WO2016176850A1

WO2016176850A1 - Method for extracting germanium by thermally reducing and volatilizing germanium ore

Info

Publication number: WO2016176850A1
Application number: PCT/CN2015/078431
Authority: WO
Inventors: 普世坤; 包文东; 胡德才; 朱知国; 谢天敏; 李光文; 姚才伟; 鲍开宏; 吴王昌; 杨再磊; 谢高
Original assignee: 云南临沧鑫圆锗业股份有限公司; 云南东昌金属加工有限公司
Priority date: 2015-05-07
Filing date: 2015-05-07
Publication date: 2016-11-10

Abstract

Provided is a method for extracting germanium by thermally reducing and volatilizing germanium ore. Sodium hypophosphite is added to the germanium ore, air is isolated, the temperature is increased to carry out roasting, volatilization and enrichment so as to obtain a germanium concentrate.

Description

Method for extracting lanthanum by thermal reduction of bismuth ore

[0001] The invention belongs to the method for extracting strontium in the field of non-ferrous metallurgy technology, in particular to a method for extracting cerium by thermal reduction and enrichment of strontium ore by using sodium hypophosphite as a reducing agent.

Background technique

[0002] Lignite is a favorable carrier for the enrichment of alfalfa. There are a large number of organic matter in the lignite that can fix the alfalfa. The lignite in the basin of Linyi City, Yunnan Province is one of the most important sources of plutonium in the world. High, the coal quality is too bad, the calorific value is only 30%-40 <3⁄4 of ordinary lignite, so it has been approved by the Ministry of Land and Resources to be changed into antimony ore. The metal reserves are around 800 t, which is the Xinyuan industry in Linyi, Yunnan. Co., Ltd. is used in the development of the company, which mainly uses pyrophoric combustion enrichment to extract plutonium, and uses the reducing gas generated by carbon under high temperature conditions to reduce the volatilization in the antimony ore and into the soot, but the smelting of the plutonium The volatility rate has been difficult to break through 75%, and the cost of secondary recovery of ruthenium in the smashing residue is not satisfactory, which results in the loss of 锗 resources, so it is necessary to find a more effective technical method to increase the volatility of lanthanum. The existence of strontium in lignite is complicated and diverse. The enthalpy of high-valent compounds requires stable volatilization at very high temperatures, while the low-valent cerium compounds volatilize at 800-900 °C. Carbon has a strong reductive effect at high temperatures, but because the carbon content of antimony ore is too low, it does not promote the volatilization of plutonium to the greatest extent. Therefore, we consider adding a more effective reducing agent to promote the volatilization of plutonium.

technical problem

[0003] The invention mainly solves the problem that the recovery rate of the existing antimony ore enrichment process is difficult to break through 75%, and the secondary fire recovery process of the tasting furnace is high in production cost and low in recovery rate. Concentrate grade low-humidity treatment costs are high, and so on.

Problem solution

Technical solution

[0004] Bismuth exists in ore ore in the form of many complex organic and inorganic compounds. Among these complex compounds, there are many stable Ge 4+, a small amount of Ge 2+ , and a Ge compound. It needs to be volatilized above 1150 °C, and the Ge 2+ compound is obviously volatilized at 750 °C, so the fire method is rich. It is the principle of using this principle to reduce the certain Ge 4+ compound to Ge 2+ compound to achieve obvious volatilization. However, due to the complex form of 锗Ge 4+ in the antimony ore, the reduction of carbon does not result in the enthalpy. For maximum volatilization, it is necessary to add a reducing agent to increase the volatilization rate of the crucible, improve the grade of the antimony concentrate, reduce the crucible content of the crucible furnace, and avoid the secondary treatment of the crucible furnace.

