On September 13, the National Development and Reform Commission and other 15 ministries and commissions jointly issued a notice on the implementation plan for expanding the production of biofuel ethanol and promoting the use of ethanol gasoline for vehicles. It is determined that the promotion of the use of ethanol gasoline in many provinces and cities in Northeast China will be promoted from 2020 to 2020. In the year, the country basically implemented full coverage of ethanol gasoline. The previously introduced standard for ethanol gasoline for vehicles requires that the oxygenate in ethanol gasoline should not exceed 0.5% by weight. This means that components such as methyl tert-butyl ether (MTBE), etherified light gasoline, etc. will not be used as a gasoline blending component. In the future, will there be a way out for carbon four in oil adjustment? How should relevant enterprises quickly change their ideas in advance? Zhang Yong, general manager of Kairui Environmental Protection Technology Co., Ltd. (hereinafter referred to as “Kerry”), recently accepted an interview with this reporter. .
[CCN] In the process of upgrading oil quality in China, MTBE, etherified light gasoline and other oil-regulating components have been widely used. With the large-scale promotion of ethanol gasoline, to meet the standard of oxygen content not exceeding 0.5% by weight, the use of these components, especially MTBE, will be limited. How do you think about this problem? How should companies deal with it? Is there any way to learn from abroad?
[张勇]
MTBE is produced by reacting isobutylene component in the by-product liquefied petroleum gas from the refinery for crude oil catalytic cracking and thermal cracking. It is used as a substitute for tetraethyl lead and is an additive for clean gasoline to improve gasoline. Octane number. According to statistics, China's current MTBE production capacity is about 17 million tons, involving nearly 10 million tons of isobutylene carbon four resources (removing unusable olefins). If the New Deal is enforced, not only will MTBE production enterprises be affected, but if these carbon four resources cannot find a new way out, they will also trigger new resource and environmental problems.
However, MTBE companies do not have to be overly pessimistic and can change their minds to develop. According to the experience of the United States, some states began to develop ethyl tert-butyl ether (ETBE) after the MTBE was banned, that is, the existing MTBE plant was transformed into ETBE. ETBE is formed by the reaction of isobutylene in carbon four with ethanol. ETBE is a high-octane gasoline blending component that is superior to MTBE. It can utilize bioethanol and avoid the defects of ethanol gasoline. To take a step back, even if the country does force the promotion of ethanol gasoline by 2020, neither MTBE nor ETBE can be used as a gasoline additive component. Adding alkylated oil to gasoline can also find a new way to digest isobutylene. Alkylation oil is an important gasoline component whose constituents are isooctane-based carbon eight isoparaffins. The isooctene can be formed by the isobutylene superposition reaction, and the isooctane component can be obtained by hydrogenation.
[CCN] As a leading enterprise in the domestic resin catalyst and catalytic distillation component industry and a well-known petrochemical process technology development unit, what support can Kerry provide for the enterprise in the transformation of the carbon four industry chain?
[张勇]
In fact, the modification of the MTBE unit can be converted to ETBE or indirect alkylation. Due to the relationship between foreign export business, and often contact with foreign customers, and insight into the development of the industry, Kerry has a long-term layout in this field. We have considered and planned and developed new technologies to solve gasoline upgrades when the country introduced the ethanol gasoline policy more than a decade ago. The company developed ethyl tert-butyl ether (ETBE) technology and ethanol light gasoline etherification technology to produce ETBE and ethanol etherified light gasoline by reacting bioethanol with isobutylene and catalytic light gasoline. Ethanol light gasoline etherification can also reduce the olefin content of 3 to 5 percent in gasoline, and solve the problem of lower olefin content required by the national VI gasoline standard.
At the same time, the indirect alkylation technology we developed can well handle the problem of producing non-oxygen high-octane gasoline blending components using carbon tetraolefins, which utilizes the catalytic action of carbon tetraolefins under the action of a resin catalyst. The superposition (dimerization) reaction produces isooctene, and then the isooctene is hydrogenated to give isooctane.
Among the above technologies, the ETBE production technology has completed the operation of the 1,000-ton demonstration unit, and its catalyst has been applied to many sets of ETBE devices in Europe and the United States in the early years. The indirect alkylation production technology has been completed in the pilot test, and the isobutylene superposition technology and catalyst have been successfully industrialized. Look forward to working with interested companies.
Digesting carbon four and bioethanol to open up new roads
[CCN] What are the advantages of ETBE compared with MTBE? As you just mentioned, ETBE has been sought after in developed countries. What is the domestic technological breakthrough?
[张勇]
Compared with MTBE, ETBE only has slightly lower oxygen content, and other performance indexes are better than MTBE. Especially, its Reid vapor pressure is very low, it is more miscible with gasoline than MTBE; the solubility in water is less than 1/3 of MTBE. It has little pollution to groundwater. At present, foreign ether synthesis technology is very mature, and ETBE also realizes large-scale industrial production. Foreign companies with ETBE production technology mainly include the French Petroleum Institute (IFP), American Catalytic Distillation Technology (CDTECH), Alco Chemical Technology (ARCO), United Oil (UOP), and Phillips. . There is no industrial production equipment in domestic ETBE. Kerry Environmental has been engaged in the research of etherification technology and is in a leading position in China. In order to meet the increasing market demand and respond to the country's use of clean energy and increase the use of renewable energy sources such as biomass ethanol, we have developed ETBE synthesis process technology.
