Revolutionary breakthrough in the history of hydrometallurgy - ultrasonic hydrometallurgy

Traditional hydrometallurgy is basically a process of high input, high energy consumption, high pollution, and low output. The added value of products is extremely low, and the hydrometallurgical companies have long lived by eating rice. The so-called price of rice includes national prices for resources, energy, and environmental protection, low labor prices and helpless market prices. The national price and labor price are two bowls of soft rice, and it is difficult for the company to die. The market price is a bowl of hard rice. When the market price is good, if you buy or sell more, you will make money. When the market price is poor, there will be less sales and you will lose money. When the market price is very low, the sale will be difficult and you will be bankrupt. It is almost a law that the hydrometallurgical enterprises in China rely on eating rice for survival and development.

I have worked in hydrometallurgical companies for many years and come to a conclusion: whether the benefits are good or not, it's basically the price. The market is good, increase production, profit rise, who is the director of the factory are well-led; the market is not good, reduce production pressure, who is when the director is powerless. Science and technology are the primary productive forces. They are talking about every year and are making progress year by year. However, hydrometallurgical production technology has been consistently implemented for decades. No company has broken this barrier.

Holding the courage to innovate and pursue the ideal of breakthrough, I resigned from my career, used 8 years to accumulate capital, spent 8 years of research and development, and finally established the patented ultrasonic hydrometallurgy technology system in 2008, invented “Using Ultrasonic Wave to Improve Zinc Powder Activity Method, Device, and Use, "Method, Process, and Use for Ultrasonic Removal of Coated Particles in Solution," "A Method, Device, and Use for Ultrasonic Purifying of Wet Zinc Metallurgy," and "A Solution for Removal of Zinc Sulfate Medium calcium ion method, device and use". Relying on patented ultrasonic hydrometallurgy technology, we cooperated with Western Mining Co., Ltd. and Hunan University to accelerate the industrialization of ultrasonic hydrometallurgy engineering technology and complete sets of equipment.

Ultrasonic flotation technology was used to complete an ultrasonic flotation test for a certain cyanide leaching gold abandonment tailings in Qinghai, stably obtaining over 70% gold recovery rate and commodity grade gold concentrate, which was used to regenerate the nationwide cyanide leaching gold over the years. Tailings resources have created a new technology for ultrasonic gold selection. Daily processing of 400 tons cyanide leaching gold tailings complete set of equipment design and manufacturing. Ultrasonic flotation technology was applied to complete the ultrasonic flotation test of a silver-bearing ore in Jiangxi Province, breaking through the traditional flotation and roasting production of silver-containing calcined sand concentrates, which can reduce production costs by 50%.

Ultrasonic leaching technology was used to leach test the gold sulfur concentrate cinder from Shuikoushan Nonferrous Metals Group Co., Ltd. The gold leaching rate was increased from 70% to 81%, and the leaching time was shortened by 50%. Shuikoushan Nonferrous Metals Group is applying ultrasonic leaching technology to conduct a pilot test to accelerate the industrialization of the country by reclaiming more than 10 million tons of austenitic sulfide ore deposits annually.

Application of ultrasonic purification technology to the Western Mining and Zinc Branch, Yunnan Chihong Zinc Industry Co., Ltd., Baiyin Nonferrous Metals Group Northwest Lead-zinc Smelting Plant, Shaanxi Zinc Industry Shangluo Smelter, Henan Kaili Zinc Industry Co., Ltd., Shuikoushan Nonferrous Metals Group Zinc The plant's middle and upper qing qing successfully completed the ultrasonic purifying test; followed by the Western Mining and Zinc Branch, the Baiyin Non-ferrous Group Northwest Lead-zinc Smelting Plant, the Shaanxi Zinc Industry Shangluo Smelter, the Henan Kaili Zinc Industry Co., Ltd. and Shuikoushan Nonferrous The Group's zinc plant's middle and top grade successfully completed the on-site ultrasonic cleaning test. The results of the small-scale test and the pilot test confirmed that the application of the ultrasonic cleaning technology can reduce the time required for the purification of the medium-upper cleansing from 250 minutes to 25 minutes and reduce the energy consumption by 70%; the purification of the zinc in the medium-upper cleansing can be achieved by the consumption of zinc per ton. More than 50 kilograms to less than 30 kilograms per ton of electrozinc, reducing zinc powder consumption by more than 40%; the content of impurities in the middle and upper bound can be expanded to cobalt ≤ 200mg/L, nickel ≤ 200mg/L, copper ≤ 2000mg/L and/or Or cadmium ≤ 2000mg/L, which significantly enhances the production capacity of high-grade Zinc ore in the wet smelting smelting plant. It can directly produce high-grade copper slag, cadmium slag, and cobalt slag, which greatly improves the comprehensive recovery capacity of the wet smelting plant. benefit.

