First, glycine specifications
Glycine, also known as aminoacetic acid, has a chemical structural formula of NH2CH2COOH, which is the smallest relative molecular mass and the simplest structure in the amino acid series. According to the synthesis process and product quality of glycine, it can be divided into four product specifications: industrial grade, feed grade, pharmaceutical grade and food grade.
Glycine is an important chemical intermediate, in each field according to the proportion of consumption from high to low for pesticides, food, feed, medicine and so on. In China, about 80% of glycine is used to produce the herbicide glyphosate, while domestic glyphosate production increased from 400,000 tons in 2015 to 550,000 tons in 2019, with an annual growth rate of 9.3%. In the food industry, glycine can be used as a nutritional supplement, flavoring agent, preservative, and in the feed and pharmaceutical industry, glycine is used as a feed additive and pharmaceutical intermediate.
Source: Compiled by Huajing Industry Research Institute
Second, glycine production process
At present, the main methods of glycine synthesis with industrial and industrial prospects are chloroacetate ammonia solution, Stryker method, hydroxyacetonitrile method, direct heine method, biosynthesis method and so on.
At present, the improved Technical Route of Streck and Hein method is currently used abroad. Almost all of the domestic use of chloroacetic acid ammonia solution technology (aqueous phase chloroacetic acid process), only Chongqing Three Gorges Yingli adopts the Hine method process, the process system has the problem of sodium chloride and other inorganic salt separation difficulties, has not been able to produce normally.
The ammonolysis method of chloroacetate is based on chloroacetic acid and ammonia water as the starting material, and the glycine is synthesized under the action of the catalyst ulotine. The advantages of this method are that the reaction raw materials come from a wide range of sources, the synthesis process is simple, the reaction conditions are mild, the requirements for the material of the equipment are not high, and the operation is simple, which is easy to industrialize. The disadvantage lies in the long synthesis cycle, the by-product ammonium chloride is not easy to separate, the product quality is poor, and the ulotin catalyst is difficult to recycle, resulting in higher production costs.
At present, the ammonolysis method of chloroacetate is still the main method of production of glycine by domestic enterprises. Shen Meizhong proposed a new process of glycine synthesis, that is, the introduction of electrodialysis treatment of crystallization mother liquor, the separation of glycine and ulotine mixture back to the reactor for recycling, ammonium chloride aqueous solution through evaporation concentration crystallization to obtain ammonium chloride, the process not only greatly reduced the amount of catalyst ulotine, reduce production costs, but also improve the quality of by-product ammonium chloride.
A new process for glycine synthesis
Hydrocyanic acid toxic, volatile characteristics of the transport, storage is more difficult, in order to find alternatives to hydrocyanic acid, people have developed a direct heine process, the process is simple, high atomic utilization, clean and environmentally friendly, very promising application. At present, the direct hyne method synthesis process of glycine is still in the laboratory small test and pilot stage, and has not yet seen industrial reports.
Feng Zhiwu et al. provide a process of continuous preparation of glycine from hydroxyacetonitrile, using hydroxyacetonitrile and ammonia source and carbon source as raw materials, and then through the tubular packing reactor and kettle reactor, Hine synthesis and Hine hydrolysis reaction occurs, and then through evaporation, concentration, crystallization, separation, drying and other processes to obtain high-purity glycine products. The process not only ensures that the glycine yield and purity are above 99%, but also realizes the continuous production of glycine with hydroxyacetonitrile as raw material, and there is no waste liquid discharge during the production process.
A method for continuous preparation of glycine by hydroxyacetonitrile
Related report: "2021-2026 China Glycine Industry Market Supply and Demand Pattern and Industry Prospect Report" released by Huajing Industry Research Institute
3. Glycine production analysis
The annual output of glycine in China is about 400,000 tons. Of these, about 300,000 tons are mainly used for the production of the herbicide glyphosate, and the remaining 100,000 tons are used in other industries. The total production capacity of the main domestic glycine production enterprises is 462,000 tons, of which Shijiazhuang Donghua Jinlong Chemical Co., Ltd. has the highest production capacity, reaching 140,000 tons / year, followed by Hubei Yichang Jinxin Chemical Co., Ltd., with an annual production capacity of 100,000 tons / year.
Since 2012, China's glycine production has shown an upward trend, from 290,200 tons in 2012 to 355,800 tons in 2017, but the increase has begun to slow down. With the tightening of environmental protection policies in the future, glycine enterprises will reduce production due to wastewater pollution, and China's glycine production will decline.
Source: Collation of publicly available information
Fourth, the future development trend of glycine in China
The production of foreign glycine has completely eliminated the process technology of ammonia solution of chloroacetate, the main production technology is to hydrocyanic acid, hydroxyacetonitrile as raw materials of the Strecker method and Hydantion method, through the continuous update and improvement of the process technology, so that the product yield and product quality have been greatly improved, and there is a trend of using biotechnology to synthesize glycine from glycine, focusing on the study of high-tech such as catalysis, radiation, biosynthesis and so on applied to the glycine synthesis process, Some progress has been made.
Domestic production of glycine is currently widely used chloroacetic acid ammonia solution process technology, since the realization of industrialization in 1969, although it has been a number of process technology improvement studies, so that the glycine yield from the initial 70% to the current 85% or so, the content of glycine increased from 95% to 98.5%, but its key indicator chloride content is still as high as 0.06%-0.50%, due to the low purity of the obtained products, impurities and can not meet the requirements of the food and pharmaceutical industry production, This process technology mainly produces industrial grade glycine. In addition, a small number of manufacturers with chloroacetic acid ammonine solution repeatedly refined to obtain food grade glycine, due to high production costs, lack of market competitiveness and product quality is not high, can not meet the needs of pharmaceutical and food and other industries, resulting in China's pharmaceutical and food industry needs glycine to rely on imports.
The main downstream product of industrial grade glycine is glyphosate, which has been recognized by the market as a non-selective, residue-free herbicide. From the demand point of view, the area planted with genetically modified crops has been growing steadily, especially the increase in the land arable land area in Brazil and the increase in the penetration rate of glyphosate-resistant genetically modified crops, which will also drive the demand for glyphosate, and the global demand for glyphosate is expected to maintain a growth of about 5%. Many domestic glyphosate enterprises have supporting glycine production lines, glyphosate production capacity of 1.2 million tons / year, while the actual production of 800,000 tons / year, there are nearly 400,000 tons / year production capacity has not been released, the main reason is constrained by the price of glycine. The demand and price of glyphosate show an upward trend, which will drive the rapid development of the glycine industry. Now That China has become the world's largest producer of glycine, the demand for glycine will continue to grow in the next few years, and the development prospects of the glycine industry are very broad.
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