Carbon dioxide is the culprit for global warming, but its use as an industrial raw material is very extensive. Today, low-carbon and emission reduction have become the subject of world economic development. Many new uses of carbon dioxide have been developed at home and abroad—power generation, washing, and insect killing... Among these various new technologies, there is a technology that promises The disruptive impact of the petrochemical industry and even the entire industrial development deserves special attention. This is the carbon dioxide hydrogenation to methanol.
What does it mean that overseas research is heating up carbon dioxide to make methanol to the sustainable development of the petrochemical industry and even the world?
"If carbon dioxide is used to make methanol, industrialization will lead to a change in the source of raw materials in the petrochemical industry. Because on the one hand, methanol is one of the most widely used basic petrochemical raw materials, not only can it be directly used as a fuel or to make gasoline, but also methanol can be produced. Aromatic hydrocarbons, olefins and other chemicals; On the other hand, once this technology is broken through and promoted, it means that the carbon emission reduction pressures faced in economic development will be effectively mitigated, and the burden of emission reduction before human development will become a green one. The growth point of the industry.†An associate professor at Beijing University of Chemical Technology told CCIN reporters.
It is understood that carbon dioxide from methanol production once sparked a global debate on the “methanol economyâ€. Nobel Prize-winning scientist and renowned organic chemist George A. Ola once proposed that the cyclical model of hydrogen production from renewable energy and the use of carbon dioxide hydrogenation to synthesize methanol can be used as a solution to the energy shortage problem after the oil and gas era. Nobel Prize-winning physicist Carlo Lubia has also publicly proposed to substitute carbon dioxide for methanol to replace the now-popular carbon capture and storage, and to reduce emissions while providing raw materials for industry.
"It is precisely for the above reasons that this technology has become one of the world's most concerned CO2 application technologies." Associate Professor of Beijing University of Chemical Technology, said that in recent years, the developed countries have stepped up their exploration of carbon dioxide to methanol technology, and their exploration The pace is also twists and turns.
As early as 2002, the Nanotechnology Research Center of the Korea Science and Technology Research Institute had developed a medium-sized test apparatus for hydrogenation of carbon dioxide to produce methanol by using a transition metal catalyst under the condition of heating and pressurization. However, due to various reasons, the apparatus was followed. The trial was stranded.
In 2009, researchers from the Institute of Bioengineering and Nanotechnology in Singapore announced through a well-known professional journal, Applied Chemistry, that they have successfully developed a catalytic process for converting carbon dioxide to methanol at room temperature using an N-heterocyclic carbene organic catalyst. . When the industry was full of expectations, the feasibility of the process was quickly met with Doris Kunz, an expert at the Institute of Organic Chemistry at the University of Heidelberg, Germany, who questioned the energy level of the catalyst itself because of the consumption of the organic catalyst. Energy absorbs and reduces more carbon dioxide than the process.
Not long ago, the results achieved by Mitsui Chemicals Japan in this field once again made the industry shine. In May of this year, Mitsui Chemicals announced that it had made a breakthrough in carbon dioxide separation, catalyst improvement, and separation of methanol and water. In 2009, they invested US$16 million to build the world’s first 100 tons/year carbon dioxide to methanol. Pilot plant and succeeded. This is the most leading result of the carbon dioxide produced by carbon dioxide in the announced news.
The CCNI reporter who has reached the pilot level in China has learned in the interview that domestic research institutes and companies are paying attention to the development of the technology as much as abroad.
“The domestic high-energy-consuming companies, especially coal chemical companies, have a very high degree of attention to the technology of carbon dioxide hydrogenation and methanol production. It is estimated that 30 to 40 companies are closely following the progress of this technology, and there are also many companies such as Datang. Shen Hua and other companies are doing related research,†Zhang Chunlei, executive vice president of the Shanghai Huayi Group Technology Institute, said in an interview with CCIN reporters.
It is understood that during the "Eleventh Five-Year Plan" period, with the rapid growth of the national economy, China's annual carbon dioxide emissions have only increased, but the amount of its recycling and recycling is very poor. According to the data provided by the China Industrial Gas Association, by the end of the “Eleventh Five-Year Plan†period, China’s annual recycling of carbon dioxide is about 7.5 million tons, of which 70% of the collected amount is about 5 million tons. According to the German renewable energy organization IWR announced the calculation of China's carbon emissions of 7.43 billion tons in 2009, China's carbon dioxide utilization is less than one-thousandth of the emissions.
Zhao Min, secretary-general of the Carbon Dioxide Committee of the China Industrial Gas Association, told CCIN that the main business that domestic companies are involved in is the recycling and direct application of carbon dioxide products. These direct applications include carbonated beverages, injection well flooding, tobacco puffing, and food preservation. More mature areas.
