Medium-high-pressure low-temperature sulfur-resistant pre-shift catalyst for CO and preparation method thereof

Abstract

The invention relates to a CO medium-high-pressure low-temperature sulfur-tolerant pre-shift catalyst and a preparation method thereof, and relates to the technical field of sulfur-tolerant pre-shift catalyst preparation. In the CO medium-high-pressure low-temperature sulfur-tolerant pre-shift catalyst, an active component is a binary component of a cobalt-containing compound and a molybdenum-containing compound; a carrier raw material is a composition of boehmite and nano-grade titanium dioxide; and a rare earth auxiliary agent is a mixture of a lanthanum-containing compound and a cerium-containing compound. The CO medium-high-pressure low-temperature sulfur-tolerant pre-shift catalyst provided by the invention has the characteristics of high strength, high stability, high erosion resistance, high toxin resistance, uniformly active component dispersion, and good shift activity stability. The active component is not prone to loss. The invention also provides the simple and feasible preparation method of the catalyst.

Description

technical field

[0001] The invention relates to a medium-high-pressure, low-temperature sulfur-resistant pre-shift catalyst for CO and a preparation method thereof, belonging to the technical field of preparation of sulfur-resistant pre-shift catalysts. Background technique

[0002] In recent years, with the technological progress and rapid development of the coal chemical industry, the corresponding gasification process is also constantly introducing new ones, and the CO content in the produced syngas is getting higher and higher. For example, the newly introduced German Siemens GSP gasification technology syngas CO content The CO content of the syngas in the Shell coal gasification process is even higher than 60%. At the same time, the scale of coal gasification is also continuously expanding. For example, the gas volume of the conversion part of the 4 sets of chemical fertilizer renovation and expansion units of Sinopec has increased by more than 50%. The designed convers...

Examples

Embodiment 1

[0052] Dissolve 5.9g of ammonium molybdate in 20.0mL of deionized water to obtain ammonium molybdate solution A; dissolve 7.7g of cobalt nitrate in 20.0mL of deionized water, then add 3.0g of citric acid and 3.0g of oxalic acid to the above cobalt nitrate solution, stirring and dissolving to obtain solution B containing cobalt. Dissolve 0.80 g of lanthanum nitrate and 1.51 g of cerium nitrate in 40 mL of deionized water to obtain rare earth additive solution C.

[0053] Weigh 74g of gibbsite, 18g of nano-titanium oxide, and 6g of scallop powder, mix evenly, add solution A, knead evenly; then add solution B, knead, shape, dry naturally, and then use high-temperature steam to roast at 380°C for 4h , naturally lowered to room temperature to obtain a catalyst semi-finished product. The semi-finished catalyst was impregnated with rare earth additive solution C for 3 hours, dried naturally, and then calcined at 380°C for 4 hours with high-temperature steam to obtain CO medium-high-...

Embodiment 2

[0055] Dissolve 4.91g of ammonium molybdate in 20.0mL of deionized water to obtain ammonium molybdate solution A; dissolve 7.70g of cobalt nitrate in 20.0mL of deionized water, then add 3.0g of citric acid and 3.0g of oxalic acid to the above cobalt nitrate in sequence solution, stirring and dissolving to obtain solution B containing cobalt. Dissolve 1.33g of lanthanum nitrate and 2.52g of cerium nitrate in 40mL of deionized water to obtain rare earth additive solution C.

[0056] Weigh 72g of gibbsite, 20g of nano-titanium oxide, and 5g of polyvinyl alcohol, mix them evenly, add solution A, and knead evenly; then add solution B, knead, shape, dry naturally, and then use high-temperature steam to roast at 375°C for 5h , naturally lowered to room temperature to obtain a catalyst semi-finished product. The semi-finished catalyst was impregnated with rare earth additive solution C for 3 hours, dried naturally, and then calcined at 370°C for 5 hours with high-temperature steam to...

Embodiment 3

[0058] Dissolve 7.36g of ammonium molybdate in 21.0mL of deionized water to obtain ammonium molybdate solution A; dissolve 11.65g of cobalt nitrate in 23.0mL of deionized water, then add 3.0g of citric acid and 3.0g of carboxymethyl cellulose in sequence into the above-mentioned cobalt nitrate solution, boiled and stirred to dissolve to obtain cobalt-containing solution B. Dissolve 1.33g of lanthanum nitrate and 2.52g of cerium nitrate in 42mL of deionized water to obtain rare earth additive solution C.