The production process of ETBE is basically the same as that of MTBE, but in the process of technology development, the purity of ETBE obtained by the same process as MTBE is much lower than that of MTBE, mainly because the azeotrope of ethanol and carbon four is lower than that of methanol. In addition, ethanol can form an azeotrope with water and ETBE. These characteristics result in the presence of ethanol in ETBE, low purity, how to recover ethanol, and improve the purity of ETBE is the key to the development of ETBE technology. After long-term research and development, Kerry has achieved technological breakthroughs and solved the problem of low purity of ETBE and difficult recovery of high-purity ethanol. Compared with similar foreign technologies, the process technology has the characteristics of simplified process flow, investment and energy consumption.
The promotion of ETBE in developed countries is the idea: it consumes both ethanol and finds the outlet end for isobutene, a carbon tetra-product of the refinery. In addition, ethanol cannot be blended into gasoline in the refinery. It can only be reconciled at the sales stage and cannot be stored for a long time. This problem is solved by using ETBE as a blending component. The practice of gaining more from one fell swoop is worth learning from.
[CCN] ETBE is also a way to consume bioethanol. If ETBE is added, what is the ratio of this addition? How much ethanol is consumed?
[张勇]
According to the current oxygen content limit of conventional gasoline, the addition amount of MTBE is generally between 10% and 12%. Because the oxygen content of ETBE is low, if it is replaced by ETBE, the added amount can be increased to 13%~15%. The ethanol content in ETBE is about 45%.
[CCN] There will be huge market space for retrofitting ETBE devices with existing MTBE devices. Does Kerry have sufficient confidence to seize this opportunity?
[张勇]
Kerry's ETBE catalyst has been exported to foreign countries and has been successfully applied in many sets of equipment. The development of ETBE production technology has also progressed. In the first half of 2012, the company has completed the ETBE pilot test of fixed bed synthesis, which mainly includes catalyst screening, process condition test and macroscopic kinetics research. In the second half of the year, based on the results of the small test, the catalytic distillation pilot test was carried out. The content mainly includes fixed-bed and catalytic distillation combined etherification 100-ton pilot scale amplification, catalytic distillation column reaction section catalyst bed flow capacity test and gasoline blending test. Our technology has matured, the catalyst has already realized the industrialization of multiple sets of equipment, and the industrialization of technology is our next step.
Indirect alkylation opportunities highlight
[CCN] According to the latest national standards, all ether compounds can not be added to ethanol gasoline, including ETBE, then the use of by-product carbon four to produce alkylated oil will be the main utilization direction of by-product carbon four. Is there any application of alkylated oil in China? What are the differences between domestic alkylation technology and technology in developed countries?
[张勇]
Making full use of carbon tetraolefin resources to produce oxygen-free high-octane gasoline blending components will be a research and development direction under the current ethanol gasoline standard. The alkylated oil is composed of isooctane-based carbon eight isoparaffins, which are free of olefins and aromatic hydrocarbons and are ideal components for increasing the octane number of gasoline. In the United States, the proportion of alkylated oil in gasoline is very large. In the domestic gasoline upgrading process in the past few years, PetroChina and Sinopec have also vigorously built alkylated oil plants.
China's refining industry is currently using large-scale direct alkylation technology. Generally, isobutane is reacted with C3-C5 olefins in the presence of a strong acid catalyst to form alkylated oil. The alkylation theory theoretically reacts the molar ratio of alkane to olefin consumption. For 1:1, the ratio of alkylene to 8-12 is controlled during the actual reaction, while the ratio of isobutane to olefin is about 1:5 in catalytic by-product carbon four. The direct alkylation technology still has a large amount of carbon four. Olefins cannot be utilized.
Indirect alkylation technology is used abroad, and indirect alkylation technology can well handle the problem of producing non-oxygen high-octane gasoline blending components by using carbon tetraolefins. More than 30 sets of indirect alkylation units, represented by UOP, CDTECH and IFP, are in operation. Due to the ban on MTBE devices in foreign countries, foreign technology tends to be slightly modified in recent years with the existing MTBE devices, producing isooctene under the action of resin catalysts, and then generating high-octane isooctane products by hydrogenation. .
Compared with direct alkylation technology, indirect alkylation has the advantages of wide raw material range, environmental friendliness, low investment and high product quality.
[CCN] What is the layout of Kerry's indirect alkylation technology?
[张勇]
Since 2008, Kerry has begun to study the solid acid alkylation, indirect alkylation technology and related catalysts for the regulation of the addition of oxygenates to ethanol gasoline. Especially in the indirect alkylation technology, great progress has been made. The modification of the existing MTBE device adopts an external circulation fixed bed to generate an isooctene intermediate product under the catalytic action of the resin catalyst. At present, the indirect alkylation production technology has completed the pilot test, and its catalyst has been used in industrial applications at home and abroad.
If the country implements ethanol gasoline by 2020 and cannot add ETBE, the existing MTBE plant will face full shutdown, and there will be a large excess of olefins, and there will be a price decline. Indirect alkylation technology can produce low-value excess olefins to produce high-octane anaerobic gasoline blending components, which will be the next development direction of carbon four utilization, and will be an opportunity for our company.