阅读说明：本技术 一种电解铝废弃炭块的无害化利用工艺 (Harmless utilization process of waste carbon blocks of electrolytic aluminum ) 是由 李玉新 吴汉元 王强 俞海明 刘鲁新 陈红 崔兵 王伟 蒲翠娥 王洪林 段建勇 于 2019-10-29 设计创作，主要内容包括：本发明公开了一种电解铝废弃炭块的无害化利用工艺,其工艺步骤如下：1)将铝厂废弃的炭块拉回厂区,堆存在专用防雨防潮的厂房待用；2)采购炼化厂废弃的重油,拉运到厂区待用；3)将重油和废弃炭块按照重量百分比为5：95的比例混合,加入到球磨机内磨细制成粒度为0.5mm的混合粉待用；4)回转窑生产石灰时,将煤粉和上述混合粉按照100：1的重量比例,加入到喷吹罐,在生产石灰的工艺中喷吹；5)生产的石灰,供应给炼钢、铁水脱硫专项工艺使用。本发明能够有效地对电解铝废弃炭块进行无害化处理,有利于消除环境污染。(The invention discloses a harmless utilization process of waste carbon blocks of electrolytic aluminum, which comprises the following process steps: 1) pulling the waste carbon blocks of the aluminum plant back to the plant area, and piling up the carbon blocks in a special rainproof and moistureproof workshop for later use; 2) purchasing waste heavy oil of a refinery and transporting the heavy oil to a factory area for standby; 3) the heavy oil and the waste carbon blocks are mixed according to the weight percentage of 5: 95, adding the mixture into a ball mill, and grinding the mixture into mixed powder with the granularity of 0.5mm for later use; 4) when lime is produced in the rotary kiln, mixing the coal powder and the mixed powder according to the ratio of 100: 1, adding the mixture into a blowing tank, and blowing in the process of producing lime; 5) the produced lime is supplied to special processes for steel making and molten iron desulphurization. The invention can effectively carry out harmless treatment on the waste carbon blocks of the electrolytic aluminum, and is beneficial to eliminating environmental pollution.)

1. A harmless utilization process of waste carbon blocks of electrolytic aluminum is characterized in that: the process comprises the following steps:

1) pulling the waste carbon blocks of the aluminum plant back to the plant area, and piling up the carbon blocks in a special rainproof and moistureproof workshop for later use;

2) purchasing waste heavy oil of a refinery and transporting the heavy oil to a factory area for standby;

3) the heavy oil and the waste carbon blocks are mixed according to the weight percentage of 5: 95, adding the mixture into a ball mill, and grinding the mixture into mixed powder with the granularity of 0.5mm for later use;

4) when lime is produced in the rotary kiln, mixing the coal powder and the mixed powder according to the ratio of 100: 1, adding the mixture into a blowing tank, and blowing in the process of producing lime;

5) the produced lime is supplied to special processes for steel making and molten iron desulphurization.

Technical Field

The invention relates to a harmless utilization process of waste carbon blocks of electrolytic aluminum.

Background

The modern electrolytic aluminum industry adopts cryolite-alumina molten salt electrolytic process. The molten cryolite is solvent, alumina is solute, carbosome is anode, aluminium liquid is cathode, strong direct current is introduced, electrochemical reaction is carried out on two poles in the electrolytic cell at 950-970 ℃, namely electrolysis.

The aluminum electrolysis process is carried out in an electrolysis cell. The electrolytic bath is composed of carbon material and refractory material. In the production process of electrolytic aluminum, the cathode carbon block is deformed and broken due to the permeation and corrosion of high-temperature electrolyte to lining materials, and aluminum liquid and electrolyte in the electrolytic cell permeate downwards along cracks and reach the bottom of a hearth, so that the electrolytic cell cannot be normally produced and needs to be stopped for overhaul.

During overhaul, the carbon material of the electrolytic cell, namely the cathode carbon block, is dismantled and discarded, so that the electrolytic cell becomes dangerous waste.

The physical phase analysis of the waste cathode carbon block of the aluminum electrolytic cell is carried out to obtain the specific components of the waste cathode (shown in Table 2), namely carbon (C) and cryolite（Na₃AlF₆) Alumina (alpha-Al)₂O₃，β-Al₂O₃) Sodium fluoride (NaF), calcium fluoride (CaF)₂) And the content of each component is different according to the position of the electrolytic bath. The contents and compositions of substances contained in different parts of a waste cathode of a certain plant are shown in the following table.

Because the easily soluble sodium fluoride and sodium fluoroaluminate exist in the cathode carbon block, the cathode carbon block is a main factor for polluting the environment. The small amount of cyanide formed in the carbon block is a lethal, highly toxic substance.

