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Ni-based solid acid catalyst for preparing C6 olefin through propylene dimerization as well as preparation method and application of Ni-based solid acid catalyst

A solid acid catalyst and solid acid technology are applied in the preparation of carbon hexaolefins, the preparation of nickel-based solid acid catalysts, and the field of nickel-based solid acid catalysts, which can solve the problems of complicated catalyst synthesis steps, complex synthesis process, poor dimerization selectivity, etc. problems, to maintain the conversion rate and product selectivity, the process is simple, and the effect of improving the conversion rate and

Pending Publication Date: 2022-02-18
CHINA PETROLEUM & CHEM CORP +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] In order to solve the above problems, Chinese patent application CN110002936A discloses a method for dimerizing propylene into 2,3-dimethyl-1-butene. The catalyst uses organophosphorus ligands, but the system is complicated, the synthesis is difficult, and the environment is polluted.
[0005] Chinese patent application CN106565404A discloses a method for dimerization of propylene with high activity and selectivity. The cocatalyst methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) reacts with water in air, and the catalyst synthesis step cumbersome and unfriendly to the environment
[0006] Chinese patent application CN108246342A discloses a method for in-situ synthesis of a nickel-based propylene oligomerization molecular sieve catalyst, the synthesis process is complicated, and the dimerization selectivity is poor

Method used

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  • Ni-based solid acid catalyst for preparing C6 olefin through propylene dimerization as well as preparation method and application of Ni-based solid acid catalyst
  • Ni-based solid acid catalyst for preparing C6 olefin through propylene dimerization as well as preparation method and application of Ni-based solid acid catalyst

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Experimental program
Comparison scheme
Effect test

Embodiment approach

[0019] According to a most preferred embodiment of the present invention, the solid acid carrier is niobic acid. In this preferred embodiment, the catalyst can realize high-efficiency conversion of raw materials, and the product selectivity and yield are high.

[0020] According to the present invention, the heteropolyacid is specifically defined in the art. Specifically, the heteropolyacid is composed of heteroatoms (such as P, Si, Fe, Co, etc.) and polyatoms (such as Mo, W, V, Nb, Ta, etc.) is a class of oxygen-containing polyacids composed of oxygen atom coordination bridges according to a certain structure. In order to further improve the catalytic performance of the catalyst of the present invention, the heteropolyacid is selected from at least one of silicotungstic acid, phosphotungstic acid, silicomolybdic acid and phosphomolybdic acid, more preferably silicotungstic acid, silicomolybdic acid and phosphorus At least one of molybdic acid, more preferably phosphomolybdic...

Embodiment 1

[0050] NiSO used to illustrate different nickel sulfate loadings 4 / Nb 2 o 5 Catalyst preparation and its performance

[0051] (1) Nickel sulfate hexahydrate (NiSO 4 ·6H 2 O) The solid is placed in deionized water, fully stirred to make it dissolve to obtain NiSO 4 solution.

[0052] (2) The NiSO obtained in step (1) was subjected to the excess volume impregnation method 4 solution and carrier niobic acid (Nb 2 o 5 ·nH 2 O) Mix evenly and stir at room temperature for 12h (stirring speed 600rpm). The solvent water was evaporated under vacuum condition, and then the obtained solid was dried in an oven at 120° C. for 12 h.

[0053] (3) By roasting the dried solid in step (2) at 400°C in dry air, NiSO 4 / Nb 2 o 5 catalyst. Wherein, based on the total dry weight of the nickel-based solid acid catalyst, the loadings of nickel are respectively 3 wt%, 6 wt%, 9 wt%, 12 wt% and 15 wt% in terms of simple substance.

[0054] (4) each catalyzer of step (3) is packed in the c...

Embodiment 2

[0059] Used to illustrate the preparation and performance of Ni-based catalysts supported on different supports

[0060] Carry out the preparation of the catalyst and the dimerization of propylene according to the steps of catalyst preparation in Example 1, the difference is that the catalysts supported by different solid acid carriers are prepared, and the carriers are respectively Nb 2 o 5 ·nH 2 O (niobic acid), P 2 o 5 ·nH 2 O (solid phosphoric acid), H 3 PW 12 o 40 / SiO 2 (phosphotungstic acid), H 4 SiW 12 o 40 / SiO 2 (silicotungstic acid), H 3 PMo 12 o 40 / SiO 2 (phosphomolybdic acid) and H 4 SiMo 12 o 40 / SiO 2 (silicomomolybdic acid), and in terms of simple substance, the nickel loading of each catalyst is 9% by weight, and the calcination temperature is 400°C.

[0061] The conversion rate of propylene, dimerization selectivity and dimerization yield are shown in Table 2.

[0062] Table 2

[0063] catalyst Nickel loading (wt%) Conversi...

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PUM

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Abstract

The invention relates to the field of catalysts, in particular to a Ni-based solid acid catalyst for preparing C6 olefin through propylene dimerization as well as a preparation method and application of the Ni-based solid acid catalyst. The catalyst is composed of a solid acid carrier and an active metal component nickel loaded on the solid acid carrier. The catalyst provided by the invention takes solid acid as a carrier to load the metal active component Ni, catalyzes oligomerization of high-pressure liquid propylene in a fixed-bed reactor, and has the advantages of mild reaction conditions, environmental friendliness, high C6 olefin yield and good stability.

Description

technical field [0001] The invention relates to the field of catalysts, in particular to a Ni-based solid acid catalyst for the dimerization of propylene to carbon hexaolefins, a method for preparing a nickel-based solid acid catalyst, the nickel-based solid acid catalyst prepared by the preparation method, the nickel The application of the based solid acid catalyst in olefin polymerization reaction, and a preparation method of carbohexaolefin. Background technique [0002] Propylene dimerization can obtain carbon hexaolefins with different structures, and its various isomers are important fine chemical raw materials and intermediates, which are widely used. For example, 1-hexene and 4-methyl-1-pentene are new Thermoplastic resin material (comonomer of linear low density polyethylene (LLDPE), wherein 4-methyl-1-pentene can also be polymerized to obtain poly-4-methyl-1-pentene (TPX). In addition, 2, 3-Dimethyl-2-butene is an important pesticide and fragrance intermediate, ma...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/053B01J23/755B01J23/20B01J27/16B01J27/188B01J27/19B01J23/28B01J37/02B01J37/08C07C2/18C07C2/16C07C2/14C07C11/107
CPCB01J27/053B01J23/755B01J23/20B01J27/16B01J27/188B01J27/19B01J23/28B01J23/002B01J37/0201B01J37/088C07C2/18C07C2/16C07C2/14C07C2527/053C07C2523/755C07C2523/20C07C2527/16C07C2527/188C07C2527/19C07C2523/28C07C11/107Y02P20/52
Inventor 黄朝晖梁长海凌雨陈霄陈平李闯仝洪凯李中丹
Owner CHINA PETROLEUM & CHEM CORP
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