Written by / Qian Yaguang
Editor/ Zhang Nan
Design / Shi Yuchao
Entering 2022, domestic oil prices have achieved six consecutive increases, and No. 95 gasoline has entered the "9 yuan era".
The National Development and Reform Commission notified that from 24:00 on March 31, each ton of gasoline will be raised by 110 yuan and the amount of diesel fuel will be raised by 110 yuan. Since the beginning of the year, the wholesale price of gasoline has risen by 1985 yuan / ton, and the wholesale price of diesel has been raised by 1915 yuan / ton. After this increase, the retail price of gasoline in Beijing is 8.74 yuan / liter, No. 95 gasoline is 9.3 yuan / liter, and No. 0 diesel is 8.49 yuan / liter.
After the outbreak of the Russo-Ukrainian War, Europe and the United States took further sanctions against Russia, so that the supply of energy markets continued to be blocked, and the price of crude oil soared all the way to break through the $100 / barrel mark. As of March 30, the global benchmark Brent crude oil (Brent region of the North Atlantic North Sea) oil price was $111.00 / barrel, and WTI crude oil (West Texas Intermediate Oil) price was $107.46 / barrel. The rise in crude oil prices will naturally drive downstream price fluctuations.
Not only the price of oil has risen, but also the electric vehicles that people have high hopes for emission reduction, but also because the supply of battery raw materials and car chips has been affected, the price has risen collectively, and the enthusiasm of some people to replace fuel vehicles with electric vehicles has also been weakened.
Global greenhouse gas emissions are increasing year on year, keeping the Earth's temperature rising and threatening living systems. Countries around the world have reduced greenhouse gas emissions in the form of global compacts, and continents have proposed carbon peaking and carbon neutrality targets.
If in the past, everyone looked for oil alternatives to cope with the shortage of fossil energy, at present, in the case of increasing oil reserves, the energy transition is more to reduce carbon emissions and improve the earth's climate and environment.
On March 15, the International Energy Agency (IEA) released the "Global Energy Review: Carbon Dioxide Emissions in 2021" report, according to the global energy sector carbon dioxide emissions reached 36.3 billion tons in 2021, up 6% year-on-year, exceeding the pre-COVID-19 level and setting a record high.
To achieve the goal of carbon reduction and decarbonization in the automotive industry, electrification is not the only way. Even if electric vehicles grow faster, a large number of cars on the road will be powered by gasoline or diesel engines. Only if these vehicles are also involved in the process of reducing CO2 emissions can the bi-carbon target be achieved more quickly.
An important means of energy saving and emission reduction of fuel vehicles - a new type of high thermal efficiency, low emission advanced hybrid technology is gradually being promoted, methanol, hydrogen as fuel directly used in the internal combustion engine technology is also under development, and another direct neutral carbon dioxide synthetic fuel technology, recently in the efforts of researchers and automotive supply chain enterprises, has also made breakthrough progress.
As early as November 2007, the Los Alamos National Laboratory in the United States proposed the concept of "Green Freedom", that is, the synthesis of combustible chemical products using carbon dioxide.
Based on the research and development of cutting-edge scientists, car companies, parts companies and some energy companies in the automotive industry are trying to commercialize new fuels synthesized with carbon dioxide and hydrogen. In 2009, Audi was the first in Europe to develop a carbon dioxide-based fuel and named it e-Fuel. Subsequently, Porsche, BMW, Continental, Shell, Sunfire and other automotive or energy-related companies have participated in the research and development of e-Fuel, and some products have entered the mass production stage.
In February this year, researchers from the United States and China greatly improved the efficiency of carbon dioxide into combustible products through the improvement of catalysts in chemical reactions, which will further promote the commercialization of carbon dioxide to gasoline technology. However, due to the current high cost of synthetic fuels including raw materials, equipment, processes and so on in the production process, large-scale mass production will take time.
A new hope for synthetic fuels
In February 2022, a new study from the Proceedings of the National Academy of Sciences (PNAS) pointed out that The team of Matteo Cargnello of Stanford University increased the conversion efficiency of carbon dioxide hydrogenation to butane by 1,000 times through a ruthenium-based catalyst, giving people new hope in synthetic fuel technology.