In the review of literature (1), the liang wen is on the fourth stage of "Gansu metallurgy" in 2017, and a paper entitled "disposal and recycling scheme of aluminum ash, carbon slag and overhaul slag" is published, and in the paper, the process of treating the waste tank lining carries out harmless treatment on the impermeable material, the heat-insulating material and the waste cathode material in the waste tank lining, and the curing agent and the additive are added in the treatment process, so that the impermeable material and NaF contained in the heat-insulating material at the bottom of the electrolytic tank are converted into insoluble fluoride salt. The purpose of solidifying the fluorinion in the waste heat-insulating material is achieved. Cyanide in the waste tank lining is removed through the oxidation of the oxidant and the additive, and the purpose of adding the oxidant is realized. "is described; (2) li hong published a paper entitled "pollution prevention and comprehensive utilization of aluminum cell overhaul residues" in nonferrous metals journal of volume 55 in 2003, and the paper contains "aluminum cell overhaul residues which are valuable materials and cannot be easily discarded without use because the aluminum cell overhaul residues contain 70% of C and the calorific value is estimated to be 7000-12000 kJ/kg. Among the most valuable compounds are the fluoride salts, accounting for approximately 30%. Thus, some aluminum plants, such as the austria lunsfen (ranshoffen) and the american national stuttera (Lister) aluminum plants, leach their electrolyte with alkaline liquors, which are used to synthesize cryolite, and carbon is used as a fuel. "while in this paper there is also" the composition of the cement is CaO-SiO₂-Al₂O₃-Fe₂O₃Is a cheap building material produced in bulk. The carbon in the electrolytic cell overhaul slag is just used as a supplementary fuel in cement production. The alkali metal fluoride can be used as a catalyst in the sintering reaction of the charging, thereby reducing the sintering temperature of clinker and reducing the fuel consumption. The waste carbon blocks are crushed and then added into a cement clinker kiln to replace part of fuel, so that energy is saved, fluorine contained in the carbon blocks can be used as a mineralizer to improve the firing conditions in the kiln, and the fluorine is generated into solid CaF₂When entering the cement, the cement can not pollute the environment, achieves the aim of comprehensive utilization, and cement plants are arranged in various places, thereby having wider utilization conditions. "is expressed in terms of content; (3) in the journal of "industrial safety and dust prevention" of the 9 th phase of 2000, li-chaonan, a paper entitled "innocent treatment of overhaul slag of aluminum electrolysis cell" was published, in which "(1) a waste cathode carbon block is used for sintering process alumina production and succeeds in Shandong aluminum factories, the waste carbon block is crushed to below 25mm and enters the alumina production process together with anthracite to improve the dissolution condition, and (2) the waste cathode carbon block is crushed and then added into a cement clinker kiln to replace part of fuel, because the hardness of the carbon block is higher, the crushing and grinding consumption is more, the application is limited to a certain extent unless encouragement measures are taken, and" the content expression "is provided.

The above description shows that the existing treatment process of the waste carbon blocks mainly adopts two major types of processes of cement production by a rotary kiln and wet flotation, and no literature reports about an application process applied to metallurgical lime production.

Disclosure of Invention

The invention aims to provide a harmless utilization process of waste carbon blocks of electrolytic aluminum, which can effectively perform harmless treatment on the waste carbon blocks of electrolytic aluminum and is beneficial to eliminating environmental pollution.

The invention aims to realize the harmless utilization process of the waste carbon blocks of the electrolytic aluminum, which comprises the following process steps:

1) pulling the waste carbon blocks of the aluminum plant back to the plant area, and piling up the carbon blocks in a special rainproof and moistureproof workshop for later use;

2) purchasing waste heavy oil of a refinery and transporting the heavy oil to a factory area for standby;

3) the heavy oil and the waste carbon blocks are mixed according to the weight percentage of 5: 95, adding the mixture into a ball mill, and grinding the mixture into mixed powder with the granularity of 0.5mm for later use;

4) when lime is produced in the rotary kiln, mixing the coal powder and the mixed powder according to the ratio of 100: 1, adding the mixture into a blowing tank, and blowing in the process of producing lime;

5) the produced lime is supplied to special processes for steel making and molten iron desulphurization.

The inventor proposes and implements the carbon block as fuel in the production of lime by combining the lime production process according to the principle of slagging by using lime and fluorite in steel making. In the using process, fluoride in the lime is converted into calcium fluoride in the production process of lime through chemical reaction, sodium salt becomes sodium silicate, the using amount of fluorite can be reduced in the steelmaking process, the steelmaking process is optimized, and the value maximization of the waste carbon blocks is realized.

