[Ten years of major development in chemical technology] 008-2017 The world's first coke oven gas to ethanol project in Tangshan, Hebei Province

Technical Routes for Coal-to-Ethanol Currently, there are three main technical routes for coal-to-ethanol.: One is the direct production of ethanol from synthesis gas ； The second is bio-based ethanol production from syngas, which uses microbial fermentation technology to produce ethanol from syngas (including waste gas containing carbon monoxide and hydrogen). ； Third, synthesis gas is hydrogenated with acetic acid to produce ethanol. ▲Syngas bio-method production of ethanol requires a period of time for fermentation, so it is difficult to produce continuously, the cost will not be very low, and the reaction is relatively slow, which will cause problems during scale-up. ▲The process route for directly producing ethanol from syngas is relatively long, and currently none of the catalysts in the world has passed the standards. The product comes out as a mixture and needs to be purified. The direct production of ethanol from synthesis gas is still in the small-scale trial stage, and expensive rhodium catalysts are used, and the reaction rate is slow. ▲Among the coal-to-ethanol routes, the hydrogenation of syngas to ethanol via acetic acid is the most promising and potentially the lowest cost. According to reports, hydrogenation of acetic acid to produce ethanol theoretically consumes 1.304 tons of acetic acid, 973 cubic meters of hydrogen, and produces 391 kilograms of water per ton of ethanol. At present, acetic acid is cheap and the acetic acid production technology is mature, so the hydrogenation of acetic acid to produce ethanol is expected to be large-scale. If acetic acid is hydrogenated to produce ethanol, this technical route will only be competitive when the price of acetic acid is below 4,000 yuan/ton. This route is mainly to solve the problem of domestic overcapacity of acetic acid. If the price of acetic acid reaches more than 6,000 yuan/ton, this route will be completely uncompetitive. At the same time, acetic acid is carbonyl synthesized from methanol and carbon monoxide, while methanol is synthesized from hydrogen and carbon monoxide. Originally, hydrogen and carbon monoxide can be synthesized to directly produce ethanol. If it is used to produce acetic acid and then hydrogenated to produce ethanol, it is equivalent to going back to the production process, with many detours and low energy efficiency, which is not advisable. Therefore, in the long run, direct synthesis of ethanol from syngas is considered the most promising and easy to scale.

The industrial progress of coal-to-ethanol is accompanied by breakthroughs in key technologies and enrichment of process paths. The construction of domestic coal-to-ethanol projects is quietly heating up, and planned projects are increasing. ▲In January 2011, the global chemical giant Celanese announced that it planned to invest US$300 million in each of China's Nanjing Chemical Industry Park and Zhuhai Gaolan Port Economic Zone to build a 400,000 tons/year synthesis gas through acetic acid hydrogenation to produce industrial ethanol plant. ▲In June 2011, Celanese announced that it would spend US$180 million to improve the existing coal-chemical integrated unit in Nanjing Chemical Industry Park and increase industrial ethanol production capacity by approximately 200,000 tons/year. ▲In 2011, Shanghai Wuzheng Engineering Technology Co., Ltd. developed the catalytic hydrogenation of acetate to ethanol technology and built a 60-ton/year pilot plant. Its acetate conversion rate is greater than 96%, and the ethanol selectivity is over 98%. ▲On July 17, 2012, the acetate hydrogenation to ethanol technology independently developed by Southwest Chemical Research and Design Institute passed expert appraisal. The conclusion was that the developed special catalyst has high activity, good stability, and high selectivity, with a conversion rate as high as 97% and a selectivity for ethanol of more than 98%. ▲On April 16, 2012, the construction of a 200,000 tons/year coal-to-ethanol industrialization demonstration device using the ethanol production technology of acetate esterification and hydrogenation of Southwest Chemical Industry Research Institute was officially launched at Henan Shunda Technology Co., Ltd. ▲On March 13, 2014, Huludao City, Liaoning Province, together with Fude Holding Group, Sino-Sino Life Insurance Co., Ltd. and Jilin Cornell Group, planned to spend 64 billion yuan to build a 3.6 million tons/year coal-to-fuel ethanol and methanol reserve and transfer base project in the first phase, and a 1.2 million tons/year coal-to-paraxylene or olefins and related downstream product production project in the second phase. ▲In May 2015, Zhonghong Environmental Protection New Energy Co., Ltd. and Wuhai City, Inner Mongolia * * An investment cooperation agreement was signed. The two parties plan to invest 10.3 billion yuan to build 1 million tons/year coal-to-industrial ethanol and 300,000 tons/year epoxy propane projects. ▲In August 2015, the 300,000 tons/year coal-to-ethanol project of Tangshan Zhongrong Technology Co., Ltd., which plans to invest 1.6 billion yuan, started construction. The project will build a 100,000 tons/year ethanol production line, and the second phase of the construction scale will be 200,000 tons/year coke oven gas to ethanol. ▲In the fourth quarter of 2015, Beijing Shougang Langze New Energy Technology Co., Ltd.’s 45,000 tons/year industrial gas to fuel ethanol project was officially launched. ▲On April 28, 2016, the 30,000 tons/year acetic acid hydrogenation to ethanol industrial demonstration unit of Jiangsu Thorpe (Group) Co., Ltd., which was constructed using technology from the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, was successfully put into operation at one time and achieved smooth operation. According to Ding Yunjie, a researcher at the Dahua Institute of Chemistry, the operation results of the Thorpe Company’s demonstration device showed that: Under basically the same material and energy consumption conditions, the acetic acid hydrogenation to ethanol technology developed by Dahua can produce absolute ethanol with a purity of more than 99.6%. This indicator is nearly 5 percentage points higher than the acetic acid hydrogenation technology of Celanese Company in the United States, indicating that Dahua Institute’s technology is already at the leading international level. ▲At 9:00 on January 11, 2017, Yanchang Petroleum’s 100,000-ton syngas-to-ethanol industrial demonstration project constructed using methanol-dimethyl ether-methyl acetate-hydrogenation technology to produce anhydrous ethanol was successfully put into operation in Xinghua, producing qualified anhydrous ethanol with a purity of 99.71%, marking the success of the world’s first syngas-to-ethanol industrial demonstration project. The project started construction in January 2015, and is another major breakthrough in the application of new coal chemical industry technology in my country.

[Ten Years of Development in Chemical Technology] A series of summary posts, which are being updated continuously! https://bbs.hcbbs.com/forum.php?mod=viewthread&tid=3594069 (Source: Haichuan.com-Huahaichuanliu)

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