[0005] There are thousands of chemical reducing agents, and there are several types, such as metal reducing agents: active metals such as potassium, sodium, iron, zinc, magnesium, etc.; low-oxide oxide reducing agents, such as carbon monoxide, Ferrous oxide, NO, etc.; hydride reducing agent, such as hydrogen sulfide, ammonia, BH _{3 ,} etc.; inorganic compound reducing agent, such as sodium borohydride (potassium); in addition, there are a large number of organic compound reducing agents, such as formaldehyde, A compound such as an aldehyde or sodium ethoxide. The experimental group conducted exploratory experiments from the aspects of economy, safety, environmental protection, etc., and selected several representative reducing agents to repeat the selective test in the laboratory stage. The test method steps were consistent, sampling The amount is 5 g, the volatilization temperature is 1000 °C, and the time is 1 h. The comparison test is shown in Table 1.

[0006] Table 1 Comparison of the enthalpy volatilization of several reducing agents.

[XXXX

[0007] It can be seen from Table 1 that the reduction effect of some common industrial reducing agents is far less than the last sodium phosphite. Sodium hypophosphite is a highly efficient reducing agent for reducing hydrazine, so considering safety and environmental protection, industrial input costs, and reduction According to the efficiency and other factors, sodium hypophosphite is a suitable reducing agent for the enrichment and extraction of antimony ore. It can directly reduce the high price of antimony to cerium oxide to promote the volatilization of antimony in antimony ore. Most of the products after the reaction of sodium hypophosphite are sodium pyrophosphate and sodium metaphosphate, and the environment is not polluted. The production test can be carried out by considering various factors such as safety and environmental protection, cost input and evaporation rate improvement effect. In summary, the present invention selects sodium hypophosphite as a reducing agent: First, sodium hypophosphite is a commonly used industrial product, easy to buy, and the price is relatively cheap; second, the reductive property of sodium hypophosphite is better, the proportion of addition Lower, the decomposition temperature is low, and other reducing agents such as carbon and active metals require high temperature and moisture to decompose to produce reducing components such as carbon monoxide and hydrogen. Third, the sodium phosphate produced by decomposition is easy to combine with silica. Coking at a lower temperature can reduce the volatilization of other volatiles in the volatilization process, thereby improving the grade; Fourth, the sodium phosphite is easily broken, and does not generate a large amount of flammable and explosive gases during use, and the process is safe and reliable.

[0008] After the experiment, it was found that the thermal reduction of volatile lanthanum by sodium phosphite in the strontium ore was effective and feasible to increase the enthalpy of lanthanum. Compared with the existing direct fire extraction method, the lanthanum volatility was significantly improved, and the sputum volatility was reduced. The taste. Under the same conditions, it can reduce the volatilization temperature of smelting and smelting 100~200 °C; it can reduce the enthalpy of lanthanum, save fuel and save production cost; under the same conditions, the furnace coke temperature is reduced by 100-200 °C, adding The higher the ratio, the easier it is to coke. The volatilization at 1000 ° C is more than 97%, and the volatilization at 1100 ° C is close to 100.

[0009] Principle Chemical Reaction Equation:

NaH ₂ PO ₂ .H ₂ 0 + 2GeO ₂ = 2GeO†+ NaPO ₃ + 2H ₂ 0

[0011] The antimony ore targeted by the present invention contains 100.010%-0.050%, ash 40%-65%, fixed carbon 18%-25%, moisture ^^-Ιδ^, ^2%-4% 10.2%-0.6 %^ Lead 2%-6%, 3⁄412%-16%^, etc. Its low calorific value and low carbon content require industrial coal to provide heat. Industrial coal provides both heat and reduction. The addition of sodium hypophosphite is further complicated by its strong reduction. Ge ⁴⁺ compound.

[0012] The present invention proposes a method for the thermal reduction of volatile cesium by the addition of a reducing agent sodium hypophosphite to the strontium ore. The factors affecting the enthalpy volatilization are: the amount and proportion of the sodium phosphite, the calcination temperature, the muffle The temperature rise of the furnace or the new type of bismuth volatilization furnace, the amount of oxygen in the furnace, and the constant temperature volatility.

