Sulfur-tolerant CO shift conversion catalyst and preparation method thereof

Abstract

The present invention discloses a sulfur tolerant carbon monoxide shift conversion catalyst, prepared by the following materials: magnesium source, aluminum source, oxide flux, crystal growth agent, rare earth additive, CoO, MoO.sub.3 and an acidic aqueous solution. A preparation method of the catalyst is provided, comprising the steps of: S1, Adding an aqueous acidic solution and a specific amount of rare earth additive to a specific amount of magnesium source, aluminum source, oxide flux and crystal growth agent, followed by kneading to produce a mixture; S2, Extruding the mixture to obtain an extruded strip product; S3, Drying the extruded strip product to give a semi-finished product; S4, Calcining the semi-finished product to obtain a catalyst carrier; S5, Impregnating the catalyst carrier with the active components CoO and MoO.sub.3 by an incipient-wetness impregnation method to obtain an impregnated product; and S6, Calcining the impregnated product to obtain the catalyst. The oxide flux and crystal growth agent can participate in a solid phase reaction between the magnesium source and aluminum source to form spinel structure, thereby improving the mechanical strength and stability of the spinel. The nano-sized active component can effectively improve the dispersion of the active component, and improve the catalytic activity of the granular boundary of the active component.

Claims

1. A sulfur tolerant CO shift conversion catalyst, at least prepared by the following materials: a magnesium source, 8.9-18.5 parts by weight; an aluminum source, a molar ratio of the magnesium source to the aluminum source is 0.92-1.36 wherein the magnesium source is calculated in the form of MgO and the aluminum source is calculated in the form of Al.sub.2O.sub.3; an oxide flux, 1.5-3.0 parts by weight; a magnesia-alumina spinel powder as a crystal growth agent, 1.5-3.6 parts by weight; a rare earth additive, 0.9-3.0 parts by weight; CoO, 0.2-1.5 parts by weight; MoO.sub.3, 1.4-3.2 parts by weight; and an acidic aqueous solution, 37.8-63.3 parts by weight.

2. The catalyst of claim 1, wherein, the oxide flux is one or a mixture of two selected from the group consisting of CaO, K.sub.2O, PbO and B.sub.2O.sub.3, and has a particle size of 150-200 mesh.

3. The catalyst of claim 2, wherein, the rare earth additive is selected from the group consisting of La.sub.2O.sub.3, Pr.sub.2O.sub.3, CeO.sub.2 and mixtures thereof.

4. The catalyst of claim 3, wherein, the acidic aqueous solution is selected from the group consisting of nitric acid, oxalic acid, citric acid, acetic acid or mixtures thereof, and has a concentration of 0.56 mol/L.

5. The catalyst of claim 4, wherein, the CoO and MoO.sub.3 constitute an active component of the catalyst, and a main phase of the active component is MoS.sub.2 having a sheet structure with a size of 5 nm.

6. The catalyst of claim 3, wherein, the aluminum source is selected from the group consisting of pseudo-boehmite powder, Al.sub.2O.sub.3, Al.sub.2O.sub.3.H.sub.2O, Al.sub.2O.sub.3 3H.sub.2O, aluminium nitrate and mixtures thereof.

7. The catalyst of claim 6, wherein, the magnesium source is selected from the group consisting of basic magnesium carbonate, Mg(OH).sub.2, light MgO and mixtures thereof.

8. The catalyst of claim 1, wherein, the magnesia-alumina spinel powder has a particle size of 150-200 mesh and a specific surface area of 20-40 m.sup.2/g.

9. The catalyst of claim 8, wherein, the oxide flux is one or a mixture of two selected from the group consisting of CaO, K.sub.2O, PbO and B.sub.2O.sub.3, and has a particle size of 150-200 mesh.

10. The catalyst of claim 9, wherein, the rare earth additive is selected from the group consisting of La.sub.2O.sub.3, Pr.sub.2O.sub.3, CeO.sub.2 and mixtures thereof.

11. The catalyst of claim 10, wherein, the magnesium source is selected from the group consisting of basic magnesium carbonate, Mg(OH).sub.2, light MgO and mixtures thereof.

