CN109706327B - Method for harmlessly treating beryllium slag - Google Patents
Method for harmlessly treating beryllium slag Download PDFInfo
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- CN109706327B CN109706327B CN201811624398.0A CN201811624398A CN109706327B CN 109706327 B CN109706327 B CN 109706327B CN 201811624398 A CN201811624398 A CN 201811624398A CN 109706327 B CN109706327 B CN 109706327B
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Abstract
A method for harmlessly treating beryllium slag comprises the steps of taking the beryllium slag as a slag-matching type auxiliary material for lead smelting in a blast furnace, crushing and uniformly mixing the beryllium slag and raw materials for traditional lead smelting in the blast furnace, pressing and forming a block furnace charge, putting the furnace charge into the blast furnace, smelting according to a traditional lead smelting method, thermally decomposing soluble beryllium sulfate in the beryllium slag in the smelting process, oxidizing the soluble beryllium sulfate into beryllium oxide, dispersing the beryllium oxide into slag-forming components of silicon, iron and calcium in the furnace charge, and coating the beryllium oxide with ferrosilicon calcium slag after slag forming and melting, so that the soluble beryllium sulfate in the beryllium slag can be subjected to magnitude reduction and can not be dissolved out by an acid rain environment. The method can utilize the equipment and mature technology of the existing lead smelting enterprises to carry out large-scale harmless treatment, can save a large amount of investment of special environment-friendly funds, and has higher economic benefit and environmental benefit; the disposed slag is reduced in magnitude and harmless and can be reused.
Description
Technical Field
The method relates to the field of non-ferrous metal lead smelting slagging technology and environmental protection, in particular to a method for harmlessly treating beryllium slag.
Background
In the beryllium production process, after the beryllite ore containing beryllium is treated by the Texas method, a large amount of leaching residues, commonly called beryllium residues, are left. When the leaching residue is subjected to liquid-solid separation, the residue contains a certain proportion of water more or less, and toxic and soluble beryllium salt (beryllium sulfate) often exists in the water. Because the industrial production emphasizes the production efficiency, the actual control index of the residual beryllium in the beryllium slag is generally 0.1-0.5%. This index is unacceptable relative to environmental protection, so manufacturers have established dedicated sites for the reliable storage of beryllium residues, which are highly harmful once dispersed in the living environment.
Although the method is an effective method for professional sealing of the beryllium slag, hidden dangers exist all the time. The fundamental method is to carry out harmless treatment and even resource treatment on the waste water. Some people try to treat the beryllium slag by a high-temperature roasting method, but the treated beryllium slag is tested according to GB5085.3-2007 hazardous waste identification standard leaching toxicity identification, and the detected beryllium content exceeds the standard. And the crushed beryllium slag roasted at high temperature is used as a blending material for cement concrete for curing treatment, and the test of GB5085.3-2007 standard shows that the treatment has obvious environment-friendly effect, but the blending amount is sensitive to the influence of the strength of the concrete, and hidden danger exists on the construction quality of buildings, so the popularization and the application are difficult, and the large-scale treatment cannot be realized.
Disclosure of Invention
The purpose of the invention is: in order to solve the problems in the prior art, the method for harmlessly treating the beryllium slag is provided, soluble beryllium salt in the beryllium slag is baked into beryllium oxide through the traditional lead-smelting technology, the beryllium oxide is reduced in magnitude, and the beryllium oxide is coated by slag so that the beryllium oxide can not be dissolved out in an acid rain environment. Because beryllium oxide is stable and insoluble with respect to water, but in an acid rain environment, beryllium oxide risks being dissolved out.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for harmlessly treating beryllium slag comprises the following steps:
a. taking beryllium slag as a slag-matching type auxiliary material for lead smelting in a blast furnace, adding the beryllium slag into a raw material for traditional lead smelting in the blast furnace, crushing, uniformly mixing, and pressing to form a block furnace burden; wherein the addition amount of the beryllium slag is 5-15% of the total weight of the beryllium slag and the traditional lead smelting raw materials, the addition amount is too small to be large, and the production economy of a lead system is greatly influenced if the addition amount is too large;
b. and (2) putting the pressed briquette furnace burden into a blast furnace to be smelted according to a traditional lead smelting method (during smelting, the addition of coke and combustion-supporting air, the generation of crude alloy and the treatment process of flue gas are the prior art and are not described herein), wherein soluble beryllium sulfate in beryllium slag is thermally decomposed and oxidized into beryllium oxide in the smelting process, the beryllium oxide is dispersed in slagging components of silicon, iron and calcium in the furnace burden, and the beryllium oxide is coated by ferrosilicon calcium slag after slagging and melting.
