Huanxisha, drizzle and oblique wind made Han Xiao.
Su Shi
Drizzle and oblique winds made Han Xiao,
Light smoke clears the beach.
The time to enter Huaihai and Luo Qing is getting longer and longer.
Snow foam and milk flowers float in the afternoon light,
Try Artemisia annua and Polygonum multiflorum bamboo shoots.
Human taste is pure happiness.
As the saying goes, "after many vicissitudes, the taste of the world is pure joy." Facing the change of the pattern, Pingtou Brother made a highly comprehensive review of the development history of the global refining and chemical industry, taking history as a mirror, with a view to tracing the source and providing directional guidance for the development of the refining and chemical industry in China.
1. Review of the technical development history of global refining and chemical plants: from the birth of distiller.
1849, JamesIbung, Scotland produced paraffin oil for lighting. The raw material was originally oil from coal mines, and later coal. This method was patented in Britain. This technology has been transferred to many factories in Britain and America.
At the same time, according to the history of American petroleum industry, it was the Canadian geologist Dr. Abraham Gesner who first extracted kerosene for lighting from coal. 1852, he developed a similar process and obtained an American patent. The patent right is to produce kerosene from coal (Greek is wax and oil). ) 1853, a company in new york used his technology to produce kerosene and put it on the market.
However, the American name is Sam. M.Kier is the founder of the oil refining industry, because he not only successfully applied the distillation principle to process crude oil and produce petroleum products, but also made the first commercial still. Kilburn was a drug dealer in Pittsburgh. He owns a coal mine and an iron foundry, and is one of the founders of Pittsburgh-Philadelphia Shipping Company. For many years, he operated a salt well on the Al Hani River near Talaton, Pennsylvania. Some salt wells ooze crude oil. The saltworks owner threw it into the river as an annoying by-product, which made the boaters very annoyed. Kiel collected them and sold them in glass bottles as medicine. The product name is "petroleum" or "paraffin oil".
Kiel got some crude oil samples and sent them to Professor James Booth in Philadelphia (he is the president of the American Chemical Society), asking him to do analysis and find a way for tarantula crude oil. Booth did an experiment in the laboratory, which proved that crude oil can be processed into good lighting oil by distillation, and drew a sketch of the distiller for Kiel. Therefore, Booth is also considered as the first chemist in the oil industry.
Photo: The first stills in the world.
Kiel made the first distiller in the United States according to Booth's sketch, with a diameter of 1 10.5cm, a height of 142.2cm and a capacity of 0.8m3 The kettle was filled with Tarantun crude oil, and coal was burned under the kettle. The oil vapor generated in the kettle enters the bucket through a small tube and condenses into light yellow kerosene. /kloc-in 0/850, Kiel began to sell kerosene for lamps on the seventh street in Pittsburgh, which was called "carbon oil". The price is $65438+0.50 per gallon. This oil burns brightly, but it has an unpleasant smell.
A. C.Ferris, a coffee and spice retailer in new york, took a fancy to this lamp oil and bought back 12 gallon. He came up with a way to treat it with sulfuric acid and caustic potash, and the refined oil was lemon-colored and almost odorless. He called this process "coal-oil" process. This oil is very popular. So, he searched for crude oil everywhere and expanded the source of raw materials. First, he bought all the crude oil produced by the Kiel Tarantula Salt Field. Then, send people to California, Dutch East India and other places to inspect. He promised to buy it at $20 a barrel.
In Canada, Ferris approached Jeames Miller Williams, who runs Enning skilling Oilfield, and bought crude oil from him. 1858, Ferris processed crude oil 1 183 barrels (16 1 ton) and became the largest refiner in the United States at that time. According to records, in 1859, there were more than 50 refineries in the United States, which produced kerosene from bituminous coal, shale or natural asphalt respectively.
Thermal cracking technology was invented about 19 10 years ago, when automobiles began to be produced on a large scale, and then tractors and airplanes were widely used. The market demand for gasoline is growing rapidly, and gasoline has replaced kerosene as the most important petroleum product.
Figure: Continuous research on refining process.
Then the question is, how can we extract more gasoline from unit crude oil?