[0013] When the 锗锗率减少减少减少减少减少炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉炉The increase in the volatilization rate of lanthanum also means that the sputum grade in the received soot will also increase, which can improve the industrial production input of the later wet method, reduce the amount of reagents such as hydrochloric acid and auxiliary materials, and reduce the treatment of waste water and waste. , saving production costs and so on. Therefore, a method of adding an effective reducing agent to promote the volatilization of hydrazine based on the original fire method has been proposed. The method does not need to add or modify equipment, and does not need to change many original process routes and basic operating procedures, and has little environmental pollution and safety can be controlled. It can reduce the volatilization temperature of smelting and smelting 100~200°C; it can reduce the enthalpy of lanthanum, save fuel and save production cost. It is an effective method with simple process, high recovery efficiency, low energy consumption, simple and convenient operation, low labor intensity and improved enrichment by fire method.

[0014] The present invention mainly solves the problem that the recovery rate of the existing antimony ore enrichment process is difficult to break through 75%, and the secondary fire recovery process of the tasting furnace is high in production cost and low in recovery rate. Concentrate grade low-humidity treatment costs are high, and so on.

[0015] The method for extracting lanthanum by thermal reduction of bismuth ore in the present invention is characterized in that the specific steps are as follows:

[0016] In the first step, a certain amount of antimony ore that has been crushed to less than 1 cm is taken, and sodium hypophosphite is broken up to 120 mesh or more. The weight of the antimony ore is 2.5%-7.5 <3⁄4, and the sodium hypophosphite is dissolved by adding water having a weight of 0.1-0.5 times the weight of the antimony ore, and then uniformly mixed with the antimony ore;

[0017] In the second step, the uniformly mixed antimony ore is placed in a muffle furnace previously heated to 900 ° C - 1000 ° C or a new bonfire extraction device, and then the furnace door is closed, the air is insulated, and the temperature is raised. When the temperature rises to 1000 °C -1100 °C, the temperature is increased for l-2h, and the roasting is enriched and enriched. The ruthenium is enriched in the volatilized smoke, and the soot that enters the dust collection bag is collected, thereby obtaining the bismuth concentrate.

[0018] After the calcination is completed, the mixture is cooled to room temperature, the weight of the volatile residue is weighed, the calcination amount of the antimony ore is calculated, and the residual residue is ground to less than 120 mesh, and the niobium grade is analyzed and tested, and the niobium volatilization rate is calculated. .

[0019] wherein, the novel bonfire extraction device is a Chinese patent, and the patent number is the device described in CN 201320436249.8.

Advantageous effects of the invention

Beneficial effect

[0020] The method for the thermal reduction of strontium in the slag-burning sodium hypophosphite of the present invention has the following advantages compared with the existing method for enriching and extracting strontium by fire method:

[0021] (1) The existing enrichment method for the extraction of lanthanum requires a secondary recovery treatment, and it is necessary to burn more industrial coal to reheat the sputum. After the bitter burning of sodium hypophosphite, the calcination temperature is above 1000 °C, and the calcination time is above lh, the veneer content in the volatilization residue can be reduced to below 50 g/t, which can eliminate the secondary recovery treatment. Save a lot of production costs.

[0022] (2) The calcination of sodium hypophosphite to the thermal reduction extraction of bismuth has a higher enthalpy evaporation rate than the direct combustion of sodium phosphite, and the grade of Chengzhong is much lower. When the calcination is 1100 °C, the volatilization rate of bismuth in the 2.5% sodium hypophosphite bismuth ore is close to 100%, and the volatility of the sulphur coal is only ₉₀ <3⁄4 when the sodium phosphite is directly heated and burned; When the calcination temperature is 1000 °C, the volatilization rate of the antimony ore of 2.5 <3⁄4 times of sodium phosphite can reach 96 <3⁄4 or more, and the volatilization rate of the antimony ore which is not directly burned by the sodium hypophosphite is only 55 <3⁄4 or so.

[0023] (3) Under the same conditions, the volatilization temperature of the smelting smelting can be reduced by 100 ° C ~ 200 ° C; the enthalpy of the lanthanum can be reduced, the fuel burned and the production investment can be saved, and the coking temperature of the furnace is reduced by 100 °. C-200 ° C.

[0024] (4) Compared with the method of directly extracting strontium by direct fire method without sodium phosphite, the recovery rate can improve the grade of strontium in the collected soot, and the next wet chlorination distillation is rich. In the process of extracting bismuth It can save the amount of reagents such as hydrochloric acid and auxiliary materials, and save the investment in wet production cost.

