Who in China is researching ETBE and TAME?

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I venture to post this – I was involved in the development of the entire project. However, I recommend using only TAME; it is necessary to take into account the company’s resource allocation (we can discuss this in detail). The use of isoprene is not recommended. 1. Overview Methyl tert-butyl ether (TAME) is another ideal oxygenate, following MTBE, for producing lead-free, oxygenated gasoline with high octane ratings. Although TAME has a slightly lower octane rating than MTBE, it outperforms MTBE in terms of vapor pressure and energy density, and its production can also reduce the presence of olefins in gasoline that are highly reactive in atmospheric photochemistry. Furthermore, TAME cleavage can produce isopentene, an important raw material for the fine chemical industry. The development of TAME technology abroad began in the 1980s; in 1988, the German company Erdorchemie built the world’s first TAME production facility with a capacity of 12,000 tons per year. To date, more than forty such facilities are in operation. Currently, the catalytic distillation technique for synthesizing TAME is the most advanced method; the conversion rate of tert-pentene exceeds 90%. Compared with other TAME production techniques, it offers advantages such as high conversion rates, a simple process, lower investment costs, and reduced energy consumption. TAME is formed from isoprene in the C5 fraction and methanol; among the three types of isoprene present in the C5 fraction, only 2-methyl-1-butene and 2-methyl-2-butene participate in the reaction, while 3-methyl-1-butene does not participate, although it can be converted into 2-methyl-2-butene. Currently, the C5 feedstocks used for the synthesis of TAME mainly come from the catalytic cracking (FCC) units in refineries and from pyrolysis-derived C5 fractions; the tertiary amylene content in typical extracted C5 and FCC C5 fractions is about 20% (m/m). In the early 1990s, China developed catalytic cracking process technologies for producing large amounts of low-carbon olefins or isomeric olefins, namely the DCC process and the MIO process. The tert-pentene content in the C5 fraction produced by these two processes is 40%–55% (m/m). At present, there are only four TAME manufacturers in our country, all with a production capacity of around 15,000 tons each, and they are all used for the production of isoprene. 2. Technical Overview: Terpineol in the carbon pentane fraction (including 2-methyl-1-butene and 2-methyl-2-butene) reacts with methanol in the presence of macroporous sulfonic acid resin catalysts to produce TAME; this reaction is a reversible exothermic reaction. In the etherification reaction, side reactions such as the hydration of tert-pentene, methanol condensation, and tert-pentene polymerization also occur. However, as long as operating conditions such as temperature and the alcohol-to-olefin ratio are properly controlled, these side reactions can be ignored, allowing the reaction selectivity to exceed 98%. The TAME production process includes units such as raw material purification, etherification, and methanol recovery. Raw material purification employs washing and selective hydrogenation techniques; washing removes metal ions and basic nitrogen compounds from the C5 fraction, while selective hydrogenation eliminates dienes from the same fraction. Raw material purification helps to extend the service life of the etherification catalyst. The etherification reaction employs a process that combines pre-etherification with catalytic distillation. The use of catalytic distillation disrupts the equilibrium of the etherification reaction, enabling high conversion rates of tert-pentene ； At the same time, the reaction heat is used for product separation, reducing energy consumption. The methanol recovery unit employs washing and methanol distillation processes to recover unreacted methanol. 3. Key process technical parameters: l Metal ions and basic nitrogen compounds in the purified C5 fraction are ≤1 ppm, with dienes at ≤300 ppm. l The total conversion rate of tert-pentene is ≥90%, the selectivity for TAME is ≥98%, and the purity of the TAME product is ≥98%. l The TAME production technology is used for gasoline upgrading; for FCC gasoline, it increases the octane rating by about 1.0 unit and reduces the olefin content by about 6 mass percentage points ； For DCC gasoline, the octane rating increases by about 2.0 units, while the olefin content decreases by approximately 18 mass percentage points. 4. Scope of services: Optimized process technologies can be provided based on the customer’s resources and development needs, thereby enhancing the competitiveness of the products in the market ； According to customer requirements, supporting options such as hydrogenation catalysts, etherification catalysts, and catalyst packages can be provided ； It can provide a complete process software package that fully meets the requirements specified in the 2003 version of \"Process Design Package for Petrochemical Plants (Comprehensive Technical Process Package)\" ； I can provide feasibility study reports and engineering designs for projects.

Dear teacher, ETBE seems to be quite popular abroad, but given China’s national conditions, its cost is likely higher than that of MTBE. The performance of TAME appears to be slightly inferior. Do you have any information comparing ETBE, TAME, and MTBE?

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Properties: MTBE, ETBE, TAME; Mixed Octane Number (R+M/2): 110, 111, 105; RON: 112–130, 120, 105–115; MON: 97–115, 102, 95–105; Raoult’s Vapor Pressure in psi: 7.8, 4.0, 2.5; Boiling Point: 55, 72, 88; Density, g/ml: 0.742, 0.743, 0.788; Heat of Combustion, kcal/L: 89.3, 92.5, 98.0; Heat of Vaporization, kcal/L: 0.82, 0.79, 0.86; Oxygen Requirement (2.7% V): 15.0, 17.2, 16.7; Solubility, wt%: 4.3, 1.2, 1.2; Water Absorption, %wt: 1.4, 0.5, 0.6; Heat of Reaction, kcal/mol: 9.4, 6.6, 11. More details are provided below.

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Could that person tell me which are the few companies in the domestic market? Thank you!

This is a post by an expert; I’m just here to reply to it

Hello, teacher! Thank you very much for the information you provided. I also have a question: the United States is currently using octane to replace MTBE. Do you have any knowledge on this topic? Also, where in China does the technical expertise for the production of TAME and ETBE exist? Or which research institutes are conducting research?

It has potential; with more effort, the MTBE process will be replaced