The first breakthrough in this respect is thermal cracking. The inventor of thermal cracking is William m Burton. Burton was born in Cleveland, USA. 1886 graduated from WesternReserve university, and 1889 received his doctorate from Hopkins university. 1890 joined standard oil company as a chemist, and later served as assistant and general manager of refinery. 19 1 1 became the director of Indiana standard oil company, 19 15 became the vice president, and 19 18 became the president. During World War I, he was at the Whiting Refinery, and then he was the director of the laboratory, Robert Humphries. Rogers and Bransky also participated in the study. They are both doctors at Hopkins University.
They set the reaction temperature to 850 degrees Fahrenheit (454 degrees Celsius). At that time, there was no welding technology, and the cylinder made of steel plate could only be riveted. Is it strong enough? We must try again and again.
After more than two years of work, by the end of 19 10, Burton and Humphrey had been convinced that it was feasible and safe to produce "synthetic gasoline" at high temperature and high pressure. To this end, he made a report and suggested 65,438,000 sets of industrial pyrolysis kettles with a capacity of 8,000 gallons. But at that time, Indiana Standard Oil Company was still a subsidiary of Rockefeller Standard Oil Company, and its parent company was overwhelmed by the lawsuit of "anti-monopoly law". Some people on the board of directors were also worried that high temperature and high pressure would cause an explosion like a boiler and did not approve his proposal.
Figure: The world oil refining industry is developing rapidly.
19 1 1 year, Standard Oil Company was forced to disband and Indiana Standard Oil Company became independent. Burton built the world's first semi-industrial pyrolysis device. Its diameter is still 8 feet (2.44 meters), its height is 10 feet (about 3.05 meters), and its capacity is 150 barrels (about 20 tons). The recovery rate of gasoline has more than doubled. 191365438+17 October, the company obtained the patent right of Burton pyrolysis process. At that time, the raw oil of thermal cracking was gas oil in crude oil, and the distillate oil obtained initially accounted for about 25% ~ 30% of the raw oil; Quickly increased to 65% ~ 70%, and the final recovery rate of gasoline was about 50%. Thermal cracking process has shown great advantages, and new devices have been established in many places.
At this time, a new technology conforming to the development of the times was born, that is, catalytic cracking process, and the birth of this technology also marked an important achievement of oil refining process.
The so-called catalytic cracking is the cracking reaction under the action of catalyst. Compared with thermal cracking, the yield of light oil is higher, the octane number of gasoline is higher and the stability of diesel oil is better. At the same time, it produces a large amount of liquefied gas rich in olefins, which is a good organic chemical raw material. Up to now, catalytic cracking is still the main secondary processing technology in almost all refineries.
The inventor of catalytic cracking process is French engineer and industrialist EugeneHoudry. 1On March 5th, 937, a fully commercialized Hudeli FCC unit was born in its Markus Hook Refinery, with a daily processing capacity of12,000 barrels (about 600,000 tons/year). At the annual meeting of api gravity in 1938, Arthur Pew announced the success of this new technology, and oil companies demanded technology transfer in succession.
Photo: Eugene Hadri
Indiana Standard Oil Company organized a team headed by Paulos, vice president and director of oil refining department. After argumentation, it is considered that the technology transfer fee is too expensive, and the imported technology is not as good as its own research. Several other companies have the same view. From 1938 to 10, a cooperative research institution-catalytic research society was formed. Participants include: Indiana Standard Oil Company, New Jersey Standard Oil Company, German National Industrial Company and Kellogg Company (note: this is a specialized petroleum engineering and construction company).
Soon, InBev Oil Company, Royal Dutch Shell Group, Dezhou Company and Dahua Oil also joined in. The group cooperated in the research and development of fluid catalytic cracking technology.
The concept of fluidized bed was put forward by William odell of Standard Oil Company of New Jersey and patented in 1936. Because little is known about the control of catalyst regeneration and carbon deposition combustion, the problem of fluidized bed is put on hold for the time being. Hu Deli's paper on catalytic cracking published in the American Oil and Gas magazine has aroused the enthusiasm of scientific and technological personnel to study fluid catalytic cracking. Researchers from Standard Oil Company of New Jersey broke through the key problem of "up-flow" catalytic cracking, making catalyst, feed oil, product and flue gas flow upward in the reactor and regenerator respectively, and then separate from the top.
