Recycling magnesium waste residue combined with citric acid to produce hydrogen energy (2)
Recycling magnesium waste residue combined with citric acid to produce hydrogen energy (2)
The recovery rate of refined magnesium in the production of magnesium metal is about 94%, that is, the content of magnesium in the refined slag is about 6% of the amount of magnesium produced, and the recovery rate of refining for crystallized and small crystalline magnesium. Only about 80%, the magnesium content in the refining slag is as high as 20%. If the magnesium refining slag with high magnesium content is not used well, it is not only a waste of resources, but also brings us a living environment. Serious destruction. How to use refining slag has become a matter of great concern to the industry.
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The recovery rate of refined magnesium in the production of magnesium metal is about 94%, that is, the content of magnesium in the refined slag is about 6% of the amount of magnesium produced, and the recovery rate of refining for crystallized and small crystalline magnesium. Only about 80%, the magnesium content in the refining slag is as high as 20%. If the magnesium refining slag with high magnesium content is not used well, it is not only a waste of resources, but also brings us a living environment. Serious destruction. How to use refining slag has become a matter of great concern to the industry. At present, there are reports on the use of refined magnesium slag to recover MgCl2 and the use of flux refining to recover magnesium from refining slag. Although these methods can greatly increase the output value of the plant, the production cost of the plant is also high due to the need for secondary refining. Amazing, and the subsequent refining slag also caused serious damage to the environment.


The production of metal magnesium in China is basically smelting by hot method, which belongs to industries with high energy consumption, high pollution and resource performance. Although the pollution of the metal magnesium industry has been well controlled in recent years, there is still no good method for the treatment of refining slag produced in the production of magnesium and magnesium alloys. The composition of magnesium and magnesium alloy refining slag is magnesium and antimony. Some salts. According to the above, the output of magnesium and magnesium alloy refining slag produced in China is 6%-10% of the magnesium production, that is, about 10,000-100,000 tons of refining slag per year. See Table 2, these refining slags are almost 100% were transferred to Dashangou and treated by burial. During transportation and storage, serious secondary pollution was caused to ambient air and surface water.
Table 2 Sources and production of various types of waste

Similar to magnesium metal, China is also the world's largest producer and exporter of citric acid, and its production scale is still expanding. A large amount of by-products and wastes are produced in the citric acid production process because many of the ingredients in the raw materials are not fully utilized, so that the wastewater contains a large amount of organic matter. When the concentration of wastewater is high, if it is not treated, it will consume a large amount of dissolved oxygen in the water, causing the water body to be deficient in oxygen, making the water body black and smelly, causing fish and aquatic organisms to die, deteriorating water quality and polluting the environment.

Rich in hydrogen energy application mode, it can help low-carbonization of major end-use applications such as industry, construction and transportation, including as a fuel cell vehicle for transportation and as an energy storage medium to support the integration and generation of large-scale renewable energy. Distributed generation or cogeneration provides electricity and heat to buildings, providing clean energy or raw materials directly to the industrial sector. The project "Recovering Magnesium Waste Residues Combined with Citric Acid to Produce Hydrogen Energy" can create profits through technology transfer, cooperation and cooperation in various fields:

Hydrogen use and target: fuel, hydrogen chemistry, hydrogen fuel cell
Large-scale magnesium plants in Shanxi, Shaanxi, Inner Mongolia, Xinjiang, etc., the reduction of slag, pure magnesium ingot slag, magnesium alloy magnesium slag, etc. can be reduced by 90%~95%
Solid non-hazardous waste can be used as road building materials
Large-scale citric acid plant in the country, which can reuse waste liquid
Purification and storage of magnesium hydrogen alloy (chemical gas industry) sales


At present, China has established a base for hydrogen energy industry. The national hydrogen production capacity exceeds 20 million t/a, but production mainly relies on fossil energy. Consumption is mainly used as industrial raw materials. The energy utilization of clean energy hydrogen and hydrogen energy is small. Domestically produced coal from fossil fuels such as coal, natural gas and petroleum accounts for nearly 70% of hydrogen, and industrial by-product gas produces about 30% of hydrogen, and electrolyzed water produces less than 1% of hydrogen. See Figure 1. Domestic and foreign energy companies have chosen different technical routes in combination with their respective advantages, and have arranged hydrogen energy production and supply. Coal-based hydrogen, natural gas hydrogen production, and alkaline electrolysis water hydrogen production technology and equipment have been commercialized.

In contrast, the overall industrialization of hydrogen storage and refueling lags behind. Compressed hydrogen is relatively mature compared to liquid, solid and organic liquid hydrogen storage technologies, but still has a distance compared to industrialization. Compressed hydrogen is mainly transported through two ways: gas hydrogen trailer and hydrogen pipeline. At present, the hydrogen in the domestic hydrogen refueling station is transported by gas-hydrogen trailer. Since the hydrogen weight of the gas-hydrogen trailer is only 1%~2% of the total weight of the transportation, it is more suitable for users with a relatively short transportation distance, a low transportation volume, and a daily hydrogen consumption of tons or less.
Economic and initial benefits
(1) The cost of magnesium and magnesium alloy and magnesium product waste residue and undercut material: At present, the treatment of metal magnesium reduction slag is mainly buried, and the plant needs to be pretreated before burying, including in-plant transportation, dehumidification, watering, and use. Forklift accumulation, loading and unloading, dustproof and other costs, while metal magnesium and alloy refining slag is mainly the management, accumulation, loading and unloading, dustproof and other costs of the warehouse, in addition to the above standards for the production of magnesium alloy die castings and other magnesium alloy products in the production process In addition to the operating procedures, the resulting scraps should be fire-proofed, remelted, etc., and the existing magnesium waste slag and undercut processing technology should be combined. The cost is about RMB 50/ton, and the national comprehensive treatment of magnesium-magnesium reducing slag, magnesium and magnesium. The cost of alloy and magnesium product waste and undercuts is 233 million yuan/year. The above process for the production of magnesium and magnesium alloys and magnesium products and undercuts is shown below.

Figure 7 Production process of various types of magnesium slag and undercuts
(2) Revenue of hydrogen: The country produces 165,000 tons of various types of magnesium and alloy wastes every year. According to the test data, every 10 grams of refining slag produces 1L of hydrogen, 5000L of hydrogen is used for tanks, and 50 yuan/tan is calculated. The value of hydrogen is :
165,000 tons * 10 grams * 1L / 5000L / cans = 3.3 million cans * 50 yuan = 1.65 billion yuan.
    The hydrogen produced is stored for commercial sale or used immediately for local power generation or for industrial use. In order to alleviate the shortage of energy, the demand for hydrogen will only increase, the price is good, and there are huge benefits available.
(3) Magnesium oxide revenue: Neutral wastewater can be filtered to obtain magnesium oxide for resale.
(4) Government subsidies.
    Hydrogen can be used as a strong reducing agent in the production of magnesium to replace carbon or coke to reduce carbon dioxide emissions. Reduce waste and environmental pollution through reduction of magnesium and magnesium alloy refining slag. At the same time, through the implementation of this project, the discharge of citric acid waste liquid can be reduced or even eliminated.

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