After the briquette furnace burden is put into a blast furnace, in the process of carrying out high-temperature reduction smelting according to the traditional lead smelting method, lead and other valuable metals are reduced into metal and are co-melted with a main product lead to form crude alloy, and the crude alloy flows out from a hearth; the soluble beryllium sulfate in the beryllium slag is thermally decomposed at high temperature in the furnace, the beryllium is quickly oxidized into beryllium oxide, the generated beryllium oxide is dispersed in slag-making components of silicon, iron and calcium of furnace charge, and the beryllium oxide and the slag-making components are melted in the furnace according to the slag type selected during burdening to form network calcium silicon slag (also called calcium silicon glass ceramic), and the beryllium oxide is coated in the calcium silicon glass ceramic. The slag generated in the lead smelting process flows through the coke layer at the bottom of the furnace, is fully overheated, flows out of the furnace from a slag hole, flows into a slag flushing water channel, is dispersed by high-pressure water and is quenched into fine slag (commonly called water quenching slag) with the granularity of 1-3 mm.
In the step a, the shape of the briquetting furnace burden can be brick shape, cylindrical shape and the like, and the briquetting is carried out according to the requirement of the traditional blast furnace lead smelting method for raw materials.
The beryllium slag is taken as a slag-matching type auxiliary material and is mixed with the lead smelting raw material and then is put into the blast furnace, and the method is completely carried out according to the traditional lead smelting method of the blast furnace. The method is characterized in that the beryllium content in a terminal product is greatly reduced by batching the beryllium slag with low content, namely, the beryllium slag is commonly called as 'magnitude reduction'; the micro-level soluble beryllium salt in the beryllium slag is uniformly dispersed in the slag-forming component ferrosilicon calcium through thermal decomposition and oxidation, and is co-melted into ferrosilicon calcium slag through slag forming, and the beryllium oxide is coated by the networked ferrosilicon calcium glass ceramic, so that the beryllium oxide can not be dissolved out by acid rain, and the aim of harmlessness is fulfilled. The ferro-silicon calcium slag containing trace harmless beryllium can be used for adding iron to cement clinker in the cement industry as the beryllium-free slag because of high iron content, and can also be used as a cheap filling ingredient of a soil-mixing stirring station after being finely ground and crushed.
The beryllium slag treated by the method has the following advantages: firstly, the equipment capacity of the existing lead smelting enterprises can be utilized to carry out large-scale harmless treatment, so that a large amount of special capital investment for environmental protection can be saved; secondly, the mature technology and management operation of lead enterprises are utilized, so that the disposal cost is low, and the economic benefit and the environmental protection benefit are high; thirdly, the disposed slag is reduced and harmless, and can be recycled, thereby achieving the highest level of resource environmental protection disposal.
Detailed Description
Example 1
Take an enterprise which utilizes secondary resources at the first time of the Leishui river, namely, smelts the lead from various raw materials such as smoke dust, leaching slag and the like as an example. The enterprise has a 6 square meter blast furnace, and produces and processes 200T lead smelting raw materials every day, and the production raw materials and the components of the beryllium slag are detailed in the following table 1:
TABLE 1 composition table of traditional lead-smelting raw material and beryllium slag in blast furnace
According to the lead smelting process requirements of the enterprises, the charging materials entering the blast furnace meet the following requirements in weight ratio: 25-30% of Pb, 0.5-3.5% of As, and SiO25-8% of Fe, 18-23% of Fe and 4-6% of CaO. Therefore, the ingredient formula (weight ratio) obtained by combining the raw material ingredient table through design calculation is as follows: the lead ash, lead mud, iron powder, calcium stone powder and beryllium slag are 38: 10: 18: 20: 4: 10, and the components (weight ratio) of the materials prepared according to the formula are as follows: pb 29.71%, S4.31%, As 1.1%, Be 0.03%, SiO26.04 percent, 22.4 percent of Fe and 5.1 percent of CaO, except the micro-beryllium, the ingredients of the ingredients meet the furnace charge standard of the enterprise and can be normally smelted. After the smelting in a blast furnace, 55-65 wt% of iron in furnace burden is mixed with sulfur and arsenic to generate pyrite cinder and arsenic iron cinder, the rest iron in ferrous oxide form and silicon and calcium form silicate molten slag, and trace soluble beryllium sulfate in the beryllium slag is subjected to thermal decomposition, oxidation and ferrosilicon calcium combined slagging process in the furnace. Because trace beryllium oxide is melted in a large amount of ferrosilicon calcium slag, the surface is completely surrounded by networking to form actual isolation from the outside, and the generated beryllium-containing slagThe typical components (weight ratio) of the silicon-iron-calcium slag are as follows: SiO 2228-35%, 18-22% of Fe, 14-17% of CaO and 0.06-0.08% of BeO. After water quenching, the mixture is in the shape of sand grains with the diameter of 1-3 mm. GB5085.3-2007 hazardous waste leaching toxicity identification tests show that beryllium is not detected in the leaching liquid, so that the beryllium slag treatment substance is considered to be nontoxic. In the process of the embodiment, 200 tons of beryllium residues are co-processed, the trial production time is 10 days, the disposal cost of each ton is about 850 yuan/ton, in addition, because the lead content of the beryllium residues is about 2.7%, the beryllium residues are recycled together during the smelting disposal of a blast furnace, the direct yield is 88%, the additional value is added, the disposal cost of each ton of beryllium residues is about 475 yuan/ton, and the actual disposal cost of each ton of beryllium residues after the phase impact is about 375 yuan/ton.
