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Method for catalyzing selective hydrogenation of 1, 3-butadiene by using NiPdRu catalyst

A catalyst and butadiene technology, applied in the direction of catalyst activation/preparation, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of difficult separation, reduce the catalytic effect of sulfuric acid, etc., and achieve the effect of improving catalytic activity

Inactive Publication Date: 2019-12-13
ANHUI UNIVERSITY OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] As the demand for isooctane increases, it is of great significance to carry out energy saving and consumption reduction of isooctane synthesis technology. At present, the alkylation feedstock contains a small amount of 1,3-butadiene, and this part of 1,3-butadiene is not used. Completely removed, it will react with the catalyst sulfuric acid to form a by-product that is difficult to separate, and at the same time reduce the catalytic effect of sulfuric acid as a catalyst. Therefore, the selective hydrogenation of 1,3-butadiene is of great significance for the synthesis of isooctane

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Catalyst preparation process

[0026] Weigh 1mmol Ti 3 AlC 2 Placed in 25wt% HF solution for 4.5 hours, washed with water and freeze-dried to obtain Ti 3 C 2 ; Add 1mmol Ti 3 C 2 Put 7mmol melamine in 40mL deionized water, ultrasonically disperse for a period of time, place it at a certain temperature and stir until dry, and the drying temperature is 85°C to obtain Ti 3 C 2 @melamine; Will Ti 3 C 2 @Melamine is placed in a tube furnace, roasted at 520°C for 3.5h under 5% oxygen / nitrogen atmosphere, and TiO is obtained after roasting 2 @C / g-C 3 N 4 ; Weigh 14mmol TiO 2 @C / g-C 3 N 4, placed in a solution containing 1mmol of nickel nitrate, 0.2mmol of palladium chloride and 0.01mmol of ruthenium chloride, and reduced with 0.1mol / L hydrazine hydrate solution at 3°C ​​for 8.5h to obtain a catalyst, denoted as NiPd 0.2 Ru 0.01 / 14TiO 2 @C / g-C 3 N 4 Catalyst, sealed and stored.

[0027] Hydrogenation process

[0028] First, 1.5 mL of the prepared catalyst w...

Embodiment 2

[0031] Catalyst preparation process

[0032] Weigh 1mmol Ti 3 AlC 2 Placed in 60wt% HF solution for 8.5 hours, washed with water and freeze-dried to obtain Ti 3 C 2 ; Add 1mmol Ti 3 C 2 and 15mmol melamine were placed in 40mL deionized water, ultrasonically dispersed for a period of time, placed at a certain temperature and stirred until dry, and the drying temperature was 120°C to obtain Ti 3 C 2 @melamine; Will Ti 3 C 2 @Melamine is placed in a tube furnace and roasted at 560°C for 7.5 hours under 1% oxygen / nitrogen atmosphere, and TiO is obtained after roasting 2 @C / g-C 3 N 4 ; Weigh 21mmolTiO 2 @C / g-C 3 N 4 , placed in a solution containing 1mmol nickel nitrate, 0.5mmol palladium chloride and 0.04mmol ruthenium chloride, and reduced with 0.4mol / L hydrazine hydrate solution at 9°C for 4.0h to obtain a catalyst, which is recorded as NiPd 0.5 Ru 0.04 / 21TiO 2 @C / g-C 3 N 4 Catalyst, sealed and stored.

[0033] Hydrogenation process

[0034] Firstly, 1.5 mL ...

Embodiment 3

[0037] Catalyst preparation process

[0038] Weigh 1mmol Ti 3 AlC 2 Placed in 50wt% HF solution for 7.5 hours, washed with water and freeze-dried to obtain Ti 3 C 2 ; Add 1mmol Ti 3 C 2 Put 13mmol melamine in 40mL deionized water, ultrasonically disperse for a period of time, place it at a certain temperature and stir until dry, and the drying temperature is 110°C to obtain Ti 3 C 2 @melamine; Will Ti 3 C 2 @Melamine is placed in a tube furnace, roasted at 550°C for 6.5h under 3% oxygen / nitrogen atmosphere, and TiO can be obtained after roasting 2 @C / g-C 3 N 4 ; Weigh 19mmolTiO 2 @C / g-C 3 N 4 , placed in a solution containing 1mmol nickel nitrate, 0.4mmol palladium chloride and 0.03mmol ruthenium chloride, and reduced with 0.3mol / L hydrazine hydrate solution at 8°C for 5.0h to obtain a catalyst, which is recorded as NiPd 0.4 Ru 0.03 / 19TiO 2 @C / g-C 3 N 4 Catalyst, sealed and stored.

[0039] Hydrogenation process

[0040] First, 1.5 mL of the prepared catal...

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Abstract

The invention discloses a method for catalyzing selective hydrogenation of 1, 3-butadiene by using a NiPdRu catalyst, and belongs to the technical field of chemistry and chemical engineering. The method comprises the following steps: putting the NiPdRu catalyst into a tubular reactor, heating a catalyst bed to a certain temperature, introducing a mixed gas of the 1, 3-butadiene and hydrogen into the reactor, and carrying out a reaction at a certain pressure and airspeed. Different from the traditional supported catalyst, the high-activity and high-stability supported NiPdRu catalyst for selective hydrogenation of the 1, 3-butadiene can be prepared by adjusting the contents of metal nickel, palladium and ruthenium and the content of TiO2@C in the catalyst according to the invention. When the catalyst is used for selective hydrogenation reaction of the 1, 3-butadiene, the content of the 1, 3-butadiene in the product is lower than 595ppb, the content of butane is lower than 1.2%, and thecatalyst still keeps good catalytic activity after continuous operation for 150h.

Description

technical field [0001] The invention belongs to the technical field of chemistry and chemical engineering, in particular to the use of NiPdRu / TiO 2 @C / g-C 3 N 4 The catalyst catalyzes a process for the selective hydrogenation of 1,3-butadiene. Background technique [0002] As the country vigorously promotes clean fuel technology and the large-scale application of the national "VI" standard, isooctane as a clean fuel additive has received more and more attention. At present, isooctane is mainly produced by the alkylation reaction of by-product C4 resources such as refineries. At present, the more mature technologies include HF catalytic alkylation and sulfuric acid catalytic alkylation. There are many alkylation technologies in my country. Sulfuric acid is used as a catalyst for alkylation to synthesize isooctane. [0003] As the demand for isooctane increases, it is of great significance to carry out energy saving and consumption reduction of isooctane synthesis technolog...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/24B01J37/02B01J37/16B01J37/06B01J37/08B01J37/34C07C7/163C07C9/16
CPCB01J27/24B01J37/0201B01J37/06B01J37/082B01J37/16B01J37/343C07C7/163C07C9/16
Inventor 万超吴胜华王嘉佩孙林许立信张代林
Owner ANHUI UNIVERSITY OF TECHNOLOGY
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