Ultrasonic hydrometallurgy is a hydrometallurgical method that uses ultrasonics to enhance physical and chemical reactions in hydrometallurgical processes. Ultrasonic waves are used to apply ultrasonic vibration and/or ultrasonic cavitation on the hydrometallurgical solution and its particulate solutes to achieve particle removal. The purpose of the cladding, accelerating the kinetic diffusion rate.

The technical principle of ultrasonic hydrometallurgy is: ultrasonic wave is a kind of elastic mechanical wave transmitted in a straight line. Applying a certain sound field to the solution by ultrasonic wave can cause the particles in the solution to produce mechanical vibrations. The particles are shattered in the solution. Or shattering, the effective contact area between the particles and the solution increases, the kinetic diffusion process on the particle surface is accelerated, and the expected physical and chemical reaction process is accelerated. Ultrasonic removal of particles on the surface of the cladding is classified as follows: removal of particulate neo-cladding and removal of particulate self-cladding. The granular neo-coatings usually belong to the chemical bond coats with lower bond energy such as molecular bonds and hydrogen bonds; the self-cladding of the particles usually belongs to the chemical bonds such as ion bonds or covalent bonds with higher bond energy. Remove the neo-clad layer and use ultrasonic vibration; remove the self-cladding and use ultrasonic cavitation. Ultrasonic waves exfoliate the particles and expose the surface of the particles. Ultrasonic waves exfoliate the granules, and the particles are exposed on the surface. When the ultrasonic energy is high enough, ultrasonic cavitation will be induced in the solution: the distance between the molecules in the liquid will change with the ultrasonic vibration and cause a large number of cavitation bubbles; the ultrasonic stretching zone forms a negative pressure zone, empty Bubbles are rapidly generated and grow; a positive pressure zone is formed in the ultrasonic compression zone, and the cavitation bubbles rapidly close and collapse. At the instant of collapse of cavitation bubbles, extreme environmental conditions such as transient high-temperature, high-pressure, strong shock waves, and high-speed jets are generated in the extremely small space around the cavitation bubbles, and the surface of the particles themselves are shattered or shattered, and the expected physical and chemical reaction progresses. Further accelerate. This realizes the ultrasonic hydrometallurgical process.

It is the fundamental purpose of flotation to allow the flotation agent to efficiently adsorb to the surface of the target ore and provide rapid uplift of bubbles. However, the target ore surface is always surrounded by various other particles. Ultrasonic waves are used to remove the surface ore of the target ore, which improves the surface activity of the target ore, strengthens the affinity of the flotation agent for the target ore surface, significantly shortens the flotation time, and greatly improves the flotation efficiency. Ultrasonic flotation provides a more efficient method for flotation of oxidized ores when low-grade oxidized ore lacks efficient flotation collectors or is not suitable for direct leaching.

Slag leaching includes leaching of oxidized ore and leaching of sulphide ore. The leaching process is a process in which the target metal element in the ore powder is separated from the main body of the ore powder, and is also a process in which the ore powder volume tends to become smaller or the quality tends to decrease. When the leaching process is controlled by the kinetic diffusion rate, the leaching rate of the target metal element is reduced, resulting in a long leaching process and a large area of ​​equipment. Ultrasonic waves are used to remove the surface coating of the ore powder, so that the mineral powder is always exposed to the fresh active surface, the leaching rate is accelerated, and the leaching efficiency is improved. The use of ultrasound leaching technology includes applications for leaching of various oxidized ores and sulphide ore, such as zinc roasted sand, zinc sulphide ore, copper sulphide ore, nickel sulphide ore, bauxite, rare earth ore, and precious metal ore. Tests have shown that it is of great economic significance to use normal pressure ultrasonic leaching instead of wet zinc smelting or wet smelting of high-temperature and high-pressure leaching to accelerate atmospheric leaching.

