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Catalyst used for preparing propylene and ethylene by cracking and preparation method thereof

A technology of propylene ethylene and catalyst, which is applied in the field of cracking propylene ethylene catalyst and its preparation. It can solve the problems of poor propylene selectivity, poor thermal stability, and inability to meet long-term operation, and achieve long-term operation and good high-temperature hydrothermal stability. , the effect of not easy to coke and deactivate

Active Publication Date: 2013-02-20
李昕
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0011] The technical problem to be solved by the present invention is to provide a catalyst for cracking propylene and ethylene, so as to solve the problem that the existing catalysts have poor high-temperature hydrothermal stability and poor propylene selectivity in the process of cracking olefin mixed cracking raw materials to produce ethylene and propylene, and cannot meet the requirements of long-term operation. Asked technical questions

Method used

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  • Catalyst used for preparing propylene and ethylene by cracking and preparation method thereof
  • Catalyst used for preparing propylene and ethylene by cracking and preparation method thereof

Examples

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Effect test

Embodiment 1

[0043] It is 50 grams of HZSM-5 molecular sieves that the silicon-aluminum ratio produced by the commercially available Fudan University Catalyst Production Plant is 60, and 1.44 grams of Na 2 CO 3 Exchange 200ml of the solution, at 60°C, quickly stir and exchange for 1.5-2 hours, then filter the slurry, dry at 120°C for 1.5-2 hours, and after crushing, a modified HZSM-5 molecular sieve a is obtained, in which the sodium content is 0.25 %.

[0044] Examples 2-8 are HZSM-5 molecular sieve modification, the unspecified raw materials, sources and preparation process are the same as in Example 1, and the SiO of the molecular sieve is changed 2 / A1 2 o 3 The molar ratio and alkali metal content were used to obtain the modified ZSM-5 molecular sieve, listed in Table 1.

[0045] Embodiments 9 to 10 are modified HZSM-5 molecular sieves. The unspecified raw materials and preparation process are the same as in Example 1, but 200ml of sodium hydroxide solution containing 1.08 grams i...

Embodiment 11

[0049] 70 grams of the modified HZSM-5 molecular sieve obtained in Example 1 on a dry basis, 60 grams of the SAPO-34 molecular sieve produced by Tianjin Fusheng Dye Factory on a dry basis, and the content produced by Baotou Rare Earth Group Company with a total weight of 0.1% LaO is 36%, CeO 2 The content of 11% rare earth chloride for catalytic cracking is dissolved in JA-25 and SiO produced by Qingdao Ocean Chemical Co., Ltd. containing 70 grams of silica. 2 The content is 25.0% in silica sol, which are mixed together, extruded, dried at 120°C for 2 hours, and calcined at 550°C for 4 hours to obtain the catalyst. Calculated on a dry basis, it contains 35% by weight of modified ZSM-5 molecular sieve and 30% by weight of modified SAPO-34.

[0050] Examples 12-17 adopt the same preparation process as Example 11, modify the SAPO-34 molecular sieve and carrier by changing the rare earth content, and prepare catalysts, which are listed in Table 2. But the binding agent that embo...

Embodiment 18

[0054] exist figure 1 On the shown continuous flow fixed bed reaction device, load 1 ml of the catalyst prepared in Examples 11-17 and ground to 40-60 mesh. Under normal pressure, using carbon-containing four-olefin mixed hydrocarbons as raw materials, the mass space velocity is 2 h -1 , the reaction temperature was 550°C for the reaction, and the product was analyzed by online gas chromatography. Table 3 is the raw material composition of carbon tetraolefins. Table 4 shows the results of the propylene production reaction when the mixed feedstock containing carbon tetraolefins is used as the feed.

[0055] Table 3 Composition of carbon-containing tetraolefin raw materials, m%

[0056] project composition C 2 0.1 C 3 h 6 0.2 C 3 h 8 0.7 i-C 4 h 10 10 n-C 4 h 10 45 n-C 4 h 8 13 i-C 4 h 8 2 t-C 4 h 8 10 c-C 4 h 8 15 ≥C 5 + 3

[0057] Table 4 The reaction results of producin...

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Abstract

The invention relates to a catalyst used for preparing propylene and ethylene by cracking and a preparation method thereof. The catalyst comprises the components of a ZSM-5 molecular sieve with molar ratio of SiO2 to Al2O3 being 60-1000, a SAPO-34 molecular sieve loaded on the ZSM-5 molecular sieve, alkali metal loaded on the SAPO-34 molecular sieve, thulium or oxide of the thulium, and a binder which can be monox, alumina, aluminium silicate or a mixture of monox, alumina and aluminium silicate in any proportion, where the ZSM-5 molecular sieve accounts for 20-60% of the total weight, the SAPO-34 molecular sieve accounts for 5-30% of the total weight, the alkali metal accounts for 0.10-5% of the total weight, the thulium quantity calculated in terms of the thulium or the oxide thereof accounts for 0.10-5% of the total weight, and the binder accounts for 20-60% of the total weight. The catalyst disclosed in the invention is superior to traditional similar catalysts on the aspects of percent conversion, propylene yield, ethylene yield, gasoline yield, service life and the like.

Description

technical field [0001] The invention relates to a petrochemical catalyst, in particular to a catalyst for cracking propylene and ethylene and a preparation method thereof. Background technique [0002] Mixed C4 olefins are by-products of FCC units in ethylene plants and refineries, and can only be used as low value-added products such as liquefied gas fuels. It is economically and technically feasible to further process it into propylene and ethylene and make full use of this considerable amount of precious olefin resources. [0003] Chinese patent 200410024732.0 discloses a catalyst comprising the following components in weight percent: a) 40-80% silicon-aluminum molar ratio SiO 2 / A1 2 o 3 A ZSM-5 molecular sieve of 60-1000; and carried thereon. b) 0.01-5% of rare earth metal elements or their oxides; c) 25-60% of binder. In the above-mentioned technical scheme, the preferred range of the consumption of ZSM-5 molecular sieve is 50-70% by weight percentage, and th...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/85C07C4/06C07C11/02C07C11/06C10G11/05
CPCY02P20/52
Inventor 龚旭辉
Owner 李昕
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