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TAME catalyst
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In the past 30 years, the macroporous strong acid ion exchange resin represented by MTBE synthesis at home and abroad has been widely used in industry as a catalyst in the etherification field due to its unique pore structure and excellent catalytic performance. MTBE catalyst is also under continuous development and improvement. With the passage of industrial application time, the resin catalyst will be inactivated or poisoned for various reasons, resulting in the reduction of isobutene conversion and shortened service life. Production managers, especially manufacturers, should have sufficient knowledge to correctly select catalysts and take corresponding effective measures.
1. Characteristics and development of macroporous strong acid resin catalyst
1. Characteristics of resin catalyst
The catalysts used in the synthesis of MTBE at home and abroad are basically macroporous strong acidic cation exchange resins. This kind of resin catalyst is a polymer with macroporous network structure formed by styrene and divinylbenzene under the action of an appropriate amount of porogen, and then sulfonated with sulfonic group. Polystyrene is the skeleton, divinylbenzene is the cross-link, and the sulfonic group on the benzene ring is the active center for catalysis. Businessmen usually supply in the form of hydrogen. The physical and chemical properties of the catalyst mainly include the following aspects:
(1) Water content - The resin usually contains about 50% water, which can provide air-dried products with low water content and is convenient to use.
(2) Volume exchange capacity - milligram equivalent number of hydrogen ions per milliliter of dry resin. The exchange capacity of catalyst is an important factor to determine its catalytic activity, so it is one of the key indicators of catalyst product specification.
(3) Pore structure characteristics - mainly pore volume, specific surface area and average pore size. Numerous network channels of catalyst are channels for reactants to reach the active center. High pore volume and large specific surface area are conducive to etherification reaction, and proper pore size is also conducive to reaction and prevention of blocking of dimerization by-products.
2. Improvement and development of resin catalyst
Since the 1980s, macroporous strong acid ion exchange resin catalysts have been widely used in MTBE synthesis. The A-15 resin catalyst (A-15 exchange capacity ≥ 4.7mmol/g) produced by Pwrolite Company is one of them. In the middle and late 1990s, A-35 produced by the company was applied in MTBE devices in some European and American countries. Under the same conditions, compared with A-15, the conversion of isobutene can be increased by 2% - 5%, and the liquid space velocity can be increased by more than 10%. The main reason is that A-35 has higher exchange capacity than A-15 (exchange capacity of A-35 ≥ 5.2mmol/g), that is, A-35 has higher catalytic activity than A-15. In the early 1990s, the exchange capacity of domestic catalysts reached 4.7mmol/g like A-15, and 5.2mmol/g like A-35 in the 1990s. However, the service life of the same exchange capacity is quite different. For example, after the localization of several imported equipment, it is obvious that the service life of Z is only half of that of the imported equipment. It can be seen that the pore structure has a great impact on the service life, so the current development direction of catalysts is to develop in the direction of appropriate pore size, appropriate pore volume and larger specific surface area.
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