[0059] Weigh 72g of gibbsite, 20g of nano-titanium oxide, and 8g of cinnamon powder, mix them evenly, add solution A, and knead evenly; then add solution B, knead, shape, dry naturally, and then use high-temperature steam to roast at 375°C for 5h , naturally lowered to room temperature to obtain a catalyst semi-finished product. The semi-finished catalyst was impregnated with rare earth additive solution C for 3 hours, dried naturally, and then roasted at 380°C for 4 hours w...

technical field

[0001] The invention relates to a medium-high-pressure, low-temperature sulfur-resistant pre-shift catalyst for CO and a preparation method thereof, belonging to the technical field of preparation of sulfur-resistant pre-shift catalysts. Background technique

[0002] In recent years, with the technological progress and rapid development of the coal chemical industry, the corresponding gasification process is also constantly introducing new ones, and the CO content in the produced syngas is getting higher and higher. For example, the newly introduced German Siemens GSP gasification technology syngas CO content The CO content of the syngas in the Shell coal gasification process is even higher than 60%. At the same time, the scale of coal gasification is also continuously expanding. For example, the gas volume of the conversion part of the 4 sets of chemical fertilizer renovation and expansion units of Sinopec has increased by more than 50%. The designed convers...

Examples

Embodiment 1

[0052] Dissolve 5.9g of ammonium molybdate in 20.0mL of deionized water to obtain ammonium molybdate solution A; dissolve 7.7g of cobalt nitrate in 20.0mL of deionized water, then add 3.0g of citric acid and 3.0g of oxalic acid to the above cobalt nitrate solution, stirring and dissolving to obtain solution B containing cobalt. Dissolve 0.80 g of lanthanum nitrate and 1.51 g of cerium nitrate in 40 mL of deionized water to obtain rare earth additive solution C.

[0053] Weigh 74g of gibbsite, 18g of nano-titanium oxide, and 6g of scallop powder, mix evenly, add solution A, knead evenly; then add solution B, knead, shape, dry naturally, and then use high-temperature steam to roast at 380°C for 4h , naturally lowered to room temperature to obtain a catalyst semi-finished product. The semi-finished catalyst was impregnated with rare earth additive solution C for 3 hours, dried naturally, and then calcined at 380°C for 4 hours with high-temperature steam to obtain CO medium-high-...

Embodiment 2

[0055] Dissolve 4.91g of ammonium molybdate in 20.0mL of deionized water to obtain ammonium molybdate solution A; dissolve 7.70g of cobalt nitrate in 20.0mL of deionized water, then add 3.0g of citric acid and 3.0g of oxalic acid to the above cobalt nitrate in sequence solution, stirring and dissolving to obtain solution B containing cobalt. Dissolve 1.33g of lanthanum nitrate and 2.52g of cerium nitrate in 40mL of deionized water to obtain rare earth additive solution C.

[0056] Weigh 72g of gibbsite, 20g of nano-titanium oxide, and 5g of polyvinyl alcohol, mix them evenly, add solution A, and knead evenly; then add solution B, knead, shape, dry naturally, and then use high-temperature steam to roast at 375°C for 5h , naturally lowered to room temperature to obtain a catalyst semi-finished product. The semi-finished catalyst was impregnated with rare earth additive solution C for 3 hours, dried naturally, and then calcined at 370°C for 5 hours with high-temperature steam to...

Embodiment 3

[0058] Dissolve 7.36g of ammonium molybdate in 21.0mL of deionized water to obtain ammonium molybdate solution A; dissolve 11.65g of cobalt nitrate in 23.0mL of deionized water, then add 3.0g of citric acid and 3.0g of carboxymethyl cellulose in sequence into the above-mentioned cobalt nitrate solution, boiled and stirred to dissolve to obtain cobalt-containing solution B. Dissolve 1.33g of lanthanum nitrate and 2.52g of cerium nitrate in 42mL of deionized water to obtain rare earth additive solution C.

[0059] Weigh 72g of gibbsite, 20g of nano-titanium oxide, and 8g of cinnamon powder, mix them evenly, add solution A, and knead evenly; then add solution B, knead, shape, dry naturally, and then use high-temperature steam to roast at 375°C for 5h , naturally lowered to room temperature to obtain a catalyst semi-finished product. The semi-finished catalyst was impregnated with rare earth additive solution C for 3 hours, dried naturally, and then roasted at 380°C for 4 hours w...

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