Brief description of the drawing

DRAWINGS

1 is a process flow diagram of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1 :

[0027] The raw material components are shown in Table 3.

[XXXX

[0028] In the first step, weigh 10 tons of antimony ore that has been crushed to a particle size of 1 cm or less as shown in Table 3, weigh 250 kg of sodium hypophosphite (2.5% of the weight of the antimony ore), and add 1000 kg. The tap water is dissolved, and then the sodium hypophosphite solution and the antimony ore are mixed uniformly through a mixing mixer.

[0029] In the second step, the above-mentioned antimony ore mixture is gradually added to a coal-fired furnace which is previously passed through an industrial coal having a thickness of 5 cm to 8 cm, and heated to a temperature of 900 ° C or higher, and the thickness of the coal seam is maintained at 50. Cm -70 cm, and cover a layer of living coal above the strontium ore layer, close the furnace door, and blast the large blast to 1000 °C - 1100 °C for constant temperature roasting for 1 h, intermediate process through 2-3 The secondary turning coal seam keeps burning completely. The volatilization process maintains the negative pressure state by adjusting the size of the induced air. It can be observed through a pressure gauge or the furnace door is not fired outside.

[0030] In the third step, after the roasting and volatilization is completed, the temperature is lowered to 500 ° C, and the water is cooled to room temperature, and the weight of the residual weight is 5.83 tons, and the burning rate of the antimony ore is calculated to be 42.10%.

[0031] In the fourth step, the volatile residue was sampled and analyzed, and the grade of the volatile residue was 0.0021 <3⁄4. From this, it is calculated that the volatilization rate of antimony in the antimony ore is 96.30%.

Embodiments of the invention

[0032] Example 2:

The raw material components used are shown in Table 2. [XXXX

[0034] In the first step, weigh 50g of the antimony ore shown in Table 2 into the ash dish; weigh 2.5 g of sodium hypophosphite (5 % of the weight of the antimony ore) that needs to be added, and add it to the small beaker, and Add 25 mL of water to dissolve, then add to the sample and mix with a glass rod, then wash the small beaker and glass rod with 10 mL of water and add to the sample, then put the sample into the oven preheated to 90 °C. After drying for 30 minutes, a large amount of water was evaporated to near dryness.

[0035] In the second step, the sample was taken out from the oven and placed in a muffle furnace previously heated to 900 ° C, and then rapidly heated to 1000 ° C for constant-temperature calcination for 1 h.

[0036] In the third step, after the roasting is completed, the temperature is lowered to 500 ° C, the ash dish is taken out and cooled to room temperature, and the volatile residue after sintering is weighed to obtain a weight of 28.7 g, and the burning rate of the antimony ore is calculated to be 42.6. %, and then remove and grind to more than 120 m.

[0037] In the fourth step, a certain amount of volatile residue was taken for analysis, and the grade of the volatile residue was 0.0033%. From this, the volatilization rate of antimony in the antimony ore was calculated to be 95.50

Claims

Claim

[Claim 1] A method for extracting lanthanum by thermal reduction of bismuth ore, characterized in that the specific steps are as follows:

In the first step, take a certain amount of antimony ore that has been broken down to less than lcm, and take the sodium hypophosphite that has been crushed to above 120 mesh, and its weight is 2.5 %-7.5 of the weight of the antimony ore.

%, adding sodium hypophosphite dissolved in water having a weight of 0.1-0.5 times the weight of the antimony ore, and then uniformly mixing with the antimony ore;

In the second step, the uniformly mixed antimony ore is placed in a muffle furnace previously heated to 900 ° C - 1000 ° C or a new bonfire extraction device, and then the furnace door is closed, the air is insulated, the temperature is raised, and the temperature rises. After 1000 °C to 1100 °C, the temperature is 1-2 hours, the calcination is enriched and enriched, and the ruthenium is enriched in the smouldering smoke, and the soot that has entered the dust collection bag is collected to obtain the bismuth concentrate.