12. The catalyst of claim 11, wherein, the acidic aqueous solution is selected from the group consisting of nitric acid, oxalic acid, citric acid, acetic acid or mixtures thereof, and has a concentration of 0.56 mol/L.

13. The catalyst of claim 12, wherein, the CoO and MoO.sub.3 constitute an active component of the catalyst, and a main phase of the active component is MoS.sub.2 having a sheet structure with a size of 5 nm.

14. The catalyst of claim 10, wherein, the acidic aqueous solution is selected from the group consisting of nitric acid, oxalic acid, citric acid, acetic acid or mixtures thereof, and has a concentration of 0.56 mol/L.

15. The catalyst of claim 14, wherein, the CoO and MoO.sub.3 constitute an active component of the catalyst, and a main phase of the active component is MoS.sub.2 having a sheet structure with a size of 5 nm.

16. The catalyst of claim 10, wherein, the aluminum source is selected from the group consisting of pseudo-boehmite powder, Al.sub.2O.sub.3, Al.sub.2O.sub.3.H.sub.2O, Al.sub.2O.sub.3.3H.sub.2O, aluminium nitrate and mixtures thereof.

17. The catalyst of claim 16, wherein, the acidic aqueous solution is selected from the group consisting of nitric acid, oxalic acid, citric acid, acetic acid or mixtures thereof, and has a concentration of 0.56 mol/L.

18. The catalyst of claim 17, wherein, the CoO and MoO.sub.3 constitute an active component of the catalyst, and a main phase of the active component is MoS.sub.2 having a sheet structure with a size of 5 nm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) In order to make the content of the present invention are more likely to be clearly understood, the content of the present invention will now be described in detail with reference to FIGURES and detailed embodiments.

(2) FIG. 1 shows a transmission electron microscopy (TEM) image of sulfur-tolerant carbon monoxide shift conversion catalyst in Example 1.

DETAILED EMBODIMENTS OF THIS INVENTION

Example 1

(3) The Example 1 provides a sulfur tolerant carbon monoxide shift conversion catalyst, which is prepared by the following materials:

(4) basic magnesium carbonate, 18.5 parts by weight;

(5) Al.sub.2O.sub.3, wherein a molar ratio of the basic magnesium carbonate to Al.sub.2O.sub.3 is 0.92, and wherein the amount of the basic magnesium carbonate is calculated in the form of MgO;

(6) PbO, 3.0 parts by weight, with a particle size of 200 mesh in the Example 1;

(7) magnesia-alumina spinel powder, 1.5 parts by weight, with a particle size of 200 mesh and a specific surface area of 20 m.sup.2/g in the Example 1;

(8) CeO.sub.2, 1.5 parts by weight;

(9) CoO, 0.6 parts by weight;

(10) MoO.sub.3, 1.4 parts by weight;

(11) 1 mol/L of nitric acid solution, 56.0 parts by weight.

(12) A preparation method of the sulfur tolerant carbon monoxide shift conversion catalyst comprises:

(13) S1, Weighting basic magnesium carbonate and Al.sub.2O.sub.3 proportionally, and mixing them with 3.0 parts by weight of PbO, 1.5 parts by weight of magnesia-alumina spinel powder and 1.5 parts by weight of CeO.sub.2, then adding 56.0 parts by weight of nitric acid solution of 1 mol/L, followed by kneading to produce a mixture;

(14) S2, Extruding the mixture to obtain an extruded strip product;

(15) S3, Drying the extruded strip product at a temperature of 120 C. for a period of 5 hours to give a semi-finished product;

(16) S4, Calcining the semi-finished product at a temperature of 550 C. for a period of 6 hours to obtain a catalyst carrier labeled as T1;

(17) S5, Impregnating the catalyst carrier T1 with 0.6 parts by weight of CoO and 1.4 parts by weight of MoO.sub.3 by an incipient-wetness impregnation method to obtain an impregnated product; and

(18) S6, Calcining the impregnated product at a temperature of 300 C. for a period of 2 h to obtain the sulfur tolerant CO shift conversion catalyst labeled as F1.

