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Polynary metal oxide catalyst and preparing process thereof

A composite metal and oxide technology, applied in the direction of metal/metal oxide/metal hydroxide catalyst, physical/chemical process catalyst, catalyst carrier, etc., can solve the problem of insufficient stability, transformation activity and low temperature activity Poor activity, high low temperature activity and other problems, to achieve the effect of improving conversion activity and activity stability, improving performance, and high and low temperature activity

Active Publication Date: 2008-06-18
汤海溶 +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

US patent US 3,850,840, Chinese patent CN 87 1 07892 reported the use of γ-Al 2 o 3 As a carrier, a cobalt-molybdenum shift catalyst with an alkali metal additive is added. This type of catalyst has high low-temperature activity, but poor stability, and is not suitable for use under high pressure and high water / gas ratio conditions.
U.S. Patent US 3,529,935 reported that MgO and Al 2 o 3 It is a cobalt-molybdenum shift catalyst without adding alkali metal additives as a carrier. This type of catalyst has high activity at medium temperature and good stability. It is suitable for use under high pressure and high water / gas ratio. However, it has poor activity at low temperature and requires relatively high water gas. Sulfur content, otherwise the activity declines seriously
Chinese patents CN 1096494A, CN 1429763A and CN 148516A disclose the use of MgO, Al 2 o 3 and TiO 2 The mixture of three kinds of oxides and the cobalt-molybdenum shift catalyst without adding alkali metal promoters by adding cement as a carrier have improved the deficiency of the aforementioned cobalt-molybdenum shift catalysts without adding alkali metal promoters to a certain extent, but in terms of stability, There are still obvious deficiencies in transformation activity, low temperature activity and scope of application, and the overall performance needs to be further improved

Method used

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  • Polynary metal oxide catalyst and preparing process thereof
  • Polynary metal oxide catalyst and preparing process thereof
  • Polynary metal oxide catalyst and preparing process thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Weigh industrial γ-Al with particles less than 100 mesh 2 o 3 Powder (specific surface greater than 200m 2 / g) 440g, Ti(OH) 4 Powder 218g, Ce(OH) 4 Powder 12g and Zr(OH) 4 Powder 13g, respectively with Mg (NO 3 ) 2 ·6H 2 O1009g, 481g, 15g and 12g of magnesium nitrate aqueous solution soaked for 2h, mixed and kneaded evenly, then dried at 110°C for 12h, and roasted at 600°C for 4h to obtain MgO / Al 2 o 3 、MgO / TiO 2 、MgO / CeO 2 and MgO / ZrO 2 Solid alkali material. The materials are uniformly mixed and pulverized, and passed through a 220-mesh sieve to obtain a multi-component composite metal oxide solid alkali carrier powder. With 123g ammonium molybdate, 155g cobalt nitrate, 5gCeO 2 of cerium nitrate and 5 g of ZrO 2 The mixed solution composed of zirconium nitrate was impregnated with carrier powder, mixed and kneaded evenly, then dried at 120° C. for 12 hours, and crushed through a 150-mesh sieve to obtain catalyst powder. Finally, add 80g of cellulose pow...

Embodiment 2

[0028] The preparation method is the same as in Example 1, except that the γ-Al 2 o 3 Preparation of MgO / Al by Forming Hydrotalcite-like Precursors on the Surface of Inner Pores 2 o 3 Surface solid alkali, soak γ-Al with a mixed aqueous solution composed of 1009g magnesium nitrate and 473g urea 2 o 3 The powder was treated for 10 hours at 90°C for 2 hours, then filtered, washed until neutral, dried at 100°C for 12 hours, and dried in γ-Al 2 o 3 Hydrotalcite-like precursors are formed on the surface of the inner pores, which are transformed into MgO / Al after heat treatment 2 o 3 The surface solid base is used to prepare the catalyst B of the present invention.

Embodiment 3

[0030] The preparation method is the same as in Example 1, except that the MgO / Al is prepared by pre-preparing the hydrotalcite-like precursor 2 o 3 Solid base, both 1009g magnesium nitrate and 2463g aluminum nitrate were dissolved in 4400ml deionized water to make a mixed solution, 474gNaOH and 419gNa 2 CO 3 Dissolve in 4400ml of deionized water to make a mixed precipitant solution, quickly mix and stir the two mixed solutions in equal volume at 85°C, carry out precipitation reaction and age for 20h, then filter, wash until neutral, and dry at 110°C 12h, the precursor of magnesium-aluminum hydrotalcite was obtained, and then mixed with 622g pseudo-boehmite evenly, and transformed into MgO / Al after heat treatment 2 o 3 A solid base is used to obtain the catalyst C of the present invention.

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Abstract

The invention discloses a multi-complex-metal-oxides catalyst and the preparation method. The catalyst carrier is multi-complex-metal-oxides solid alkali or surface solid alkali or the precursors of the solid alkali or surface solid alkali. The multi-complex-metal-oxides is complex oxides by combining two or more than two selections from alumina, titania, zirconium dioxide and ceria with one or more than one selections from magnesia, calcium oxide, baryta, potassium oxide and sodium oxide. Active ingredient is composed of cobalt oxides or / and nickel oxide and molybdenum trioxide or / and tungsten trioxide. The additive added to carriers or active components is the oxide of at least one of the following elements: cerium, lanthanum, zinc, zirconium, nickel or manganese. The invention has the advantages of high activity, high activity at low-temperature, high activity stability and wide temperature range of activity; high intensity, high intensity stability and high anti-hydration and anti-pulverization ability, wide water / gas ratio adaptability and wide range for impurity content. The catalyst of the invention is applied to the promotion of dirty water gas shift reaction.

Description

technical field [0001] The invention belongs to a cobalt-molybdenum series catalyst and a preparation method for promoting dirty water gas shift reaction, in particular to a multi-component composite metal oxide catalyst and a preparation method thereof. Background technique [0002] As we all know, there are three types of water gas shift catalysts used in industry, namely iron chromium, copper zinc and cobalt molybdenum. The first two classes suffer from sulfur poisoning problems, so they are not suitable for promoting shift reactions of dirty water gas. In the late 1960s, cobalt-molybdenum shift catalysts were invented in order to meet the needs of heavy raw materials for syngas production and direct conversion of dirty water gas (mainly containing sulfide) produced by heavy oil, residual oil or coal gasification. Compared with the former two types, it has the advantages of high activity, wide activity temperature range, wide water / air ratio, strong anti-poison ability, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/882B01J32/00C10J3/72
CPCY02E20/18Y02P20/52
Inventor 汤海溶
Owner 汤海溶
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