Photo: Standard Oil Company of New Jersey.
1941February 1 1 day, Standard Oil Company of New Jersey, USA announced that the Catalytic Research Association had successfully developed the fluidized catalytic cracking process. Three sets1.20,000 barrels/day (about 600,000 tons/year) of fluidized catalytic cracking units have been built one after another. The first one was designed and built by Kellogg Company of baton rouge Refinery. The production date is1May 25th, 942.
This new technology is developing rapidly. The first generation of "upper class" was quickly replaced by the second generation of "lower class". The above-mentioned first set of upflow device has not been put into production, and the second generation 10 set of downflow device has started construction. 1947, the group developed the third generation, 195 1, and developed the fourth generation fluid catalytic cracking technology. Because this cooperative research association takes Standard Oil Company of New Jersey as the core, these technologies are collectively called ESSO fluid catalytic cracking process.
In addition, in order to further improve the output and quality of petroleum products and expand the development direction of transforming petroleum products into chemical products, technicians from global oil companies have joined the research on catalytic reforming technology. 1949 On March 29th, the company announced the method of producing high-quality gasoline by dehydroisomerization of cycloalkane under the action of catalyst, which opened up a new way to improve its octane number.
The key to the new process is to find an effective catalyst. After years of efforts, they developed a platinum catalyst. 1949, 10 year1October 28th, the world's first platinum reformer was built in the "Old Holland" refinery in Muskegen, Michigan, USA. The initial treatment capacity is 238.5 cubic meters per day. This equipment is still running after 10 years, and its processing capacity has been expanded to 477 cubic meters per day.
Figure: Platinum catalyst
Global Oil Company announced another platinum catalyst in 195 1, and another set of equipment was put into production at the end of 1953.
From 65438 to 0955, two new catalytic reforming processes appeared. One is Hudley's supporting catalytic reforming, which can recover aromatic hydrocarbons from the product under moderate intensity conditions. The other is the Rex reforming process of global oil companies, which combines platinum reforming with aromatic hydrocarbon extraction. A variety of catalysts were developed in the 1960s.
In the late 1960s, global oil companies developed the platinum reforming process into a continuous regeneration catalytic reforming process, and successfully put into operation the first reforming unit, including vertical heat exchanger, box heating furnace and vertical chimney reactor, at 197 1. The process makes the reaction system and regeneration system have higher operation rate and higher product octane number.
2. Historical review of global refining and chemical industry scale development: rapid growth driven by technology.
Oil refining is a mature process, which is mainly accompanied by the increase of scale and complexity coefficient from the historical development and evolution; In recent years, due to the demand of processing heavy oil, the general hydrogenation capacity of refineries has been improved. Since 20 14, the demand for refined oil has slowed down and the profitability of chemical products has improved, and oil refining has been committed to increasing the proportion of chemical products. Therefore, large-scale, upgrading of complex coefficient and integration of refining and chemical industry have become the new trend of refining development.
Due to the good profits of chemicals in recent years and the changes in the processing structure of crude oil light oil and heavy oil, the general direction of refining processing technology has become: to produce more light hydrocarbons as chemical raw materials, to increase the feed adjustment of light and heavy oils, and to improve the ability to process residual oil. The functions of different equipment in the refining industry chain can be summarized as follows:
Catalytic cracking (FCC): Catalytic cracking is the main means of secondary conversion of heavy oil in refineries. At present, the global FCC processing capacity accounts for about 16% of the primary processing capacity of crude oil. Catalytic cracking is the cracking reaction of heavy oil under the action of heat and catalyst, which is converted into cracking gas, gasoline fraction and diesel fraction. Its raw material is heavy distillate oil obtained by crude oil distillation, or a small amount of residual oil is mixed in the heavy distillate oil, or all of it is atmospheric residual oil or vacuum residual oil. Catalytic cracking not only produces oil products, but also produces chemical propylene, accounting for nearly 30% of the global propylene production, which is the second largest propylene source after steam cracking. Gasoline produced by catalytic cracking has a high octane number, and cracked gas (refinery gas) contains a lot of propylene, butene and isomeric hydrocarbons. The gasoline in a typical refinery is mainly composed of light straight-run gasoline, coking light gasoline, alkylated oil, reformed oil, FCC gasoline and MTBE.