In wet zinc smelting, the zinc sulfate solution produced by leaching zinc ore fines contains various impurity components such as copper, cadmium, cobalt, and nickel, and it is necessary to treat the zinc sulfate solution leached out of the zinc ore fines. At present, zinc powder is generally used as a reducing agent to remove various impurities in the zinc sulfate solution, which is a general purification process of the wet zinc refining. Due to the high consumption of zinc powder, which accounts for 5-8% of the output of zinc, and the large increase in energy consumption, it has always been a technical bottleneck for wet zinc smelting. For the problem of high consumption of zinc powder in the purification process of zinc smelting, domestic use of flocculants to improve the separation characteristics of metal impurities to reduce the consumption of zinc powder; foreign use of monitoring the oxidation - reduction potential regulation of zinc powder to prevent excessive zinc powder. These methods do not solve the problem that the zinc powder activity decreases with the progress of the reaction, and zinc powder consumption is still high. After a long period of research, we found that the use of ultrasound to strengthen some of the important characteristics of the purification process of the supernatant: 1, ultrasonic irradiation can significantly speed up the rate of zinc powder replacement reaction; 2, ultrasonic irradiation can promote the copper-cadmium cobalt nickel slag type grain reversal; Ultrasonic irradiation time is proportional to the consumption of zinc powder; 4. The timely separation of slag-type grains can significantly reduce zinc powder consumption; 5. Ultrasonic irradiation time, purification temperature and zinc powder dosage can be controlled, and high-grade copper slag and cadmium can be directly produced. Slag and cobalt slag. At the same time, it was also found that under the “one boiler” purification method of the general purification process of the zinc smelting process, the flow state of the solution in the purification tank includes horizontal circulation and vertical circulation. In the horizontal circulation, the solution tends to mix with the horizontal fluid section; in the vertical circulation, The solution tends to mix in the vertical fluid section. Under the condition of continuous purification, the solution to be purified newly entering the tank tends to rapidly mix with the purification reaction solution, and the newly introduced ion concentration of impurities in the tank is rapidly diluted from high concentration to low concentration, so that the purification reaction is always in a lower ion state. Under the impurity concentration, the purification efficiency is low. The static purification test confirmed that the conventional medium supernatant with a cobalt concentration of 10 mg/L took about 10 minutes to remove 70% of cobalt impurities, and the conventional medium supernatant of 3 mg/L for cobalt concentration took about 90 minutes to remove 70% of cobalt impurities; Under the one-pot boiling purification method, the amount of zinc powder used as a reducing agent is mainly consumed in a purification stage where the concentration of ionic impurities is relatively low. Therefore, the wet zinc metallurgical ultrasonic purification technology will rapidly improve the purification technology level of the wet zinc refining industry in China.

In summary, ultrasonic hydrometallurgy overcomes various deficiencies of traditional hydrometallurgy and provides a rapid reaction path for the slow physical reaction process or the physical reaction that is difficult to react. It is a revolutionary breakthrough in the history of hydrometallurgy in the world. China has produced over 100 billion tons of tailings and spoils over the years. Each year, it has added several billion tons of tailings and waste slag. The value of valuable metal resources for reclaimed tailings and waste slag is huge. The amount of gold contained in gold sulphide concentrate is over 30 tons per year. China's 4 million tons of zinc production capacity is used to purify the zinc powder consumed in the middle and upper reaches of more than 200,000 tons per year. Ultrasonic hydrometallurgy technology is applied. It will produce huge economic and social benefits, and then fundamentally change the historical pattern of China as a non-ferrous metal resources, production, consumption of major countries in the history of hydrometallurgy lack of main innovation. With the development of ultrasonic energy conversion technology and material science and technology, ultrasonic hydrometallurgy technology can also be applied to major energy and resource fields such as oil purification and subsea mining, and the application prospect of ultrasonic hydrometallurgy is even broader.

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