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A method for regenerating carbonaceous waste from an aluminum electrolytic cell into a raw material for the production of calcium carbide

A technology of aluminum electrolytic cells and carbon, which is applied in the field of recycling carbon waste from aluminum electrolytic cells into raw materials for the production of calcium carbide. It can solve the problems of affecting the quality of clinker, shortening recycling, and long heating time, so as to achieve resource circulation and viscosity. The effect of reducing and high carbon content

Active Publication Date: 2019-06-21
长沙紫宸科技开发有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this method obviously has the following problems: first, toxic dust and gas containing cyanide are produced during the crushing and screening process of electrolytic aluminum waste cathode carbon; The power consumption of vacuum suction is higher, and the requirements and cost of equipment are also very high; the third is that the fluoride gas volatilized at 2600-2800 ° C is absorbed by water mist, which has too high requirements on equipment, because the water vapor at 1200 ° C is enough to fluorine Calcium chloride and other fluorides are directly converted into highly toxic and highly corrosive hydrogen fluoride; fourth, serious secondary pollution is likely to occur, and the recovered carbon materials still contain 3% or more fluorides, and recycling will shorten the overhaul Deadline is not cost-effective
However, this method obviously has the following problems: first, toxic dust and gas containing cyanide are produced during the crushing and screening process of electrolytic aluminum waste cathode carbon; The power consumption of vacuum suction is higher, and the requirements and cost of equipment are also high; the third is that the flue gas purification investment after secondary combustion is high, and it is easy to produce serious secondary pollution; Carbon still contains a large amount of fluoride, because the boiling point of calcium fluoride is as high as 2497 ° C, the recycling of fluorine-containing carbon materials will shorten the overhaul period and is not cost-effective
[0010] (3) Combustion separation method: professional incinerator and fluidized bed furnace technology are used. Because electrolytic aluminum waste cathode charcoal is different from coal combustion, although the calorific value is generally as high as 4000-5500kcal / kg, the activation energy required for oxidation reaction is high. , needs to reach a high temperature of 1500°C to effectively oxidize and burn, so the combustion method has the problems of cumbersome separation process, long heating time required for burnout, high energy consumption, and difficulty in effectively recovering fluoride in it, and the problem of secondary pollution is also difficult to deal with
[0011] (4) Fuel method: Because the main component of electrolytic aluminum waste cathode carbon block is charcoal, and the theoretical calorific value of complete combustion is generally above 4000kcal / kg, and the highest is 5500kcal / kg, which is equivalent to the calorific value of commonly used anthracite. Therefore, A large number of technical workers at home and abroad have made unremitting efforts, but the results have been extremely unsatisfactory so far
However, there are still safety issues, the amount of addition, and the impact on production. After all, waste cathode carbon is not coal-fired, and the carbon in waste cathode carbon blocks is extremely difficult to burn
However, the real defect is not the erosion of refractory materials caused by fluoride and the excessive fluorine in the flue gas, because the production of calcium fluoroaluminate cement can also ensure the safety of refractory materials and the fluorine in the flue gas does not exceed the standard. After all, normal cement The kiln preheater system objectively has a preheater that realizes five-stage exchange and capture of alkaline high-concentration powder; it is not a problem of extremely high alkali content, because the coal consumption per ton of clinker is generally only 0.15-0.18t, and a small amount The electrolyte in the cathode carbon block is mainly aluminum fluoride, calcium fluoride, sodium fluoroaluminate, magnesium fluoroaluminate, sodium fluoride only accounts for a small amount, and the total alkali in sodium fluoroaluminate and sodium fluoride when the dosage is small The amount is limited, and generally has limited influence on the later strength of cement
Therefore, the real reason why Shandong Aluminum Plant has not been able to use cathode carbon normally as an alternative coal combustion is: firstly, it affects the grinding efficiency of coal mills, and secondly, the low-activity graphite carbon seriously reduces the overall combustion performance of coal powder , seriously affects the normal combustion efficiency of pulverized coal, and the carbon that cannot be effectively burned in time to release heat falls into the clinker or is wrapped in the powder to produce strong reduction, which affects the working conditions of the kiln system and the quality of the clinker
Apparently, the prior art still cannot use electrolytic aluminum waste cathode carbon block as an effective alternative fuel
[0012] (5) Safe landfill method: Due to the problems of high energy consumption, high cost and secondary pollution in the existing treatment methods, the environmental pollution problem of electrolytic aluminum waste cathode carbon blocks has not been effectively solved, resulting in the vast majority of aluminum The spent cathode carbon block of the electrolyzer is still discarded, and the high-cost safe landfill method is still mainly used at present
However, the process is complicated, the secondary pollution is large, the energy consumption is high, and the recovered graphite fine powder has high impurity content.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] The aluminum electrolytic cell carbon waste used in the embodiment of the present invention is taken from the massive carbon waste stockpiled in the warehouse of an aluminum factory, and the inorganic matter content of the mixed sample is 32.67% (among them, the aluminum content is 2.43%, and the alkali content is 11.98% %, cyanide content 0.17%), carbon content 67.16%; the strong oxidation activator used in this example is ZC-YO7 type strong oxidation activator (that is dichromate strong oxidation activator and hypochlorite strong oxidation activator The activator was purchased from Hunan Xiaoyin Wuji Environmental Energy Technology Development Co., Ltd. with a mass ratio of 1:1.