Catalytic reforming: mainly converting naphtha into reformed oil rich in aromatics and by-product hydrogen, which is the main route of PX production. The reformate can be directly used as the blending component of gasoline, and benzene, toluene and xylene can also be extracted by aromatic extraction. By-product hydrogen is one of the main sources of oil refining hydrogenation unit.
Residue hydrocracking: hydrocracking technology is one of the main technical means of heavy oil deep processing, and it is also an important technical means to directly produce clean fuel and high-quality chemical raw materials while lightening raw materials. There are two kinds of residual oil treatment, decarbonization and hydrogenation. At present, the most advanced processing technologies representing residue hydrogenation are boiling bed hydrocracking and suspension bed hydrocracking (or slurry bed). Hengli Petrochemical adopts French Axens technology, and this year, the single-line 3.2 million tons/year (23.2 million tons/year in total) fluidized bed residue hydrocracking started smoothly, successfully converting all the heavy oil in crude oil into intermediate products such as naphtha, diesel oil, wax oil and unconverted oil, providing sufficient raw material guarantee for downstream naphtha hydrogenation, diesel oil hydrocracking, wax oil hydrocracking and solvent deasphalting. However, Italy ENI Company's annual output of 654.38+350,000 tons of suspended bed hydrocracking in Sannazzaro Refinery has been industrialized.
Delayed coking: it is still a long-term trend that the proportion of heavy and inferior oil processing will increase in the future, and delayed coking is the technical route choice for decarbonization. Delayed coking is a thermal cracking process, the main purpose of which is to convert residual oil with high residual carbon into light oil. The United States is the country with the largest coking capacity, but due to the surplus of light crude oil in the United States, the utilization efficiency of coking units has decreased. Delayed coking is one of the indispensable means for refinery to process inferior heavy oil. Tailings from other plants in the plant can be further processed, including vacuum residue, visbreaking residue, FCC slurry, hydrocracking tail oil, etc. It can also be used to improve the gasoline-diesel ratio of refineries and provide raw materials for ethylene industry and reforming units. The advantages of delayed coking mainly include: strong adaptability to crude oil, increasing the ratio of diesel to steam and processing catalytic slurry with high sulfur content.
Hydrogen production in refinery: integrated refinery needs a lot of hydrogen, which is mainly used for residue hydrogenation and hydrofining. At the same time, the by-product hydrogen will also be produced in the production process of the integrated refining and chemical plant, so the comprehensive utilization of hydrogen is very important. The main sources of hydrogen in large-scale refining and chemical projects are: 1) hydrogen production from petroleum coke or coal, and hydrogen production from natural gas SMR purchased by most refineries in the United States; 2) Catalytic reforming of hydrogen. Under normal circumstances, the by-product hydrogen from reforming accounts for about 0.5- 1% of the total crude oil, and the total hydrogen refining process generally accounts for 0.8-2.7% of the crude oil processing capacity; 3) Hydrogen, a by-product of naphtha cracking; 4) propane/butane dehydrogenation by-products; 5) Recovery of low-concentration hydrogen, such as hydrogen by-products from hydrogenation, catalytic cracking and delayed coking, is extracted by three methods: pressure swing adsorption (PSA), membrane separation and cryogenic treatment.
Figure: refinery type and equipment matching relationship.
The refining capacity has entered the stage of rapid expansion since 20 18, which means that it will face the risk of downward demand in the industry in the future. According to BP energy statistics, the global refining capacity increased by10005 million barrels per day (5002.4 million tons/year) or increased by 85,683,000 tons/year. From 20 19, the growth rate of new refining capacity in the world will expand. With the expansion of the scale of a single refinery, the downstream will also be equipped with chemicals such as ethylene.
Figure: The global production capacity has rapidly increased from 1965 to 20 19.
Ethylene is an important raw material for chemical products, which plays an obvious role in driving the national economy. The investment in an ethylene project is often accompanied by the investment in many downstream fine chemical products. Investment in ethylene projects will often have a greater radiation effect, which is expected to achieve the effect of supply creating demand.
