Application and preparation of high-activity composite oxide oxygen carrier in chemical link circulation hydrogen production

An oxygen carrier and oxide technology, applied in the field of chemical chain hydrogen production, can solve the problems of low dispersity of metal oxides, low cyclic reactivity, limited oxygen carrying rate, etc. Simple method and low cost effect

Active Publication Date: 2014-08-20
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Relatively speaking, the oxygen carrier NiO / NiAl 2 o 4 (CHO P etc. Fuel, 2004, 83(9)), Fe 2 o 3 / Al 2 o 3 (MATTISSON T etc. Fuel, 2001, 80 (13)) and CoO-NiO / YSZ (JIN H G etc. Energy Fuels, 1998, 12 (6)) have better overall performance, but there are limited oxygen loading rates and cyclic reactions low resistance, inability to withstand high reaction temperature, low dispersion of metal oxides in oxygen carriers, etc.

Method used

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  • Application and preparation of high-activity composite oxide oxygen carrier in chemical link circulation hydrogen production

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Take 21.85gCo(NO 3 ) 2 ·6H 2 Put O into a 500mL beaker, add 100mL of distilled water, slowly dropwise add chloropalladium acid solution containing 4% Pd, and then add 100mL of distilled water to make the molar ratio of Co to Pd 0.95 / 0.05, then place the beaker at 80 In a water bath at ℃, the stirring speed is 400rpm, and stir until completely dissolved. Take 30.87g La(NO 3 ) 3 ·6H 2 O and 0.8g KNO 3 Put it into a beaker with 100mL of distilled water and stir until it is completely dissolved so that the molar ratio of La to K is 0.9 / 0.1. Then add the lanthanum nitrate and potassium nitrate solution dropwise to the cobalt nitrate and chloropalladium acid solution, and stir while adding dropwise. Take 40g of citric acid, the molar ratio of citric acid to the total amount of metal ions is 1.2:1, put it into a 100mL beaker and stir until it is completely dissolved. At this time, after the above mixed solution is stirred for 30 minutes, slowly add the citric acid solut...

Embodiment 2

[0021] Take 20.7gCo(NO 3 ) 2 ·6H 2 Put O into a 500mL beaker, slowly add 4% Pd-containing chloropalladium acid solution dropwise, then add 100mL of distilled water to make the molar ratio of Co to Pd 0.9 / 0.1, then place the beaker in a water bath at 80°C, Stirring speed is 400rpm, stir until completely dissolved. Take 29.15g La(NO 3 ) 3 ·6H 2 O and 1.2g KNO 3Put it into a beaker with 100mL of distilled water, stir until it is completely dissolved, so that the molar ratio of La to K is 0.85 / 0.15. Then add the lanthanum nitrate and potassium nitrate solution dropwise to the cobalt nitrate and chloropalladium acid solution, and stir while adding dropwise. Take 67g of citric acid, the molar ratio of citric acid to metal ions is 1.2:1, put it into a 100mL beaker and stir until it is completely dissolved. After the above mixed solution is stirred for 30 minutes, slowly add the citric acid solution, while adding While stirring. After stirring for 5 hours, the brown solution ...

Embodiment 3

[0023] Take 21.85gCo(NO 3 ) 2 ·6H 2 Put O into a 500mL beaker, add 100mL of distilled water, slowly dropwise add chloropalladium acid solution containing 4% Pd, and then add 100mL of distilled water to make the molar ratio of Co to Pd 0.95 / 0.05, then place the beaker at 80 In a water bath at ℃, the stirring speed is 400rpm, and stir until completely dissolved. Take 27.44g La(NO 3 ) 3 ·6H 2 O and 1.6g KNO 3 Put it into a beaker with 100mL of distilled water and stir until it is completely dissolved so that the molar ratio of La to K is 0.8 / 0.2. Then add the lanthanum nitrate and potassium nitrate solution dropwise to the cobalt nitrate and chloropalladium acid solution, and stir while adding dropwise. Take 40g of citric acid, the molar ratio of citric acid to the total amount of metal ions is 1.2:1, put it into a 100mL beaker and stir until it is completely dissolved. After the above mixed solution is stirred for 30 minutes, slowly add the citric acid solution, while add...

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Abstract

The invention discloses application and preparation of a composite oxide with perovskite structure in chemical link circulation hydrogen production. The composite metal oxide with perovskite structure is AxA'1-xByB'1-yO3, wherein A is rare earth metal lanthanum, A' is metal metallic potassium, B is transition metal cobalt, and B' is precious metal palladium, 0.7<x<1, and 0.8<y<1. The reaction temperature of an oxygen carrier in fuel is 500-1250 DEG C, and the reaction temperature of the oxygen carrier in steam is 500-1250 DEG C. A preparation method of the oxygen carrier includes utilizing cobalt nitrate, lanthanum nitrate, potassium nitrate and palladium chloride acid as precursors, utilizing citric acid or ethylene glycol as complexing agents, preparing solution, evenly mixing the solution, then conducting water evaporation till the solution is converted into thick gel from transparent sol and finally conducting drying and burning. A burnt sample is a composite metal oxide with the perovskite structure. The oxygen carrier is high in oxygen carrying rate, high in catalytic activity, strong in carbon deposit resistance, strong in high temperature sintering resistance and good in stability.

Description

technical field [0001] The invention relates to the application and preparation method of a perovskite structure composite oxide in chemical chain cycle hydrogen production technology, belonging to the field of chemical chain hydrogen production. Background technique [0002] In 1983, German scientists Richter and Knoche first proposed the concept of chemical looping combustion (CLC). The biggest difference between this combustion technology and the usual combustion technology is that it does not directly use the oxygen molecules in the air, but uses the oxygen atoms in the oxygen carrier to complete the combustion process of the fuel, and the combustion products (mainly CO 2 and water vapor) will not be diluted by nitrogen in the air and the concentration is extremely high, and almost pure CO can be obtained by simple condensation 2 , simple and low energy consumption to achieve CO 2 In addition, due to the relatively low operating temperature of the fuel reactor and the ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01B13/14C01B3/02
Inventor 倪向前梁皓张舒冬张喜文
Owner CHINA PETROLEUM & CHEM CORP
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