A thorough discussion on the issues in the coal-based ethylene glycol production process
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Dear friends, those interested in the processes related to coal-based ethylene glycol production, please come forward! Wishing you all great progress and success in the new year! Now, let me first give you an overview of the whole process: “Coal-based ethylene glycol production” refers to the use of coal as a substitute for petroleum-derived ethylene in the production of ethylene glycol. Leveraging over 20 years of technical expertise, the Fujian Institute of Research on the Structure of Matter under the Chinese Academy of Sciences has joined forces with enterprises to successfully develop a complete set of technologies for \"the catalytic gas-phase synthesis of oxalate esters from CO on a ten-thousand-ton scale, and the catalytic hydrogenation of oxalate esters to produce ethylene glycol\" (referred to as \"ethylene glycol production from coal\"). Chinese name: Coal-based ethylene glycol. Concept: Producing ethylene glycol using coal as a substitute for petroleum-derived ethylene. Raw material: Coal. Process routes: Direct method, olefin method, oxalate ester method. Table of contents: 1. Background introduction; 2. Characteristics; 3. Current status; 4. Technical process routes; 5. Core technical processes. ▪ Complete database of physical properties; ▪ Core catalysts; ▪ Mastery of key processes; ▪ Ongoing technical improvements; ▪ Comprehensive technical support and services; ▪ Thorough basic experiments and research; ▪ The most extensive portfolio of patents. Background introduction: This set of technologies was approved for evaluation by the Chinese Academy of Sciences in Danyang, Jiangsu Province, where it is implemented. Experts from the appraisal committee believe that this achievement marks China’s leadership in the world in realizing a complete set of technologies for \"coal-to-ethylene glycol\" production as well as their industrial application; it is a world-first technology with independent intellectual property rights. This achievement, resulting from long-term fundamental research, applied research, and industrialization, is backed by multiple technical patents and independent intellectual property rights ； This set of technologies complies with the three principles of the circular economy, as verified through on-site inspections by experts from the evaluation committee. Since 1982, through years of preliminary research, the Fujian Institute of Physical Chemistry has developed a series of patented technologies with full independent intellectual property rights as well as catalyst-related technical secrets. Since 2005, the institute has joined forces with Jiangsu Danhua Group Co., Ltd. and Shanghai Jinmei Chemical New Technology Co., Ltd. to officially launch the industrialization project titled “Gas-phase catalytic synthesis of oxalates from CO and catalytic hydrogenation of oxalates to produce ethylene glycol”. This research and development has received strong support from the Ministry of Science and Technology, the Chinese Academy of Sciences, and Fujian Province. After more than 3 years of effort, the design and construction of an industrial demonstration plant for producing ethylene glycol from coal on a scale of 10,000 tons were successfully completed. The plant was brought online, the entire production process was operational, and it operated stably for over 1,000 hours. A press conference on the Chinese Academy of Sciences’ \"world’s first industrial demonstration of producing 10,000 tons of ethylene glycol from coal\" was held grandly at the Great Hall of the People in Beijing. Lu Yongxiang, Vice Chairman of the REN Da** Conference and President of the Chinese Academy of Sciences, attended the meeting. Leaders from relevant departments such as the Ministry of Science and Technology, the Ministry of Industry and Information Technology, the Ministry of Land and Resources, the National Natural Science Foundation of China, and the China Petroleum and Chemical Industry Association, along with leaders from Fujian Province, Jiangsu Province, and the Inner Mongolia Autonomous Region, as well as Academician He Mingyuan, head of the expert panel for evaluating technical achievements, attended the press conference. The experts on the appraisal committee unanimously agreed that this achievement signifies that our country has taken the lead in the world in developing a complete set of technologies for \"coal-to-ethylene glycol\" production as well as in implementing their industrial application; it is a world-first technology with entirely independent intellectual property rights. The promotion and application of this technology will effectively alleviate the supply-demand imbalance of ethylene glycol products in China. It will have a significant positive impact on China’s energy and chemical industries. Therefore, it holds great scientific significance, demonstrates remarkable technological innovation, and yields notable social and economic benefits. Features: Ethylene glycol is an important chemical raw material and strategic substance, used in the production of polyesters (which can further be used to manufacture polyester fibers, beverage bottles, and films), glyoxal, etc. It can also be used as an antifreeze, plasticizer, hydraulic fluid, and solvent. ““Coal-based