Composite oxide carrier with bimodal mesopores, as well as preparation method and application of composite oxide carrier

A technology of composite oxides and oxides, which is applied in the direction of catalyst carriers, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc., which can solve the problem that the carrier’s mechanical strength and long-term running stability need to be improved, and the carrier Structural stability is not obvious, it is not easy to scale up industrial production, etc., to achieve good low-temperature catalytic activity and long-term running stability, good long-term running stability, and suitable for scale-up of industrial production

Active Publication Date: 2016-06-01
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Judging from the disclosed carrier patents suitable for preparing methanation catalysts by impregnation, the following problems still need to be improved: (1) γ-Al 2 o 3 The carriers need to be prepared by cumbersome methods, which are not easy for industrial scale-up production; (2) the catalytic promoters need to be impregnated into the prepared γ-Al once or more times. 2 o 3 On the carrier, the structural stabilizing effect on the carrier is not obvious; (3) The mechanical strength and long-term running stability of the carrier need to be improved

Method used

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  • Composite oxide carrier with bimodal mesopores, as well as preparation method and application of composite oxide carrier
  • Composite oxide carrier with bimodal mesopores, as well as preparation method and application of composite oxide carrier

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] (1-1) Weigh the Al of 100 mesh sieves 2 o 3 ·3H 2 O powder 6.5g, Al 2 o 3 ·H 2 O powder 13.0g, γ-Al 2 o 3 Powder 47.5g, ZrO 2 Mix 10.0 g of powder, 0.75 g of hydroxypropyl cellulose and 0.75 g of 425 cement in a dry mixer for 60 minutes to obtain mixed powder A for use.

[0048] (1-2) Weigh La(NO 3 ) 3 ·6H 2 O4.0g was dissolved in deionized water, and the volume was adjusted to 40ml, which was marked as solution B.

[0049] (1-3) Move the mixed powder A in step (1-1) into the wet mixer, and continuously spray the solution B obtained in step (1-2) into the mixed powder in the form of mist while the material powder is rotating. On the surface of powder A, after spraying all the mixed liquid B, continue wet mixing for 60 minutes to obtain mixed wet material C.

[0050] (1-4) Granulate the mixed wet material C obtained in step (1-3), dry at 120°C for 6 hours, and use a tablet machine to make cylindrical granules of Φ3×5mm after cooling.

[0051] (1-5) The molde...

Embodiment 2

[0055] (2-1) Weigh the Al of 100 mesh sieves 2 o 3 ·3H 2 O powder 12.3g, Al 2 o 3 ·H 2 O powder 8.0g, γ-Al 2 o 3 Mix 20.3g of powder, 1.0g of hydroxypropyl cellulose and 1.0g of 425 cement in a dry mixer for 60 minutes to obtain mixed powder A for later use.

[0056] (2-2) Weigh La(NO 3 ) 3 ·6H 2 O20.0g and Co(NO 3 ) 2 ·6H 2 O32.0g was dissolved in deionized water, and the volume was adjusted to 60ml, which was marked as solution B.

[0057] (2-3) Move the mixed powder A in the step (2-1) into the wet mixer, and continuously spray the solution B obtained in the step (2-2) into the mixing machine in the form of mist while the material powder is rotating. On the surface of powder A, after spraying all the mixed liquid B, continue wet mixing for 60 minutes to obtain mixed wet material C.

[0058] (2-4) The mixed wet material C obtained in the step (2-3) is made into Φ3×5mm cylindrical particles with an extruder.

[0059] (2-5) Dry the molded carrier at 120°C for 6 ...

Embodiment 3

[0063] (3-1) Weigh the Al of 100 mesh sieves 2 o 3 ·3H 2 O powder 10.2g, Al 2 o 3 ·H 2 O powder 7.6g, γ-Al 2 o 3 Mix 12.0g of powder, 1.0g of turnip powder and 0.5g of 425 cement in a dry mixer for 40 minutes to obtain mixed powder A for later use.

[0064] (3-2) Weigh Zr(NO 3 ) 4 ·3H 2 O40.0g and Co(NO 3 ) 2 ·6H 2 O16.7g was dissolved in deionized water, and the volume was adjusted to 60ml, which was marked as solution B.

[0065] (3-3) Move the mixed powder A in the step (3-1) into the wet mixer, and continuously spray the solution B obtained in the step (3-2) into the mixing machine in the form of a mist while the material powder is rotating. On the surface of powder A, after spraying all the mixed liquid B, continue wet mixing for 60 minutes to obtain mixed wet material C.

[0066] (3-4) The mixed wet material C obtained in the step (3-3) is made into Φ3×5mm cylindrical particles with an extruder.

[0067] (3-5) Dry the molded carrier at 120°C for 6 hours, h...

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Abstract

The invention discloses a composite oxide carrier with bimodal mesopores as well as a preparation method and application of the composite oxide carrier. An oxide carrier is used for an immersion type CO2 methanation catalyst, and comprises a basic carrier gamma-Al2O3 and structure stabilizing additives. A composite oxide carrier comprises a mixture of gamma-Al2O3, pseudo bohemite (Al2O3.H2O) and gibbsite (Al2O3.3H2O). The composite oxide carrier is prepared by adding the structure stabilizing additives such as alkaline-earth metal, transition metal, rare-earth metal and the like, a pore former and a binder in a process including impregnation, mixing, granulation, forming and calcination. The composite oxide carrier provided by the invention has relatively large specific surface area and a bimodal distributed mesoporous structure, and has the advantages of high carrier water absorption rate, stable structure and good mechanical strength; the preparation process facilitates enlarged production. A supported Ni-based CO2 methanation catalyst prepared by adopting the carrier disclosed by the invention has relatively good low-temperature catalysis activity and long-time operation stability.

Description

technical field [0001] The invention relates to a synthetic gas methanation catalyst carrier, in particular to a bimodal mesoporous composite oxide carrier and its preparation method and application. Background technique [0002] From coal to synthesis gas (CO+H 2 ) methanation process to substitute natural gas (Substitute Natural Gas, SNG) is an important development direction of modern coal chemical technology, and it is also one of the important ways of efficient and clean utilization of coal. The main reactions in the process of producing SNG from syngas through methanation reaction are as follows: [0003] CO+3H 2 →CH 4 +H 2 O△H 0 =-206kJ / mol(1) [0004] 2CO+2H 2 →CH 4 +CO 2 ΔH 0 =-247kJ / mol(2) [0005] CO 2 +4H 2 →CH 4 +2H 2 O△H 0 =-165kJ / mol(3) [0006] Reactions (1) and (2) are the main reactions and core processes in the syngas methanation system, called bulk methanation (Bulk Methanation). Since the CO content in the reaction gas is relatively hig...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J32/00B01J35/10B01J23/83B01J23/889C10L3/08
Inventor 王树东袁中山彭家喜周谨张建国杨晓野
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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