[0049] (1) Pretreatment: impact-crushing 1t of aluminum electrolytic cell carbon waste into granular materials with a particle size of ≤12mm;

[0050] (2) Recovery of activated carbon and alkali aluminum: put 1 ton of granular material obtained in step (1) into a rolling mixing and leaching ...

Embodiment 2

[0057] The aluminum electrolytic cell carbon waste used in the embodiment of the present invention is taken from the massive carbon waste stockpiled in the warehouse of an aluminum factory, and the inorganic matter content of the mixed sample is 30.68% (among them, the aluminum content is 2.41%, and the alkali content is 9.87% %, cyanide content 0.16%), carbon content 69.16%; the strong oxidation activator used in this embodiment is potassium ferrate, sodium dichromate, cobalt perchlorate, lithium metavanadate, calcium hypochlorite molar An oxidation activator made by mixing in a ratio of 3:1:2:1:2.

[0058] (1) Pretreatment: impact-crushing 1t of aluminum electrolytic cell carbon waste into granular materials with a particle size of ≤10mm;

[0059] (2) Recovery of activated carbon and alkali aluminum: put 1 ton of granular material obtained in step (1) into a stirring and leaching device, first add 5 tons of water, and then add 117 kg of sodium hydroxide with a mass concentra...

Embodiment 3

[0066] The aluminum electrolytic cell carbon waste used in the embodiment of the present invention is taken from the massive carbon waste stockpiled in the warehouse of an aluminum factory, and the inorganic matter content of the mixed sample is 40.59% (among them, the aluminum content is 4.93%, and the alkali content is 13.76% %, cyanide content 0.14%), carbon content 59.27%; the quicklime used in this embodiment selects the powdered lime under the sieve of the calcium carbide plant (the mass content of calcium oxide is 91.6%); the strong oxidation activator used in this embodiment It is a ZC-YO5 type strong oxidation activator (that is, a mixture of ferrate strong oxidation activator and perchlorate strong oxidation activator with a mass ratio of 1:1), and the detoxification agent solution used in this example is ZC-XJ1 Type detoxification agent solution (i.e. a saturated solution prepared with a mass ratio of ferrate detoxification agent and hypochlorite detoxification agent...

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Abstract

The invention provides a method for regenerating aluminum electrolysis cell carbon-base waste into a raw material for calcium carbide production. The method comprises the following steps that (1) the aluminum electrolysis cell carbon-base waste is broken; (2) the broken aluminum electrolysis cell carbon-base waste is placed into a leaching pond, a stirring leaching device or a rolling mixing leaching device, water is added firstly, then caustic soda or a solution of the caustic soda, quick lime and a drastic oxidation active agent are added, oxidization leaching is conducted, filtering separating is conducted, an aluminum alkali solution and solid filter residues are obtained, and after the solid filter residues are washed with water and dried, activated carbon residues containing carbon and calcium fluoride are obtained; and (3) the activated carbon residues are placed into a rolling mixing machine, a hydrocarbon binder is added, or quick lime is further added, rolling mixing and forming are conducted, and the raw material for calcium carbide production is obtained. According to the method for regenerating the aluminum electrolysis cell carbon-base waste into the raw material for calcium carbide production, the obtained raw material for calcium carbide production is high in carbon content, low in impurity content and high in aluminum and alkali desorption recovering rate; the obtained raw material for calcium carbide production is applied to calcium carbide production, the yield is increased, the average power consumption of calcium carbide of per ton is reduced, the calcium carbide gas yield is increased, and no cyanide is detected; and the method is safe, simple, large in processing quantity and low in energy consumption and cost.

Description

technical field [0001] The invention relates to a method for regenerating carbon waste from an aluminum electrolytic cell, in particular to a method for regenerating carbon waste from an aluminum electrolytic cell into raw materials for producing calcium carbide. Background technique [0002] At present, the output of electrolytic aluminum in my country and the world is developing rapidly. According to statistics, by the end of December 2016, the aluminum smelting enterprises of electrolytic aluminum in my country had built a production capacity of 43.698 million tons, and the operating production capacity had reached 36.739 million tons. With the increase of electrolytic aluminum production, the solid waste produced in the electrolysis process, such as waste cathode carbon, waste anode carbon particles, waste refractory bricks, waste insulation bricks, and waste insulation slag, has also increased rapidly, of which only my country's electrolytic aluminum The annual waste ca...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B09B3/00B09B5/00C01B32/942
CPCB09B3/00B09B5/00
Inventor 尹小林
Owner 长沙紫宸科技开发有限公司
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