ethylene glycol” refers to the production of ethylene glycol using coal instead of petroleum-derived ethylene. Experts point out that such a technical approach is in line with China’s resource profile, characterized by a shortage of oil and gas and relatively abundant coal resources. This achievement, obtained by the Fujian Institute of Research on the Structure of Matter under the Chinese Academy of Sciences through long-term basic research, applied research, and industrialization, is backed by multiple technical patents and independent intellectual property rights ； This set of technologies conforms to the three principles of the circular economy: reduction, reuse, and resource recycling. Its notable feature is that it uses industrial-grade CO, NO, H2, O2, and alcohols as raw materials, which is highly advantageous for the development of a large-scale industry. After on-site inspection, the experts from the appraisal committee concluded that the 10,000-ton industrial testing facility operates stably and meets the conditions for further development into a large-scale industrial production facility. According to experts’ estimates, about 2.5 tons of oil are required to produce one ton of ethylene glycol using the petroleum-based route. The more than 20 million tons of ethylene glycol produced worldwide from petroleum-based ethylene—if all of it were to be produced using coal as a raw material—would result in oil savings equivalent to the development of a new Daqing Oilfield capable of producing 50 million tons of oil per year. Status update: The technology for producing ethylene glycol from coal was a key scientific and technological research project during the \"Eighth Five-Year Plan\" and \"Ninth Five-Year Plan\" periods. Through years of preliminary research since 1982, the Fujian Institute of Physical Chemistry, Chinese Academy of Sciences, has developed a series of pilot-scale and model-scale technologies with complete independent intellectual property rights ； The technical team of Jiangsu Danhua Group has extensive experience in the industrialization of new chemical technologies; it was the first in China to develop various new chemical processes such as \"ammonium bicarbonate production via carbonization\", \"acetic anhydride synthesis through carbonylation\", and \"CO separation using pressure swing adsorption\". Since 2005, with an investment of around 180 million yuan by Shanghai Shengyu Enterprise Investment Co., Ltd., in collaboration with institutions such as the Fujian Institute of Research on the Structure of Matter under the Chinese Academy of Sciences, Danhua Group, and Shanghai Jinmei New Chemical Technology Co., Ltd., industrialization trials for the \"vapor-phase catalytic synthesis of oxalates from CO and the catalytic hydrogenation of oxalates to ethylene glycol\" were launched. After more than three years of hard work, and with strong support from the National Development and Reform Commission, the Ministry of Science and Technology, the Chinese Academy of Sciences, Fujian Province, Shanghai Municipality, and Jiangsu Province, two production facilities were established at Danhua Group: one for pilot-scale production of 300 tons per year and another for industrial-scale production of 10,000 tons per year. Breakthroughs were achieved in various key technical areas. In December 2007, the 10,000-ton-per-year facility was successfully commissioned, enabling the entire production process to operate. Following more than a year of actual operation and evaluation by expert groups, it was confirmed that the world’s first \"10,000-ton-per-year coal-based ethylene glycol production technology\" had been fully successful. Regarding the cooperation model for this project, Lu Yongxiang, Vice Chairman of the Ren Da** Committee and President of the Chinese Academy of Sciences, believes that in the process of applying the Scientific Outlook on Development and building an innovative country, the Chinese Academy of Sciences has implemented innovation initiatives to create a \"golden triangle\" of knowledge innovation, technological innovation, and industrialization of technologies. It has also developed a scientific and technological innovation system that takes advantage of the interactions among these three elements, and has established unique innovation mechanisms to promote scientific and technological innovation, the transfer and commercialization of technological achievements, as well as the development of high-tech enterprises. In the new context of addressing the international financial crisis, it will provide enterprises with valuable experience in enhancing their independent innovation capabilities through the transfer and application of scientific and technological achievements, thus exploring a path to innovation that fosters win-win cooperation for the steady and rapid development of China’s national economy. Editing of the technical process routes: Currently, in China, there are mainly three process routes for producing ethylene glycol from coal as raw material: Process route diagram for producing ethylene glycol from coal. 1. Direct method: Syngas (CO+H2) is produced by gasifying coal, and ethylene glycol is then synthesized directly from this syngas in one step. The key to this technology is the selection of a catalyst; it has been difficult to industrialize for a considerable period of time. 