Comparative examples
The amount of the beryllium slag added is greatly increased to 20 wt%, and the economic benefit is compared with that of the embodiment 1 only by testing for 2 days. The production equipment, raw materials and process are the same as those in the example 1, and the specific formula (weight) of the ingredients is as follows: the test components (weight ratio) of the materials prepared according to the formula are Pb 23.21%, S4.41%, As 0.95%, Be 0.06%, SiO 028.44 percent, Fe 19.4 percent and CaO 6.1 percent. The slag produced by blast furnace smelting has SiO component (weight ratio)234.8 percent, 19.5 percent of Fe, 17.5 percent of CaO and 0.13 percent of Be. The test of the GB5805.3-2007 standard detects trace beryllium, but the trace beryllium is not overproof, and the slag is still harmless, but the lead content in the ingredients is reduced, and the lead bullion alloy obtained by smelting is obviously reduced compared with the example 1. Therefore, the dosage proportion of the beryllium slag is controlled, otherwise, the dosage of the beryllium slag is too large, and the lead smelting benefit is directly influenced.
Claims (2)
1. A method for harmlessly treating beryllium slag is characterized by comprising the following steps:
a. taking beryllium slag as a slag-matching type auxiliary material for lead smelting in a blast furnace, adding the beryllium slag into a raw material for traditional lead smelting in the blast furnace, crushing, uniformly mixing, and pressing to form a block furnace burden; wherein the addition amount of the beryllium slag is 5-15% of the total weight of the beryllium slag and the traditional lead smelting raw materials;
b. and (2) putting the pressed briquette furnace burden into a blast furnace for smelting according to a traditional lead smelting method, wherein soluble beryllium sulfate in the beryllium slag is thermally decomposed and oxidized into beryllium oxide in the smelting process, the beryllium oxide is dispersed in slag-making components of silicon, iron and calcium in the furnace burden, and the beryllium oxide is coated by ferrosilicon calcium slag after the slag-making is melted.
2. The method for harmless disposal of beryllium slag as claimed in claim 1, wherein the ferrosilicon calcium slag coated with beryllium oxide is dispersed by high-pressure water and quenched into fine slag with a particle size of 1-3 mm in the process of flowing out of the furnace from the slag hole through the blast furnace bottom coke layer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105344698A (en) * | 2015-11-25 | 2016-02-24 | 上海绿澄环保科技有限公司 | Method for treating specific pollutants through high-temperature melting technology |
| CN107191943A (en) * | 2017-04-26 | 2017-09-22 | 韶关绿然再生资源发展有限公司 | Incineration disposal draff processing method |
| CN107363072A (en) * | 2017-06-30 | 2017-11-21 | 中国恩菲工程技术有限公司 | The fused bath smelting method of waste |
| CN206911916U (en) * | 2017-05-03 | 2018-01-23 | 江苏天楹环保能源成套设备有限公司 | A kind of refuse incineration flying dust electric arc melting system |
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| CA2419010A1 (en) * | 2003-02-17 | 2004-08-17 | Noranda Inc. | Strontium for melt oxidation reduction of magnesium and a method for adding strontium to magnesium |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105344698A (en) * | 2015-11-25 | 2016-02-24 | 上海绿澄环保科技有限公司 | Method for treating specific pollutants through high-temperature melting technology |
| CN107191943A (en) * | 2017-04-26 | 2017-09-22 | 韶关绿然再生资源发展有限公司 | Incineration disposal draff processing method |
| CN206911916U (en) * | 2017-05-03 | 2018-01-23 | 江苏天楹环保能源成套设备有限公司 | A kind of refuse incineration flying dust electric arc melting system |
| CN107363072A (en) * | 2017-06-30 | 2017-11-21 | 中国恩菲工程技术有限公司 | The fused bath smelting method of waste |
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