Carbon dioxide (black and red) and hydrogen molecules (blue) react with the help of a ruthenium-based catalyst. On the right, an uncoated catalyst produces the simplest hydrocarbon, methane. On the left, the coated catalyst can produce long-chain hydrocarbons such as butane, propane, and ethane▼
Ruthenium (Ru) is a rare precious metal of the platinum family, with a melting point of 2310 °C and a content of only one billionth in the earth's crust. Ruthenium is very stable even in a very strong exothermic environment, and can withstand the corrosion of nitric acid, sulfuric acid, hydrochloric acid, and also has resistance to hydrofluoric acid and phosphoric acid.
Back in 2016, Nobel laureate George Euler's team, for the first time, adopted a metal-based ruthenium-based catalyst that converted carbon dioxide captured in the air directly into methanol at a conversion rate of up to 79 percent.
When used as a catalyst, ruthenium is cheaper than other rare metals such as platinum and palladium, but when used to convert carbon dioxide, the product produced is mostly methane, and the longer chain hydrocarbon production is not high.
Chengshuang Zhou (left), the first author of the paper in the Proceedings of the National Academy of Sciences and a doctoral student in the lab of Matteo Karnello (left), and Matteo Karnello, an assistant professor of chemical engineering at Stanford University
To solve this problem, The Carneiro team coated the surface of ruthenium with a layer of porous plastic, successfully extending the carbon chain length of the conversion product, greatly improving the yield of butane, and the conversion efficiency reached 1,000 times that of the standard catalyst, which will further advance the commercialization process of carbon dioxide to gasoline technology.
Coincidentally, on March 4, 2022, the "carbon dioxide to gasoline" scientific research project led by the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences passed the evaluation of scientific and technological achievements organized by the China Petroleum and Chemical Industry Federation.
At the same time, the institute also cooperated with a company in Zhuhai to jointly build the world's first 1000 tons / year carbon dioxide hydrogenation to gasoline pilot plant, has also been successfully tested, produced in line with the national VI standard of clean gasoline products, carbon dioxide conversion rate of 85.1%, gasoline selectivity of 76.1%, carbon dioxide consumption of 4.3 tons, hydrogen consumption of 0.59 tons, gasoline product octane number, isoparaffin and aromatic hydrocarbon content reached the national VI standard.
In the actual operation of synthetic fuels, when the two are combined using catalysts, it is easier to generate methane than gasoline. At room temperature, gasoline is liquid and easier to handle, while short-chain gases such as methane, ethane, and propane are difficult to store.
In order to increase the proportion of gasoline, the Dalian Institute of Chemicals of the Chinese Academy of Sciences has taken a different approach, not using rare metals such as ruthenium as a catalyst like the United States, but using iron oxide, sodium and zeolite to form a new multifunctional catalyst (Na-Fe3O4/HZSM-5).
This new multifunctional composite catalyst has three unique advantages: one is that the conversion production conditions are not high, and the harsh conditions of the laboratory are not needed, laying the foundation for industrial large-scale production; the second is that the gasoline octane number produced by this method exceeds 90, and the exhaust emissions and other various pollutants fully meet the requirements of national regulations; the third is that the catalyst has good stability, can be used continuously and stably for more than 1000 hours, and has a very broad application prospect and development space.
Sun Jian, a researcher at Dalian Institute of Chemicals, introduced the research and development process of carbon dioxide hydrogenation to gasoline pilot technology
The research of the Dalian Institute of Chemistry of the Chinese Academy of Sciences has been honed for many years, and in 2017, a research team composed of Sun Jian, Ge Qingjie and Wei Jian began the research and development of this project, and the research results were published in NatureCommunications and selected as a research highlight by the journal Nature.
After that, it has successively undergone laboratory tests, 100-gram single tube tests, catalyst tonnage scale-up preparation and pilot process package design, and applied for patents for related processes, realizing the efficient conversion of carbon dioxide hydrogenation to gasoline.
The development of synthetic fuels
In November 2007, Jeffrey Martin of Los Alamos National Laboratory in the United States Jeffrey Martin and William L. Kubic came up with a sensational "Green Freedom" concept, which uses carbon dioxide to synthesize combustible chemical products.
The concept first uses a concentrated potassium carbonate solution to absorb carbon dioxide from the air; second, the use of electrolysis to extract carbon dioxide from the solution, while decomposing water into hydrogen and oxygen; and finally, hydrogen and carbon dioxide into synthetic fuels or organic chemicals.