2. Olefin process: Using coal as raw material, syngas is obtained through gasification, shift conversion, and purification. Through methanol synthesis and the Methanol-to-Olefins (MTO) process, ethylene is produced. Finally, through ethylene epoxidation, hydration of ethylene oxide, and product purification, ethylene glycol is obtained. This process combines coal-to-olefins with the traditional petroleum-based route to ethylene glycol; the technology is relatively mature, but the costs are relatively high. 3. Oxalate method: Using coal as the raw material, CO and H2 are obtained through gasification, shift reaction, purification, and separation. CO is then used to produce oxalates via catalytic coupling and purification, and subsequently polyester-grade ethylene glycol is obtained through a hydrogenation reaction with H2 followed by further purification. This process features a short workflow and low costs; it is currently the most highly regarded coal-to-ethylene glycol technology in China. The term “coal-to-ethylene glycol” generally refers specifically to this process. (See Figure 1 for details.) The entities in China that have announced they possess coal-based ethylene glycol production technology include: the Fujian Institute of Physical Chemistry, Danhua Group, and the Henan Coal Industry cluster ； Tianjin University, Wison Engineering, Huaben Energy Consortium ； East China University of Science and Technology, Shanghai Pujing, Huahe Group consortium ； Huayi Group, etc. It also includes the Ube Industries and Toho Engineering consortiums, represented by Nihon Kōkagaku. Editor of core technical processes: The main process for producing ethylene glycol from coal is the “oxalate ester method”. In this process, coal is used as a raw material; through gasification, shift conversion, purification, and separation, CO and H2 are obtained separately. The CO is then catalytically coupled and refined to produce oxalate esters. Subsequently, these esters undergo a hydrogenation reaction with H2, followed by further purification to yield polyester-grade ethylene glycol. Taking the syngas-to-ethylene glycol technology jointly developed by Huisheng Engineering and Tianjin University as an example, the domestic syngas-to-ethylene glycol technology features the following advantages: it possesses a complete database of physical properties. a. Experimental methods are used to obtain important physical property data such as the physicochemical properties, thermodynamic parameters, solubility, and interaction parameters of unusual substances involved in the production of ethylene glycol from coal, such as nitrites and oxalates ； b. Binary and multivariate interaction parameters in the separation processes of oxalates, carbonates, methanol, as well as ethylene glycol, 1,2-butanediol, etc ； Possesses a core catalyst: a. Two generations of oxalate synthesis catalysts – the first generation consists of traditional particle-shaped palladium-based catalysts supported on alumina (catalysts used in industry); the palladium loading is around 0.6% by weight, with an oxalate selectivity of up to 98.5%. The space-time yield of these catalysts is greater than 700 g/Lcat/h, and their lifespan exceeds 2 years ； The second-generation monolithic palladium-based catalysts maintain optimal catalyst performance while having a palladium loading of only 0.15% wt, resulting in a significant reduction in catalyst bed resistance ； b. Hydrogenation catalyst for oxalates: Industrial-scale preparation of raw powder of Cu/SiO2 catalyst with high activity, high selectivity, and high stability ； The first-generation flake-shaped hydrogenation catalyst, characterized by high strength and high stability ； The second-generation pellet-shaped hydrogenation catalyst (an industrially used catalyst) has undergone a 4,700-hour lifespan evaluation. During this period, the conversion rate of oxalate to oxalic acid by the catalyst reached 100%, while the selectivity for ethylene glycol exceeded 95%. The space-time yield was greater than 300 g/Lcat/h. The initial reaction temperature was 185°C; the average rate of temperature increase was 1.5°C per month. The maximum reaction temperature can reach 245°C. It is anticipated that the catalyst’s lifespan will exceed 1.5 years. The third-generation monolithic hydrogenation catalyst further eliminates the effects of external diffusion; both its activity and stability are significantly superior to those of the second-generation extruded hydrogenation catalyst. c. All of the above catalysts can be manufactured on an industrial scale, with 1 catalyst production line capable of producing hundreds of tons per year ； Mastering core processes: a. Higher pressure in the oxalate ester synthesis process, reducing system volume ； The synthesis cycle of oxalates offers great operational flexibility; the recovery rate of nitrites reaches 95%, and the amount of NO required for supplementation is low ； Direct supplementation with NO results in a more stable process; sodium nitrate is produced as a by-product, with no wastewater generated ； b. A unique low-energy consumption separation method for polyester-grade ethylene glycol: By using a component separation approach, polyester-grade ethylene glycol can be obtained with just 4 distillation columns, resulting in energy savings of over 20% compared to traditional ethylene glycol separation methods ； c. Wider specification requirements for the feed gases: wider requirements are applied to CO and H2; a concentration of over 98% is sufficient. There are no requirements regarding CO2, CH4, and N2 in CO, nor regarding CO, CO2, CH4, and N2 in H2 ； d. Diversification of products in the oxalate synthesis process route and development of downstream oxalate products: The coal-based ethylene glycol-related products and processes that are currently under development or have already been developed include coal-based fuel ethanol, synthetic oxalic acid, dimethyl carbonate, diphenyl carbonate, etc ； e. Comprehensive analysis and monitoring system: It combines online monitoring with the process control process, ensuring process stability while reducing the number of operators and avoiding potential risks caused by human errors. Ongoing technical improvements: Utilizing their solid foundation in research on coal-based ethylene glycol production as well as their experience in scaling up such processes, Huisheng Engineering and Tianjin University continue to improve and optimize the core catalysts and process technologies related to coal-based ethylene glycol production. They do this while ensuring that their technologies remain state-of-the-art and by incorporating new technological advancements. Robust technical support and services: Tianjin University has a team of engineering and technical professionals who work on projects ranging from laboratory stages to pilot-scale operations and finally to full-scale demonstration projects, enabling them to provide companies with detailed and reliable guidance for project implementation as well as technical support services ； With its extensive experience in EPCM and production, Huisheng Engineering is able to provide owners with comprehensive services related to the engineering field, as well as training in the production of gasification, purification, and separation processes ； It has plant bases of thousands of tons and tens of thousands of tons in order to serve as training facilities for the core technologies related to coal-based ethylene glycol production. Comprehensive basic experiments and research: Continuous and long-term research on coal-based ethylene glycol production and related areas has been carried out since 1987, with thorough studies on the scale-up process from laboratory tests, pilot tests on a tonnage scale, pilot plants operating at a hundred-ton scale, to demonstration projects on a ten-thousand-ton scale ； a. **95 Scientific and Technological Research Projects ； b. **11th Five-Year Plan Science and Technology Support Projects ； c. Project for producing oxalates, oxalic acid, and ethanol from thousand-ton-scale yellow phosphorus off-gases ； d. 10,000-ton per year syngas-to-ethylene glycol project ； It possesses the most comprehensive portfolio of patents: 19 granted patents in the areas of catalysts, processes, separation, and related technologies, along with 3 PCT international patents ； Regular catalysts for the gas-phase coupling of CO to produce oxalates and their preparation methods; ZL2010 – Regularly structured catalysts for the hydrogenation of oxalates to produce ethylene glycol and their preparation methods; ZL2010 – Catalysts for the low-pressure gas-phase synthesis of oxalates using CO and their preparation methods; ZL2007 – Methods for the coupling of CO to produce oxalates; ZL2007 – Catalysts for the hydrogenation of oxalates to produce ethylene glycol and their preparation methods; ZL2007 – Gas-phase CO coupling processes for the cyclic production of oxalates; ZL96109811.2 – Catalysts for the hydrogenation of acetates to produce ethanol and their preparation methods; ZL2012 – Methods for the hydrogenation of acetates to produce ethanol; ZL2012 – Catalysts for the hydrogenation of oxalates to produce ethanol and their preparation methods and applications; ZL2011 – Methods for preparing **-based oxalates and diphenyl oxalate; ZL02129213.2 – Supported metal oxide catalysts for the synthesis of **-based oxalates and diphenyl oxalate; ZL02129212.4 – Methods for synthesizing diphenyl oxalate from oxalates and phenol; ZL2005
I’d like to suggest some discussion topics, such as the debate over process routes； Which company has the most mature technology? ； Those weak links in the processes during actual operation ； How to extend the lifespan of catalysts, etc. I hope my colleagues will actively share their opinions and views!
Who has the contact information for the Fujian Institute of Research on the Structure of Matter?
Try this phone number: 0591-83714517. It turns out that a phone number was lost during the technical promotion presentation; it was several years ago!
The current problem with ethylene glycol is that it cannot be produced on a large scale like methanol, which results in high costs. Currently, a single ethylene glycol production unit has a capacity of around 200,000 tons per year. The high recycle ratio in the synthesis process leads to excessively large equipment and pipelines; it becomes difficult to make them any larger without changing the process itself.
Yes, 200,000 tons is currently the optimal scale. After years of experimentation, this 200,000-ton scale has become mature, and there are no longer any product quality issues. After calculation and actual operation assessment, the production cost does not exceed 5,000 yuan per ton.