"According to the requirements of the "Kyoto Protocol," China's carbon emission reduction pressure may increase after 2012, and the country's carbon emission restrictions are tightening. In April this year, the relevant person in charge of the Ministry of Finance has stated that 'twelfth five' In the later period, China is expected to levy a carbon tax, which has brought great pressure on China's large carbon emitters. However, at present, the level of large-scale utilization of carbon dioxide in China is clearly not ideal.†Zhang Chunlei analyzed that carbon dioxide can be used in terms of consumption. The production of other chemical products, but the amount is relatively small. The large-scale use of carbon dioxide in industry mainly involves the production of methanol. From an industrial development perspective, carbon dioxide production from methanol is also known to be optimal in several chemical routes.
What is the difference between China's carbon dioxide production technology and developed countries? According to reports, domestic related organizations have been engaged in the research of the basic technology of carbon dioxide hydrogenation to methanol for decades. Although applied technology research has only heated up in recent years, it is comparable to the international advanced level.
“At present, the carbon dioxide hydrogenation and methanol production technologies in developed countries are at the pilot level. After Japan’s Mitsui Chemicals completed the 100-ton pilot plant, it is said that the technology can be successfully expanded to 10,000 tons, but the current 10,000-ton device has not yet been implemented. Domestic related technologies are also close to the pilot level, and they are only slightly lacking in the details of individual applications compared to the international advanced level. It is no problem to build a one-kiloton pilot plant by relying on the existing technology, said Zhang Chunlei.
It is understood that the Shanghai Huayi Group Technology Research Institute has jointly filed a "863" project during the "12th Five-Year Plan" period with the Shanxi Coal Chemical Institute. The preliminary plan is to build a 10,000-ton carbon dioxide plus hydrogen-produced methanol in 3 years. The demonstration facility is expected to be officially launched next year.
Demonstration devices are necessary Although the domestic focus on methanol-based methanol technology and research has been a boom, but the interviewed experts all said that the technology is still facing some bottlenecks to achieve industrialization.
The first is that the reaction catalyst still needs improvement. "From the chemical reaction process point of view, domestic carbon dioxide-produced methanol catalysts have problems with poor conversion and selectivity. The current conversion rate is generally maintained at 15% to 20%, which is equivalent to 1000 liters of carbon dioxide in the existing catalyst. Only 150 to 200 liters of the reaction can complete the reaction; the target selectivity is about 70%. Therefore, if the performance of the catalyst is further improved, it will effectively reduce the production cost and help the industrialization of the technology, said Zhang Chunlei.
Shi Xianping, deputy director of the Petroleum and Chemical Industry Planning Institute, also pointed out that one of the keys to the reaction of carbon dioxide hydrogenation to methanol synthesis is the catalyst. For this reason, some leading technology companies abroad are also focusing on improving the catalyst for improving the hydrogenation of carbon dioxide to methanol. It is understood that currently Topsøe in Denmark, Kansai Electric Power Co., Ltd. and Mitsubishi Heavy Industries, Germany's Lurgi Company, Korea Science and Technology Research Institute are also researching catalysts for carbon dioxide hydrogenation to methanol.
Beyond the catalyst, the source of hydrogen is the most important reason that restricts the technology's industrialization.
“Current hydrogen production process and cost control are the key to the commercial application of carbon dioxide to methanol technology. The availability of cheap hydrogen sources from non-fossil energy directly determines the economics of the process.†According to Zhao Min, China’s hydrogen is currently The preparation method is also electrolysis through chemical raw materials or water. The former consumes existing fossil resources, and the latter consumes a lot of electricity. As far as the current hydrogen production technology is concerned, the amount of carbon dioxide emitted by the consumption of energy in hydrogen production is no less than the amount of carbon dioxide recovered from the production of methanol, which is not economically justified and actually does not reduce emissions.
Professor Liu Changjun of Tianjin University’s School of Chemical Technology believes that carbon dioxide hydrogenation to methanol, to a certain extent, also depends on the development of new energy, and can solve the problem of hydrogen sources after large-scale development of energy technologies such as wind, nuclear, and solar energy. He also said that the research on carbon dioxide to methanol has important positive significance for the sustainable development of human society. Domestically, it should pay attention to it and it cannot be used as a temporary economic benefit.
Zhang Chunlei said that it is necessary for the state to support the construction of demonstration facilities. "The same technology as coal-based oil can be used as a strategic technology reserve for the country. Once fossil resources in the future can no longer meet the needs of production and living, carbon dioxide production from methanol will play a very positive role."
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