Except CTO/ MTO of producing olefins from coal in coal chemical industry, most ethylene production in the world is formed by cracking. The core of production scale lies in the scale of cracking furnace and the power of compressor. At present, the trend of ethylene production is large-scale and integration of refining and chemical engineering. Traditional ethylene production is mostly produced by cracking purchased naphtha. Under normal circumstances, it takes 3.3 million tons of naphtha to produce 6.5438+million tons of ethylene, and at the same time, it produces nearly 50 tons of propylene, 6.5438+0.8 million tons of butadiene, 200,000 tons of pure benzene, and other aromatic hydrocarbon mixtures, isobutene, butene, C5, ethylene tar, etc. It's all by-products At present, there are nearly 270 ethylene plants in the world with an annual production capacity of 654.38+700 million tons. After 20 10, due to the shale gas revolution in the United States, a large number of ethane by-products were also brought in the development process, which is a high-quality raw material for cracking ethylene.
Figure: Since 2005, the global ethylene production capacity has increased rapidly.
Besides atmospheric and vacuum distillation, the main processing technologies of petroleum at present include hydrocracking, catalytic reforming, delayed coking, hydrofining, visbreaking and alkylation. After years of development, petroleum refining and processing technology has formed a complete system, but the principle and technology of petroleum processing have not changed much. Technical progress is mainly reflected in the scale of the plant, the ability of refining and chemical integration, the progress of catalysts, the hydrotreating ability of heavy oil and residue, and the intelligent production.
Scale is mainly reflected in the large-scale, integration and intensification of petrochemical parks. A comprehensive comparison is made between Mailiao Formosa Plastics Base in Taiwan Province Province, China, Jamnagar New Town Company Production Base in India, Ulsan SK Production Base in Korea, Jurong Island in Singapore, Jubail in Saudi Arabia, Yanbu in Saudi Arabia and Ruweis in United Arab Emirates. Through analysis, it can be concluded that the scale of the plant is conducive to reducing the investment cost of equipment, improving the yield of raw materials and increasing the stability of production. The centralized management of the park can reduce the cost of public works, increase the optimization of various products, and realize the material balance and make the best use of it.
Figure: Statistics of the largest single enterprise in the world in oil refining units.
Different processing technologies can be selected for different crude oil varieties, and suitable process routes can also be selected for different downstream application requirements. Generally speaking, crude oil processing is divided into primary processing, secondary processing and tertiary processing. Primary processing is mainly the primary processing of crude oil, that is, crude oil distillation is divided into several different boiling points (fractions), and its processing device is atmospheric distillation or atmospheric and vacuum distillation. Secondary processing is the deep processing of crude oil, that is, the fractions obtained from primary processing are reprocessed into commodities, and its processing devices include catalytic cracking, hydrocracking, delayed coking, catalytic reforming, visbreaking and so on.
The product cutting of oil refining is mainly based on fractions, hydrocarbon ratio and so on. The corresponding carbon content is: c1-c4lpg; C5-C9 naphtha; C5-C 10 gasoline; C 10-C 16 kerosene; C 14-C20 diesel oil; C20-C50 lubricating oil; C20-C70 fuel oil;
The long-term trend of heavy crude oil and the demand for ethylene feedstock after refining and chemical integration make residue hydrocracking more suitable for China's national conditions. In recent years, with the increase of shale oil production in the United States, the supply of light oil has increased; On the other hand, US sanctions against Venezuela have reduced the production of heavy crude oil. It can also be seen from the proportion of crude oil imported from Shandong refinery recently that the sulfur content and acid value of processed crude oil have decreased and become slightly lighter. Due to the long history of American refineries, the gasoline yield brought by light oil processing is high, but the diesel oil market is good; Therefore, FCC feed will decrease and diesel oil output will increase, which will lead to the decline of refinery efficiency. At the same time, refineries in the United States still mainly use processed fuels, and delayed coking accounts for a large proportion; Moreover, the ethane supply in the United States is sufficient, and the ethylene cracking raw materials are mostly ethane by-products of shale gas. The demand for light hydrocarbons in refinery residue hydrocracking is less, and the application space of residue hydrocracking is smaller.