Coal-based ethylene glycol products meet national premium standards Author: Liu Zhiyong, Song Lixin Source: China Chemical Industry News Update date: 10-11-2012 According to China Chemical New Network, on October 3, the Xinhui Yongjin coal-based ethylene glycol production facility successfully produced products that meet **premium quality standards. This represents the highest level of quality for coal-based ethylene glycol products in China to date, and it signifies that such products can now enter the polyester industry to compete with those produced from petroleum, thereby breaking the monopoly held by petroleum-based ethylene glycol. It is understood that at present, the key parameters of Xinxiang’s ethylene glycol products, such as ultraviolet transmittance, purity, and colority, all meet the **top-grade standards** for ethylene glycol produced from petroleum. At the same time, the system’s operational load rate kept rising, remaining stable at around 50% for an extended period, with the daily production of ethylene glycol reaching 300 tons. In recent years, driven by the rapid development of the polyester industry, domestic consumption of ethylene glycol has increased sharply. The reliance on imports has remained above 70%. Compared with ethylene glycol produced from oil, developing the industry for ethylene glycol produced from coal is more in line with China’s situation of having abundant coal but limited oil resources; thus, the market prospects for ethylene glycol produced from coal are very promising. It is reported that approximately 95% of the ethylene glycol produced in China is used in the manufacture of polyesters, which are then used to produce polyester fibers, beverage bottles, films, and other products. However, the ethylene glycol used for polyester production must meet **top-quality standards**. Only by crossing this threshold can coal-based ethylene glycol compete with oil-based ethylene glycol in the polyester industry. It is reported that on March 29 of this year, the project completed the entire system process flow and entered the trial production phase. To improve product quality and enable the ethylene glycol production plant to operate at high capacity, Henan Coal Chemical Group has actively strengthened technical coordination; it invited technical experts to the site to study and resolve the technical bottlenecks identified during system commissioning ； Hold a special meeting on technologies for operating the system under high load, and formulate relevant technical upgrades, countermeasures, and work plans ； A trial production experience exchange meeting was held, during which technical personnel and key operators from various units conducted focused discussions on the problems that have arisen since the start of operation as well as issues within the system, in order to further refine the coal-to-ethylene glycol technology and improve product quality.
Coal-based ethylene glycol has become an important part of China’s ethylene glycol production capacity. According to data from ICIS China, by the end of 2016, China had put into operation ethylene glycol production capacity of 7.77 million tons, of which 2.12 million tons was produced from coal. In 2016, China’s production of coal-based ethylene glycol was approximately 1 million tons, accounting for about 20% of the total ethylene glycol output. China is the world’s largest producer of polyester. It is estimated that in 2016, China’s effective polyester production capacity will be 48 million tons, with a production volume of 36 million tons; the demand for ethylene glycol will be around 13 million tons. China still needs to import large quantities of ethylene glycol, which presents good development opportunities for coal-based ethylene glycol production. The operational coal-to-ethylene glycol demonstration project is gradually performing better; some of its units have achieved stable operation at high loads, thereby driving a continuous increase in investments in new coal-to-ethylene glycol projects. Statistics from ICIS Chemical Business show that from 2017 to 2018, China will add 2.98 million tons of capacity for coal-based ethylene glycol production, accounting for 64% of the total new ethylene glycol capacity. The technical development of coal-based ethylene glycol production via the oxalate route is moving toward lower costs, higher selectivity, a longer catalyst lifespan, and greater environmental friendliness. Meanwhile, a new technology for producing polyester-grade ethylene glycol from methanol using syngas, developed through the collaboration between Eastman Chemical and JM David Company, has also been successfully created. Thanks to the continuous improvement in product quality and a deeper understanding by end-users of the applications of coal-based ethylene glycol, it has begun to be widely used in the polyester fiber industry. The 8th Technical and Economic Symposium on Coal-to-Ethylene Glycol will be held in Haikou from April 27-28, 2017. The conference will discuss the competitiveness and investment opportunities of coal-based ethylene glycol in the context of low oil prices, the optimization of operations and technological innovations in commercial plants for coal-based ethylene glycol production, the application experience of coal-based ethylene glycol in the polyester industry, recent advancements in new coal-based ethylene glycol technologies, and the industry impacts of the ethylene glycol futures market.
This post was last edited by goldliyang on 2017-4-14 at 11:44. Regarding the project of producing ethylene glycol from syngas, there are also significant shortcomings in terms of equipment and tools. The level of equipment and tools is low; traditional, simple, and inefficient gas-liquid and gas-liquid-liquid separation technologies from the 1940s and 1950s are still being used, which results in high operational costs for the projects, a low rate of high-quality products, and unsatisfactory overall performance of these projects.