The inventor learns that the main process characteristics of the fluorite for steelmaking in the steelmaking process are as follows:

the flame temperature in the oxygen flow jet impact area in the converter is as high as 2000-2600 ℃, volatile matters are easily generated in all components in metal, all components of furnace slag on the surface of the metal are volatilized to different degrees, and when fluorite is added for slagging, the main component CaF₂Under the combined action of the high temperature in the furnace and the slag, the following reactions occur:

(CaF₂)+{H₂O}=(CaO)+2{HF}

2(CaF₂)+{SiO₂}=2(CaO)+{SiF₄}

(CaF₂)+(MgO)=(CaO)+{MgF₂}

therefore, from the viewpoint of slag ion theory, it is considered that F is caused^-The ions cut the chain structure of the silicate. It can rapidly melt slag without lowering the basicity of the slag.

In addition, the melting points of the sodium fluoride and the sodium fluoroaluminate in the middle of the carbon block are 993 ℃ and 1013 ℃ (CAS data), and certain thermodynamic and kinetic conditions are required for converting the sodium fluoride and the sodium fluoroaluminate into the calcium fluoride, so the inventor combines the characteristics and adopts the following process:

1) pulverizing the carbon block, and adding 5% of heavy oil to the pulverized carbon block and mixing and grinding the pulverized carbon block and the heavy oil in a mill;

2) preparing the carbon block into fine particles of about 0.5 mm;

3) while adopting coal injection, the carbon block, heavy oil powder and coal powder are mixed according to the proportion of 1: uniformly mixing the materials according to the mass ratio of 100, and then blowing;

4) the produced lime is specially used for steel-making production and molten iron desulphurization;

the process route of the invention is as follows: waste carbon blocks → crushers → heavy oil and coal powder mixing + ball mills → powder spraying → lime production in coal-fired rotary kilns for harmless transformation → lime for metallurgy → electric furnaces + converter steelmaking → steel slag formation → resource utilization.

The innovation points of the invention are based on the following points:

1) sodium fluoride and sodium fluoroaluminate are decomposed in a high-temperature region of jet flow flame of an injection spray gun for producing lime in a rotary kiln, wherein sodium salt and fluorine react with silicon dioxide generated by combustion of coal powder to generate low-melting-point substances such as sodium silicate liquid drops, and the reaction equation is as follows:

NaF=Na⁺+F^-

4Na⁺+O₂=2Na₂O

2Na₂O+SiO₂=Na₂SiO₃

Na₃AlF₆=3Na⁺+Al³⁺+6F^-

4Al³⁺+3O₂=2Al₂O₃

nAl₂O₃+mCaO→mCaO·nAl₂O₃

4F^-+SiO₂={SiF₄}+2O^2-

2) the added heavy oil is a polar substance and also a grinding aid in the carbon block grinding process, and can be tightly combined with the carbon block powder.

3) Heavy oil combustion decomposes water, can react with SiF₄Reacting, and then reacting with CaO small particles dispersed in furnace gas in the lime calcining process to form calcium fluoride, so as to realize harmless conversion, wherein the equation of the reaction is as follows:

CnOmHy+xO₂→CO+H₂O

2H₂O+{SiF₄}=4HF+SiO₂

2HF+CaO=CaF₂+H₂O

4) the calcined lime is specially oriented for steelmaking or molten iron desulphurization.

5) The calcium aluminate and the sodium aluminate are fluxing agents in the steelmaking process, so that the using amount of a slag melting agent in the steelmaking process can be reduced, and cost reduction and efficiency improvement of steelmaking are facilitated.

6) Cyanide in the middle of the waste carbon block realizes decomposition reaction in the combustion zone, and harmless conversion is easily realized.

Detailed Description

The implementation process of the invention takes a rotary kiln process of 60 ten thousand tons of lime produced by Bao Xin Changjia company in year as an example:

a harmless utilization process of waste carbon blocks of electrolytic aluminum comprises the following process steps:

1) pulling the waste carbon blocks of the aluminum plant back to the plant area, and piling up the carbon blocks in a special rainproof and moistureproof workshop for later use;

2) purchasing waste heavy oil of a refinery and transporting the heavy oil to a factory area for standby;

3) the heavy oil and the waste carbon blocks are mixed according to the weight percentage of 5: 95, adding the mixture into a ball mill, and grinding the mixture into mixed powder with the granularity of 0.5mm for later use;

4) when lime is produced in the rotary kiln, mixing the coal powder and the mixed powder according to the ratio of 100: 1, adding the mixture into a blowing tank, and blowing in the process of producing lime;

5) the produced lime is supplied to special processes for steel making and molten iron desulphurization.