However, this technology not only has a huge investment and high operating costs, but also at that time, the technology of capturing carbon dioxide and electrolytically extracting carbon dioxide in concentrated potassium carbonate solution was still in the theoretical stage, and the specific operation had not yet been verified.
Later, on the basis of the research and development of cutting-edge scientists, car companies, parts companies and some energy companies in the automotive industry are trying to commercialize new fuels synthesized by carbon dioxide and hydrogen. In Europe, this synthetic fuel is called e-Fuel (electric synthetic fuel), which is actually a synthetic fuel made from renewable energy.
e-Fuel is a liquid fuel that generates electricity from renewable sources (solar and wind, etc.) and is synthesized by a catalytic reaction of hydrogen and carbon dioxide. The required hydrogen is extracted from electrolyzed water, while carbon dioxide is obtained from the air by direct air capture technology.
The researchers mixed hydrogen, carbon dioxide and green hydrogen to form a synthetic e-methanol (e-methanol); then, in the refinery, the use of MTG (methanol to gasoline) technology to further process methanol, and then methanol as an intermediate product to synthesize dimethyl ether, etc., through the Fischer-Tropsch process to produce synthetic fuels, including gasoline (e-petrol), diesel (e-diesel) and so on.
If the large amount of energy required at each stage of production comes from zero-carbon energy, the entire production chain can almost become carbon neutral, that is, after the production of these fuels, the carbon dioxide in the atmosphere does not increase.
e-Fuel synthetic fuel meets the specifications and standards of existing fuels, and there is no difference in octane number compared with existing fossil fuels, which means that the knock resistance and dynamics of No. 98 e-Fuel are the same as those of conventional No. 98 gasoline, but the emissions and pollution of harmful substances are lower. e-Fuels can be used in all conventional fuel engines and will not affect the fuel delivery system, injection system, combustion, etc. of existing vehicles.
The German Audi brand is the first car company in Europe to start developing co2-based fuels. In 2011, Audi unveiled the e-gas project in Hamburg. Audi also works with the French global bioenergy company to develop Audi e-gas; with Joule in the United States, using microorganisms to produce synthetic fuel oils - Audi e-diesel and Audi e-ethanol.
The Audi e-diesel project, run in partnership with Dresden energy technology company Sunfire, follows the PTE (Power-to-Liquid) principle and uses renewable energy to generate electricity to produce liquid fuel, with carbon dioxide taken from biogas plants and air capture.
The production process begins with the decomposition of oxygen and hydrogen in water by high-temperature electrolysis technology. Then, in a high-temperature and high-pressure environment, hydrogen and carbon dioxide are reacted in a synthetic reactor to generate a liquid long-chain hydrocarbon called "blue crude oil", which is finally refined to form Audi e-diesel. Audi tests have shown that the fuel is well suited for blending with diesel or can be used as a fuel alone.
The Sunfire project began in May 2012, the plant was officially put into operation in July 2013, and was put into operation on November 14, 2014, producing "e-diesel" ethan diesel fuel, which was first used on the official car Audi A8 3.0 TATtro by Professor Johanna Wanka, then Minister of Education and Research of Germany.
Porsche, which shares audis, is also making synthetic fuels, and it sees e-Fuel as an auxiliary tool for electrification.
Porsche is involved in the World's first large-scale commercial synthetic fuel project, the Haru Oni project, of which Siemens Energy is a co-developer. Porsche's goal is to use electricity generated by wind turbines to split water into hydrogen and oxygen to produce fuel. Hydrogen is then combined with atmospheric carbon dioxide to form synthetic methanol, from which synthetic gasoline, diesel and kerosene can be extracted.
The Haru Oni pilot project, which has built the world's first large-scale production plant to produce synthetic fuels in the southern Chile antarctic region, is expected to produce about 130,000 liters of e-Fuel in 2022 and increase production capacity to 55 million liters by 2024. Porsche's blend is now expensive, $10 per liter, but it is likely to fall to around $2 per liter after widespread adoption.
BMW invested in an energy company called Prometheus Fuels in 2020, and its e-Fuel is a premium gasoline that provides a high octane number, burns cleanly, and is free of heavy metals or aromatics, low nitrous oxide and sulfur dioxide. The price may be the same or lower than unleaded gasoline after large-scale production.
Sheel says it can produce GTL (Gas To Liquids) synthetic diesel from natural gas. This synthetic fuel is more energy dense than most other fossil fuels and reduces CARBON dioxide emissions during the conversion from well to wheel.
