperature desulfurization device according to claim 6, wherein in the step (6), the low melting point material crystallizer is heated to melt the condensed material on the inner wall to control the low melting point. The temperature in the material crystallizer is higher than the melting point of the low melting point material by 30 to 100 ° C, and the low melting point substance is elemental sulfur. The method for using the aluminum industrial solid waste recovery/ petroleum coke high-temperature desulfurization device according to claim 5, characterized in that in the step (8), the low-melting substance crystallizer is heated to melt the condensed material on the inner wall to control the low melting point. The temperature in the material crystallizer is higher than the melting point of the low melting point material by 30 to 100 ° C, and the low melting point substance is an alkali metal or an alkali metal compound. gold. The method of using the aluminum industrial solid waste recovery/petroleum high temperature desulfurization apparatus according to claim 6, wherein the petroleum coke has a desulfurization rate of ≥90%.

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