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

A SAPO-11, 1. SAPO-11 technology, which is applied in the field of preparation of silicoaluminophosphate molecular sieves and related catalysts, and can solve problems such as being difficult to repeat, not explaining, and limiting isomerization of single-branched chain isomers.

Active Publication Date: 2010-09-29
CHINA UNIV OF PETROLEUM (BEIJING)
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  • Abstract
  • Description
  • Claims
  • Application Information

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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

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Example 1. Synthesis of SAPO-11 molecular sieve

[0032] Mix 41.5g of deionized water and 14g of phosphoric acid (AR, 85%, Beijing Chemical Plant) in a 35°C water bath, and then add 9g of pseudo-boehmite (water content 27%, Changling Refining and Chemical 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 For 120 minutes, slowly add 7.9 g of the template 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 reaction kettle lined with polytetrafluoroethylene and crystallized at 185°C for 24 hours. The solid product obtained was taken out, cooled, filtered, and washed with deionized water to a neutral temperature. Dry it at ℃ and calcine a...

Embodiment 2

[0036] Example 2. Synthesis of SAPO-11 molecular sieve

[0037] Mix 65.2g of deionized water and 22.7g of phosphoric acid in a 35℃ water bath, then add 15g of pseudo-boehmite, stir for 90 minutes, add 10.3g of butyl orthosilicate (AR, 97%, Sinopharm Chemical Reagent Co., Ltd. ) And 23.2g of n-butanol (AR, 99%, Sinopharm Chemical Reagent Co., Ltd.) mixed solution, continue to stir for 120 minutes, then slowly add 12.7g template di-n-propylamine, continue to stir until a uniform colloid is formed, and the initial Gel mixture.

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

Embodiment 3

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

[0045] The operation of the synthesis process is the same as in Example 1, but 7.9g of di-n-propylamine is changed to a mixed solution of 7.1g of di-n-propylamine and 1.0g of di-n-butylamine (AR, 99%, Beijing Chemical Reagent Company), and the remaining components and The operation is unchanged, and SAPO-11 molecular sieve is obtained. Its X-ray diffraction pattern is as figure 1 As shown in d, the 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 silicoaluminophosphate molecular sieve and related catalysts, in particular to a preparation method of SAPO-11 molecular sieve with large aperture and SAPO-11 molecular sieve-based catalyst. Background technique [0002] The isomerization of alkanes is an important reaction in petrochemical industry. The isomerization of linear alkanes into branched alkanes has a wide range of applications in improving the octane number of gasoline. However, in the isomerization process of straight-chain alkanes, because single-branched isomers are unfavorable for obtaining high octane number, how to make straight-chain alkanes double-branched or even multi-branched isomers is important for improving FCC The octane rating of gasoline is particularly important. [0003] The early alkane isomerization catalysts were liquid acid catalysts. Although this type of catalyst has high isomerization activity, its selectivity is poor, th...

Claims

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Application Information

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Patent Type & Authority Patents(China)
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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