Solid phosphoric acid catalyst and methods of olefin dimerization reaction with the same

一种烯烃二聚反应、磷酸催化剂的技术,应用在化学仪器和方法、有机化学方法、物理/化学过程催化剂等方向,达到制备简单、催化剂寿命长、活性和二聚物选择性高的效果

Inactive Publication Date: 2008-05-28
NIPPON OIL CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] However, the oligomerization of olefins using the above-mentioned existing solid phosphoric acid catalysts does not take the dimerization of olefins as the main purpose, and the existing solid phosphoric acid catalysts cannot avoid the generation of by-products such as high polymers of olefins, so it is difficult to choose Obtain dimers of alkenes
In addition, the existing solid phosphoric acid catalyst must be in the H 2 O / P 2 o 5 When it is supplied to the reaction in a small state, it is necessary to strictly control the moisture content during the preparation and storage of the catalyst so that the moisture content is below a certain level (the remaining moisture is reduced), and the drying process of the catalyst must be carried out before the reaction. all kinds of trouble

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0025] The preparation of the catalyst, that is, the loading of phosphoric acid on the carrier can be carried out by immersing the carrier in an aqueous phosphoric acid solution and then removing the remaining aqueous phosphoric acid solution. The apparatus used for the preparation of the catalyst is not particularly limited, and a general batch tank can be used. If a reactor for dimerization of olefins is used, the catalyst can be filled simultaneously with the preparation of the catalyst. The concentration of the phosphoric acid aqueous solution used for immersion is not particularly limited, and it is preferable to reduce the amount of heat reduction to a predetermined value in the state of immersion in the case of 92% by mass or less. When the concentration is higher than this, only It is not preferable to adjust the amount of reduction in heating by immersion since it is necessary to add water and make separate adjustments. The concentration of the commonly used phosphori...

Embodiment 1

[0037] 20.0 g of 0.8 to 1.7 mmφ synthetic silica granules (Cariact Q-50 manufactured by Fuji Silicone Chemicals) were immersed in 100 ml of a 42% by mass phosphoric acid aqueous solution put into a 200 ml beaker. After immersion for 1 hour, the aqueous solution was removed on a mesh filter to prepare a solid phosphoric acid catalyst A. Under the conditions of 250°C and 20 minutes, 28 mg of the obtained catalyst was subjected to thermogravimetric analysis, and as a result, the heating loss (moisture) was 12.6 mg (45.0 mass %), and the carrier and P in the catalyst 2 o 5 The proportion of the total amount was 55.0% by mass. Then, 2.00 g of the catalyst was sufficiently washed with water, dried, and the mass was measured. As a result, it was 0.71 g, and the amount of the carrier in the catalyst was 35.5% by mass. Therefore, P in the catalyst 2 o 5 The proportion of 19.5% by mass, the amount of heating reduction relative to P 2 o 5 The ratio of 230.8% by mass.

[0038] Fill...

Embodiment 2

[0040] Fill 2g solid phosphoric acid catalyst A in the tubular stainless steel reactor (inner diameter 8mm), from the top of reactor with 21.3g / h (WHSV=30h -1 ) feed feed contains the normal hexane of 50ppm water, a part of the reaction liquid that will be taken out from the lower part is combined in the feed in the form of recirculation (recirculation ratio R / F=4), pressure and temperature are adjusted to reaction initiation condition (1.0 MPa, 80°C). About 1 hour after the start of the feed, the pressure and temperature were stable under the reaction initiation conditions, so the feed was switched to an olefin-containing feedstock (30 mass % isobutene, 5 mass % n-butene, 65 mass % n-hexane, 250 mass ppm water ), the dimerization reaction was carried out continuously for 30 days. The reaction results are shown in Table 1.

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Abstract

A solid phosphoric acid catalyst which has high activity and attains high dimer selectivity in olefin dimerization reactions; and efficient methods of olefin dimerization reaction. The solid phosphoric acid catalyst comprises a support and phosphoric acid deposited thereon. When the solid phosphoric acid catalyst is heated at 250 DEG C for 20 minutes, the heating loss of water is 50 mass% or larger based on diphosphorus pentaoxide (P2O5) derived from the phosphoric acid. One of the methods of olefin dimerization reaction comprises bringing an olefin-containing feed material containing water in an amount of 10-1,000 mass ppm into contact with the catalyst to initiate the reaction. Another method of olefin dimerization reaction comprises successively conducting the following steps: a step (1) in which a hydrocarbon containing water in an amount of 10-1,000 mass ppm and containing substantially no olefin is brought into contact with the catalyst; a step (2) in which the pressure and temperature are regulated to conditions suitable for the initiation of olefin dimerization; and a step (3) in which the hydrocarbon is displaced with an olefin-containing feed material containing water in an amount of 10-1,000 mass ppm to bring the olefin into contact with the solid phosphoric acid catalyst and thereby initiate the reaction. Still another method is the olefin dimerization reaction method described above wherein the temperature in the reaction initiation conditions is higher by 5-50 DEG C than the reaction temperature in olefin dimerization in a stationary state after the step (3).

Description

technical field [0001] The invention relates to a solid phosphoric acid catalyst formed by supporting phosphoric acid on a carrier and a method for selective dimerization of olefins using it. Background technique [0002] Oligomers of olefins are used in various applications, especially dimers of low-molecular-weight olefins (such as propylene, n-butene, isobutene, and pentenes) are important as high-octane base materials for gasoline or chemical intermediate raw materials of. Oligomerization including olefin dimerization is performed using an acid catalyst, and numerous studies have been conducted so far. As the acid catalyst, solid acids such as sulfuric acid, hydrogen fluoride, phosphoric acid, aluminum chloride, boron fluoride, amorphous or crystalline aluminum silicate, clay, ion exchange resins, mixed oxides, carrier-supported acids can be cited as common examples, and Various studies have been conducted on an inexpensive solid phosphoric acid catalyst capable of a s...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/182C07C2/18C07C11/02C07B61/00
CPCB01J27/182B01J27/16C07C2/18C07C11/02C07B61/00
Inventor 滨松辰雄木村信启高岛务森北孝志
Owner NIPPON OIL CO LTD
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