CO sulfur tolerant shift catalyst and preparation method thereof

A sulfur-resistant conversion and catalyst technology, which is applied in the direction of catalyst activation/preparation, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of failure to reach the second type of catalyst, adverse effects of subsequent stages, easy loss of alkali metal, etc. problems, to achieve the effect of increasing interaction, improving strength and stability, and highlighting substantive features

Active Publication Date: 2010-04-21
SHANDONG QILU KELI CHEMICAL RESEARCH INSTITUTE CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, there are three main types of successfully developed sulfur-tolerant shift catalysts: one is non-alkali metal-promoted Co-Mo-based sulfur-tolerant shift catalysts, the carrier is activated alumina, and MgO is used as a structural aid to form magnesium-aluminum spinels The precursor of magnesia or magnesia-aluminum spinel is used to improve the conversion activity, strength and structural stability of the catalyst; the second type is the alkali metal-promoted Co-Mo series sulfur-resistant shift catalyst, the carrier is activated alumina, and the alkali metal is used as the catalyst. Co-agents, the purpose of which is to use alkali metals can greatly improve the low-temperature activity of the catalyst and reduce the activation temperature of the catalyst. Alkali metals are easy to lose, and the carrier is prone to phase change to cause catalyst deactivation, and may even cause adverse effects on subsequent sections; the third category is based on Al 2 o 3 -MgO-TiO 2 The Co-Mo series sulfur-tolerant shift catalyst (CN1096494A) with ternary oxide as the carrier is characterized in that the low-sulfur activity and low-temperature activity of the catalyst are significantly higher than that of the first type of catalyst, but it cannot reach the level of the second type of catalyst. in between

Method used

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  • CO sulfur tolerant shift catalyst and preparation method thereof
  • CO sulfur tolerant shift catalyst and preparation method thereof
  • CO sulfur tolerant shift catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Example 1: Phase inversion of natural magnesite ore into active magnesia ore powder

[0045] Take a natural magnesite ore in Laizhou, Shandong, its composition and phase: MgO: 45.35%, CaO: 0.60%, SiO 2 : 0.2%, Al 2 o 3 : 0.6%, Fe 2 o 3 : 0.4%, CO 2 : ~46.85%. The phase composition of magnesite was analyzed by x-ray diffractometer, the main component of the ore is MgCO 3 . Pulverize the ore, put it into a muffle furnace, raise the temperature to 800°C, and heat the phase inversion at 800°C for 2 hours, then naturally cool down to obtain active magnesia ore powder; the composition of active magnesia: MgO: 92.6%, CaO: 1.2%, SiO 2 : 0.4%, Al 2 o 3 : 0.9%, Fe 2 o 3 : 0.8%. The active magnesia ore powder is analyzed by X-ray diffractometer, and its main component is MgO.

Embodiment 2

[0046] Example 2: Phase inversion of natural magnesite ore into active magnesia ore powder

[0047] Take a natural magnesite ore in Haicheng, Liaoning, its composition and phase: MgO: 46.62%, CaO: 0.86%, SiO2: 0.2%, Al2O3: 0.3%, Fe2O3: 0.3%, CO2: ~46.4%. The phase composition of magnesite was analyzed by X-ray diffractometer, and the main component of the ore was MgCO3. Pulverize the ore, put it into a muffle furnace, raise the temperature to 800°C, keep warm at 800°C for 2 hours, and then cool down naturally to obtain active magnesia ore powder; the composition of active magnesia: MgO: 93.1%, CaO: 1.5%, SiO2: 0.3%, Al2O3: 0.5%, Fe2O3: 0.5%. The active magnesia ore powder is analyzed by X-ray diffractometer, and its main component is MgO.

Embodiment 3

[0048] Example 3 Preparation of Sulfur Tolerant Shift Catalyst Using Activated Magnesia Powder

[0049] Add 220 g of the active magnesia powder obtained in Example 1, 760 g of pseudo-boehmite and 20 g of urea into a ball mill, mix and mill for 1 hour to obtain a powdery mixture, which is kneaded together with 30 g of scallop powder Dry mix in the machine for 10 minutes, add 95g ammonium paramolybdate, 150g cobalt nitrate and 30g citric acid aqueous solution and knead for 60 minutes. . The finished catalyst can be obtained, the number is LMK-01. Catalyst test results: The prepared LMK-01 catalyst and commercial catalyst A were tested according to the normal catalyst physical and chemical performance test method and the above-mentioned activity evaluation method. The test results are shown in Table 1, Table 2 and Table 3.

[0050] Directly use natural magnesite ore powder to directly produce sulfur-resistant shift catalyst, the physical and chemical properties and catalytic act...

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Abstract

The invention provides a CO high/medium voltage sulfur tolerant shift catalyst comprising a catalyst active component, a structure promoter and a carrier. The CO high/medium voltage sulfur tolerant shift catalyst is characterized in that the structure promoter is directly derived from magnesite, and the magnesite is crushed and subjected to thermal inversion and phase inversion to form active magnesium oxide mineral powder so as to substitute active magnesium oxide or magnesium salts; the use level of the magnesite powder is 5-30 percent of the total quality of the catalyst; the technical key lies in the high dispersion and thermal phase inversion of the magnesite powder; meanwhile, the invention also provides a preparation method of the catalyst, which has simple operation process and comprises the following steps of mediating, extruding, drying and roasting. The catalyst is applied to a process flow of high/medium voltage shift and has very high activity, stability and strength. The sulfur tolerant shift catalyst prepared by the natural magnesite powder has stable components, low production cost and no pollution in the production process, thereby achieving a feasible technology.

Description

technical field [0001] The invention is a CO sulfur-tolerant shift catalyst and a preparation method thereof, in particular to converting CO into H in the presence of water vapor 2 and CO 2 sulfur-tolerant shift catalyst. Background technique [0002] In the process of producing synthetic ammonia or industrial methanol with coal or oilfield gas as raw material, in the reformed gas after conversion of semi-water gas or oilfield gas produced by coal gas production, the raw material H required for the synthesis reaction is removed. 2 In addition, a considerable amount of CO gas is also produced, which must be converted into raw material gas H under a certain temperature, pressure and presence of a catalyst. 2 . [0003] CO shift catalysts have gone through the three major processes of Cu-Zn, Fe-Cr and Co-Mo. Co-Mo catalysts are widely used due to their sulfur resistance, wide operating temperature range and good catalytic activity. However, in the prior art, there are still...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/882B01J21/10B01J37/00C01B3/16
CPCY02P20/52
Inventor 谭永放田力高步良程玉春邓建利
Owner SHANDONG QILU KELI CHEMICAL RESEARCH INSTITUTE CO LTD
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