Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst

A technology of SAPO-11 and molecular sieve, which is applied in the direction of molecular sieve catalysts, chemical instruments and methods, molecular sieves and base-exchanged phosphate, etc., can solve the problems of reducing catalytic performance, not easy to repeat, and limiting isomerization of single branched chain isomers

Active Publication Date: 2009-08-12
CHINA UNIV OF PETROLEUM (BEIJING)
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Problems solved by technology

[0006] Chinese patent CN02116279.4 (CN1448336A) discloses a synthesis method of a silicoaluminophosphate molecular sieve with an AFO structure, especially SAPO-41, the key of which is the control of the process of roasting and removing the template agent, and the obtained molecular sieve is loaded with noble metal Pt or Pd When used as a hydroisomerization reaction in the future, compared with the catalyst prepared by the molecular sieve obtained in the prior art, its isomerization selectivity and isomerization product yield are obviously improved, but for the catalyst double branched chain isomerization selectivity Sex issues are also not explained in the patent
The problem with these conventional synthetic methods is that the process of synthesizing SAPO-11 is not easy to repeat, or it is easy to form more Si regions and reduce the catalytic performance, which is not conducive to application.
[0009] Chinese patent 02136301.3 (notification number CN1155519C) discloses a method for synthesizing SAPO-11 molecular sieves in view of the shortcomings of conventional hydrothermal synthesis that are not easy to repeat
The SAPO-11 molecular sieve with conventional pore structure can be prepared as described in the above patents, but when it is applied to alkane hydroisomerization, most of the obtained isomers are single-branched isomers. The reason is mainly that conventional SAPO-11 The pore size of 11 molecular sieves is comparable to the size of the single branched chain isomer, and the size of the pore size limits the further isomerization of the single branched chain isomer

Method used

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  • Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst
  • Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst
  • Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst

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Embodiment 1

[0031] Embodiment 1.SAPO-11 molecular sieve synthesis

[0032] 41.5g deionized water and 14g phosphoric acid (AR, 85%, Beijing Chemical Plant) are mixed in 35 ℃ of water baths, then add 9g pseudo-boehmite (water content 27%, Changling Refinery and Chemical General Plant Catalyst Plant), Stir for 90 minutes, add a mixed solution of 5.2g propyl orthosilicate (AR, 97%, Shanghai Jingchun Reagent Co., Ltd.) and 11.7g n-propanol (AR, 99%, Shanghai Jingchun Reagent Co., Ltd.), and continue stirring After 120 minutes, slowly add 7.9 g of template agent di-n-propylamine (AR, 99%, Beijing Chemical Reagent Company), and continue stirring until a uniform colloid is formed to obtain an initial gel mixture.

[0033] The initial gel mixture was put into a stainless steel reactor with a polytetrafluoroethylene liner, crystallized at 185°C for 24 hours, and the obtained solid product was taken out, cooled, filtered, and washed with deionized water until neutral at 120°C. °C drying, and roasti...

Embodiment 2

[0036] Embodiment 2.SAPO-11 molecular sieve synthesis

[0037] Mix 65.2g of deionized water and 22.7g of phosphoric acid in a 35°C water bath, add 15g of pseudoboehmite, stir for 90 minutes, add 10.3g of orthobutyl silicate (AR, 97%, Sinopharm Group Chemical Reagent Co., Ltd. ) and 23.2g n-butanol (AR, 99%, Sinopharm Group Chemical Reagent Co., Ltd.), continue to stir for 120 minutes, then slowly add template agent di-n-propylamine 12.7g, continue to stir until forming a uniform colloid, and obtain the initial Gel mixture.

[0038] The initial gel mixture was put into a stainless steel reaction kettle with polytetrafluoroethylene lining, sealed and heated to 185°C for constant temperature crystallization for 24 hours, taken out, cooled, filtered, washed with deionized water until neutral, and then baked at 120°C dry, and calcined at 600°C for 5 hours to obtain SAPO-11 molecular sieve, whose X-ray diffraction pattern is as follows: figure 1 As shown in c, the pore structure p...

Embodiment 3

[0044] Embodiment 3.SAPO-11 molecular sieve synthesis

[0045] The operation of the synthetic process is the same as in Example 1, but 7.9g di-n-propylamine is changed into the mixed solution of 7.1g di-n-propylamine and 1.0g di-n-butylamine (AR, 99%, Beijing Chemical Reagent Company), all the other components and Operation is all the same, obtain SAPO-11 molecular sieve, its X-ray diffraction pattern is as follows figure 1 As shown in d, its pore structure parameters are shown in Table 2.

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Abstract

The invention provides a method for preparing a large-aperture SAPO-11 molecular sieve, which comprises the following steps: adding an alcoholic solvent corresponding to an organic silicon source in a colloid admixture for crystallization and particularly adopting an admixture of dinpropylamine and long chain organic amine as a composite template agent simultaneously, thereby obtaining the large-aperture SAPO-11 molecular sieve through restraining the hydrolyzation of the organic silicon source and adjusting the molecule dimension of the template agent; and the large-aperture SAPO-11 molecular sieve can be used for the isomerization of a double-branch chain of hydrocarbons by a load active component. The invention further provides a preparation method for a catalyst adopting the obtained large-aperture SAPO-11 molecular sieve as a carrier; platinum family noble metals are loaded by using the SAPO-11 molecular sieve; and the prepared catalyst is used in the method for catalyzing the hydroisomerization reaction of matters of hydrocarbons; and meanwhile, the yield of isomers and the selectivity of the double-branch chain in a reaction product are improved.

Description

technical field [0001] The invention relates to a preparation method of a silicoaluminophosphate molecular sieve and a related catalyst, in particular to a preparation method of a SAPO-11 molecular sieve with a large aperture and a SAPO-11 molecular sieve-based catalyst. Background technique [0002] The isomerization of alkanes is an important reaction in petrochemical industry. The isomerization of straight-chain alkanes into branched-chain alkanes is widely used in improving the octane number of gasoline. However, in the process of isomerization of straight-chain alkanes, since single-chain isomers are unfavorable for obtaining high octane numbers, how to make double-branched isomerization or even multi-branch isomerization of straight-chain alkanes is crucial to improving FCC The octane rating of gasoline is especially important. [0003] Early alkane isomerization catalysts were liquid acid catalysts. Although this type of catalyst has high isomerization activity, it h...

Claims

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Application Information

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IPC IPC(8): C01B37/08C01B39/54B01J29/85C07C5/27
Inventor 范煜鲍晓军郭琳石冈刘海燕
Owner CHINA UNIV OF PETROLEUM (BEIJING)
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