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Catalyst for preparing butene/butadiene by dehydrogenation of butane and application of catalyst

A technology for butane dehydrogenation and butadiene, applied in physical/chemical process catalysts, catalyst carriers, catalyst activation/preparation, etc., can solve problems such as selectivity decline, poor single-pass stability, and low conversion rate

Pending Publication Date: 2018-01-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Chinese patent (201280062907.X) uses a zinc-manganese aluminate dehydrogenation catalyst that does not need noble metals, but the single-pass stability is poor
The U.S. patent discloses the aluminate carrier Pt catalyst (US3957688; US4041099; US5073662) that adopts the Pt catalyst (US5430220) that zinc aluminate spinel is a carrier and the auxiliary agents such as Au, Ag to promote, and catalyst all exists conversion efficiency low, in During use, the selectivity drops obviously, etc.
The above-mentioned patents are all aimed at propane and isobutane dehydrogenation catalysts, and there are few patents related to n-butane direct dehydrogenation catalysts

Method used

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  • Catalyst for preparing butene/butadiene by dehydrogenation of butane and application of catalyst
  • Catalyst for preparing butene/butadiene by dehydrogenation of butane and application of catalyst
  • Catalyst for preparing butene/butadiene by dehydrogenation of butane and application of catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Take 26.0g zirconia (ZrO 2 ), 39.2g chromium oxide (Cr 2 o 3 ), 7.0g antimony oxide (Sb 2 o 3 ), 6.0g phosphorus pentoxide (P 2 o 5) and 121.7g of alumina (Al 2 o 3 ), then add 9.0g of starch, then mix in a ball mill for 200 minutes, use a standard sieve to sieve >200 mesh powder, add about 6.5g of turnip powder, a small amount of 20% nitric acid aqueous solution and an appropriate amount of water into the kneader for kneading , extruded, dried at 120°C, and then calcined at 680°C for 10 hours to obtain a composite oxide catalyst carrier. Pore ​​volume 0.52cm 3 / g, specific surface area 86m 2 / g. The weight percent composition of the obtained catalyst carrier is shown in Table 1.

[0025] The carrier that obtains adopts impregnation technology to load active component, namely at room temperature with the carrier 15.0g impregnation containing ammonium chloroiridate (NH 4 ) 2 IrCl 6 , 0.12g) and 0.1g potassium nitrate aqueous solution (10ml) for 24 hours (me...

Embodiment 2

[0028] Take 47.0g zirconia (ZrO 2 ), 32.5g chromium oxide (Cr 2 o 3 ), 10.5g bismuth oxide (Bi 2 o 3 ), 3.6g phosphorus pentoxide (P 2 o 5 ) and 106.4g alumina (Al 2 o 3 ), then add 9.2g of starch, then mix in a ball mill for 180 minutes, use a standard sieve to sieve >200 mesh powder, add about 6.5g of turnip powder, a small amount of 25% nitric acid aqueous solution and an appropriate amount of water into the kneader for kneading , extruded, dried at 120°C, and then calcined at 680°C for 10 hours to obtain a composite oxide catalyst carrier. Pore ​​volume 0.57cm 3 / g, specific surface area 93m 2 / g. The weight percent composition of the obtained catalyst carrier is shown in Table 1.

[0029] The carrier that obtains adopts impregnation technology to load active component, namely at room temperature with the carrier 15.0g impregnation containing ammonium chloroiridate (NH 4 ) 2 IrCl 6 (0.08g), ammonium chlororuthenate (NH 4 ) 2 RuCl 6 (0.05g) and calcium nitr...

Embodiment 3

[0032] Take 25.2g zirconia (ZrO 2 ), 24.0g chromium oxide (Cr 2 o 3 ), 10.6g bismuth oxide (Bi 2 o 3 ), 5.2g cadmium oxide (CdO), 4.2g stannous oxide (SnO) and 130.8g aluminum oxide (Al 2 o 3 ), then add 8.8g of starch, then mix in a ball mill for 180 minutes, use a standard sieve to sieve >220 mesh powder, add about 7.5g of turnip powder, a small amount of 20% nitric acid aqueous solution and an appropriate amount of water in the kneader for kneading , extruded, dried at 120°C, and then calcined at 680°C for 10 hours to obtain a composite oxide catalyst carrier. Pore ​​volume 0.53cm 3 / g, specific surface area 82m 2 / g. The weight percent composition of the obtained catalyst carrier is shown in Table 1.

[0033] The carrier that obtains adopts impregnation technology to load active component, namely at room temperature with the carrier 15.0g impregnation containing ammonium chloroiridate (NH 4 ) 2 IrCl 6 (0.11g) and potassium nitrate 0.09g aqueous solution (10ml) ...

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Abstract

The invention relates to a catalyst for preparing butene / butadiene by dehydrogenation of butane and an application of the catalyst, and mainly solves the problems of low butane conversion rate, and poor single-pass stability and regeneration stability in conventional preparation technologies. According to the invention, firstly, zirconia, chromium oxide and oxides of at least one element selectedfrom a group consisting of IIIA, IVA, VA and IIB in the periodic table of elements are introduced into an aluminum oxide carrier by a dry mixing method to obtain a composite metal-oxide carrier; thenthe loading of iridium (Ir) and ruthenium (Ru) components is performed by an impregnation method, that is, water solutions of soluble salts of iridium (Ir) and ruthenium (Ru) are employed for impregnation; and the catalyst is obtained after drying and calcination. The problems are well solved with the technical scheme that n-butane is used as a raw material, under the conditions that the reactiontemperature is in a range of 530-650 DEG C, the reaction pressure is in a range of 0.1-0.4 MPa, the mass space velocity of the n-butane is in a range of 0.1-6.0 h<-1>, and the volume ratio of H<2>O toC<n>H<2n+2> is in a range of 0.1-16, the raw material contacts with the catalyst and reacts to form the butene / butadiene. The technical scheme can be used in the industrial preparation of the catalyst for preparing butene / butadiene by the dehydrogenation of n-butane.

Description

technical field [0001] The invention relates to a carrier, catalyst and use thereof for butane dehydrogenation to produce butene / butadiene. Background technique [0002] Butene / butadiene mainly comes from the co-production or by-product of steam cracking and fluid catalytic cracking in refineries, and can be widely used in the synthesis of polymers, rubber, resins, gasoline additives and various chemical intermediates. With the increasing demand for low-carbon olefins, the traditional production process is difficult to meet the rapid growth of market demand. A large amount of low-carbon alkanes obtained from refineries are the main components of liquefied petroleum gas, including a large amount of n-butane raw materials, which are mainly used as civil fuels. The development of the process of producing low-carbon alkanes from low-carbon alkanes is of great significance for the comprehensive utilization of low-carbon alkanes and the development of new sources of alkenes and d...

Claims

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Application Information

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IPC IPC(8): B01J23/26B01J23/31B01J23/652B01J27/188B01J32/00B01J35/10B01J37/02C07C5/333C07C11/08C07C11/167
Inventor 吴文海曾铁强缪长喜樊志贵
Owner CHINA PETROLEUM & CHEM CORP
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