The new large-scale refining and chemical projects in China mainly focus on increasing the proportion of chemical products, and the overall design route is to produce more PX and light hydrocarbons and minimize the output of refined oil. Hydrogen consumption is large in the process of refined oil hydrofining and residue cracking, so it is often necessary to use coal or petroleum coke to produce hydrogen to ensure hydrogen supply.
Third, the forecast of global refining and chemical industry development in the next 50 years: diversification and deepening development brought by integration
Regarding the development trend of the global oil refining industry, Pingtou Ge believes that "controlled increase in oil refining" is the normal development of global oil refining integration under the background of global supply exceeding demand of refined oil. The enterprise development model of oil refining integration has become a closely integrated development model of chemical raw material exchange, energy sharing and public facilities use, which greatly reduces the production cost of products and improves the added value of products.
For the development trend of global refining and chemical integration in the next 50 years, Pingtou Ge summarized the following directions:
(1) Global refining and chemical integration is rapidly developing to a more diversified mode.
Zhejiang Petrochemical Company mentioned at the beginning of this paper is a 40 million tons/year refinery, with 2.8 million tons/year ethylene plant and 6.5438+004 million tons/year aromatic plant downstream. The downstream chemical plant is located in the forefront of domestic comprehensive enterprises. In addition, ExxonMobil developed and applied IGCC gas-electricity cogeneration technology, which was industrialized in China Fujian Refining and Chemical Company, becoming the first IGCC cogeneration device for hydrogen supply, steam supply and power generation in China. The deoiled asphalt of its solvent deasphalting unit is used as raw material to produce hydrogen, ultra-high pressure steam and power generation, and oxygen and nitrogen are by-products, meeting all the electricity, steam and 40% of its120,000 tons/year refining and chemical integration project.
Therefore, Pingtou Ge believes that since the 1990s, with the demand of aromatic hydrocarbon market, the refinery itself has to meet the demand of hydrogen and steam, electricity or cogeneration, and the integration of refining and chemical industry has crossed the business scope of the refinery itself, covering the production of various chemical products, further increasing the output of aromatic hydrocarbons, olefins and other products and enhancing the diversified development model of the refinery. Moreover, with the surplus of oil supply scale, the global refining and chemical integration enterprises will move towards a more diversified product structure in the future, and the downstream will involve special chemicals and other fields.
(2) Global refining and chemical integration is developing in depth.
China Petroleum, Saudi Basic Industries Company and Dalian Institute of Chemical Engineering of China Academy of Sciences are cooperating to develop the technology of producing olefins/aromatics directly from natural gas. Compared with the existing traditional route of natural gas conversion, this technology does not need the preparation process of high-energy synthesis gas, which shortens the process route, realizes zero carbon dioxide emission in the reaction process itself, and the utilization efficiency of carbon atoms can reach 100%. Once it is successfully developed, it will further expand the integration of refining and chemical industry to natural gas, coal chemical industry and other fields.
ExxonMobil, Saudi Aramco and Saudi Basic Industries Company have all developed the technology of direct cracking of crude oil to olefins. By omitting the main refining links such as atmospheric and vacuum distillation and catalytic cracking, the process is simplified and the investment is reduced. In order to maximize the production of chemicals and produce more chemical raw materials such as olefins and aromatics, the chemical conversion rate can reach 50%~70%. Moreover, ExxonMobil plans to launch the world's first direct cracking technology of crude oil to olefins in Guangdong.
In addition, the global technology research direction (Pingtou Ge will focus on the research results of global new technologies in the later period, and I hope you will pay close attention to it) also includes the technology of direct olefin/aromatic hydrocarbon production from natural gas, the technology of catalytic cracking to produce more low-carbon olefins, the technology of catalytic reforming to produce more aromatic hydrocarbons and the technology of hydrocracking to produce more ethylene. Hydrocracking is becoming the core technology of refining-chemical integration. It is widely used in the production technology of adopting new catalysts, optimizing process flow or conditions and producing more naphtha or hydrogenated tail oil.
Although refining and chemical integration is an important carrier of refining and ethylene production, Pingtou Ge believes that with the development of technology, global refining and chemical integration presents a new model and development trend, and has become the main strategic choice for global refining and chemical integration enterprises to optimize resource allocation, reduce production costs and increase added value of products. The deepening development of global refining and chemical integration will also become the long-term trend of the global refining and chemical industry in the future.