Continental will mix hydrogen from electrolysis of water with carbon dioxide from power plants and steel mills to form a completely new feedstock, which is then mixed with 15% formaldehyde ether (OME) to form a synthetic fuel. This type of fuel can reduce CO2 emissions per 100 kilometers by about 800 grams compared to conventional fuel vehicles, but for engines to use it, the fuel injection system and the aftertreatment system need to be greatly adjusted.
The aforementioned Sunfire company, which works with Audi as a founding member of the Norwegian syndication of synthetic fuels (e-Fuel), is expected to start construction of its PtL workshop in Norway in 2023, producing around 10 million liters of synthetic fuel per year. Sunfire predicts that the production cost of such synthetic fuels will fall to $1.67/liter over the next 5 years.
The reason why many automotive industry-related companies are striving to develop new synthetic fuels that replace fossil fuels is also closely related to the current environment of the automotive and energy industries.
Although the automotive industry has now irreversibly turned to electrification, but the traditional car manufacturers still do not want to give up the internal combustion engine, a mature technology that has lasted for a hundred years, on the one hand, the future cannot be fully pressed on electric vehicles, after all, there is no innovative breakthrough in battery technology; on the other hand, the use of carbon dioxide synthetic fuels can achieve carbon neutrality in the production and use process, so as to maintain the combat effectiveness of the internal combustion engine industry chain, solve the problem of fuel carbon emissions, and continue to fight.
Of course, synthetic fuels made by carbon dioxide hydrogenation have other roles besides replacing the fuel of cars.
The first is that this synthetic fuel can play a role in sequestration. As carbon emissions regulations become more stringent, the conversion of carbon dioxide into synthetic fuels clearly provides an effective buffer against achieving carbon neutrality. In addition, with the implementation of the carbon credit system, carbon dioxide fuels can also obtain huge carbon credits, which has considerable economic value.
The second is used for energy storage. The use of renewable energy sources such as wind and solar energy to generate electricity is the trend of the times, but the electricity they generate is extremely unstable and will adversely affect the power grid, and the other is affected by the regional climate and may not be widely available in all regions.
The use of carbon dioxide to make synthetic fuels, will use a lot of electricity, if a large number of wind and solar energy through the electrolysis of water to prepare hydrogen, and then combined with the carbon dioxide extracted from the air, in situ into synthetic fuel, and then transported to other regions for use, it will also be wind and solar energy power in disguise storage. And this way is safer and more convenient than storing and transporting hydrogen directly.
The current limitations of synthetic fuels
In fact, only carbon dioxide can not produce gasoline, you must add hydrogen in the synthesis process, because the main component of gasoline is hydrocarbons.
For every 1 ton of octane (gasoline) synthesized, 3.09 tons of carbon dioxide and 0.44 tons of hydrogen are required. At this stage, the market price of industrial-grade carbon dioxide is 500-600 yuan / ton, industrial-grade hydrogen is 50,000-60,000 yuan / ton, and the cost of the two raw materials is 23545 yuan / ton at a low price.
After the last price increase, the price of Beijing No. 92 gasoline is 8.65 yuan / liter, and the price per ton of gasoline is 11452 yuan calculated according to the density of No. 92 gasoline of 0.755, that is, the cost price of only two basic raw materials is more than twice the current price of gasoline.
According to scientists, carbon dioxide hydrogenation to gasoline is an exothermic process, and the amount of electrical energy consumed will be much greater than the energy produced by gasoline combustion. If you add the cost of catalysts, labor costs, financial costs, investment costs, etc., the price of gasoline made of carbon dioxide is much higher than the price of ordinary gasoline.
If the carbon neutrality of synthetic fuels is emphasized, then it is necessary to use the METHOD of direct air capture (capture in the air) to prepare carbon dioxide, and the preparation of green hydrogen by electrolyzing water to produce hydrogen, which is more expensive.
It is undeniable that synthetic fuels will play a very good role in achieving carbon neutrality if they are used on a large scale, with broad prospects and great significance. However, the biggest problem of its commercialization is the cost, this conversion process involved in the materials, processes, equipment and catalysts, etc. all need expensive costs, even if the use of new catalysts, improve the conversion efficiency of carbon dioxide, want to use on a large scale, at this stage is still not very realistic, it can be said that it is far from quenching the thirst.
This article was originally produced by Automotive Business Review
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