Example 2

(19) The Example 2 provides a sulfur tolerant CO shift conversion catalyst, which is prepared by the following materials:

(20) light MgO, 8.9 parts by weight;

(21) Al.sub.2O.sub.3.H.sub.2O, wherein a molar ratio of MgO to Al.sub.2O.sub.3 is 1.36; CaO, 2.3 parts by weight, with a particle size of 150 mesh in the Example 2;

(22) magnesia-alumina spinel powder, 3.6 parts by weight, with a particle size of 150 mesh and a specific surface area of 40 m.sup.2/g in the Example 2;

(23) Pr.sub.2O.sub.3, 0.9 parts by weight;

(24) CoO, 0.2 parts by weight;

(25) MoO.sub.3, 3.2 parts by weight; and

(26) acetic acid solution of 2 mol/L, 44.6 parts by weight.

(27) A preparation method of the sulfur tolerant carbon monoxide shift conversion catalyst comprises:

(28) S1, weighting the light MgO and Al.sub.2O.sub.3.H.sub.2O proportionally, and mixing them with 2.3 parts by weight of CaO, 3.6 parts by weight of magnesia-alumina spinel powder and 0.9 parts by weight of Pr.sub.2O.sub.3, then adding 44.6 parts by weight of acetic acid solution of 2 mol/L, followed by kneading to produce a mixture;

(29) S2, Extruding the mixture to obtain an extruded strip product;

(30) S3, Drying the extruded strip product at a temperature of 140 C. for a period of 8 hours to give a semi-finished product;

(31) S4, Calcining the semi-finished product at a temperature of 550 C. for a period of 13 hours to obtain a catalyst carrier T2;

(32) S5, Impregnating the catalyst carrier T2 with 0.2 parts by weight of CoO and 3.2 parts by weight of MoO.sub.3 by an incipient-wetness impregnation method to obtain an impregnated product; and

(33) S6, Calcining the impregnated product at a temperature of 450 C. for a period of 2 h to obtain the sulfur tolerant CO shift conversion catalyst F2.

Example 3

(34) The Example 3 provides a sulfur tolerant CO shift conversion catalyst, which is prepared by the following materials:

(35) light MgO, 8.9 parts by weight;

(36) Al.sub.2O.sub.3.3H.sub.2O, wherein a molar ratio of MgO to Al.sub.2O.sub.3 is 1.36;

(37) B.sub.2O.sub.3, 1.5 parts by weight, with a particle size of 200 mesh in the Example 3;

(38) magnesia-alumina spinel powder, 3.6 parts by weight, with a particle size of 200 mesh and a specific surface area of 30 m.sup.2/g in the Example 3;

(39) Pr.sub.2O.sub.3, 0.9 parts by weight;

(40) CoO, 0.2 parts by weight;

(41) MoO.sub.3, 3.2 parts by weight; and

(42) acetic acid solution of 2 mol/L, 44.6 parts by weight.

(43) The sulfur tolerant carbon monoxide shift conversion catalyst is prepared by a method comprising:

(44) S1, weighting the light MgO and Al.sub.2O.sub.3.3H.sub.2O proportionally, and mixing them with 1.5 parts by weight of B.sub.2O.sub.3, 3.6 parts by weight of magnesia-alumina spinel powder and 0.9 parts by weight of Pr.sub.2O.sub.3, then adding 44.6 parts by weight of acetic acid solution of 2 mol/L, followed by kneading to produce a mixture;

(45) S2, Extruding the mixture to obtain an extruded strip product;

(46) S3, Drying the extruded strip product at a temperature of 120 C. for a period of 8 hours to give a semi-finished product;

(47) S4, Calcining the semi-finished product at a temperature of 650 C. for a period of 13 hours to obtain a catalyst carrier T3;

(48) S5, Impregnating the catalyst carrier T3 with 0.2 parts by weight of CoO and 3.2 parts by weight of MoO.sub.3 by an incipient-wetness impregnation method to obtain an impregnated product; and

(49) S6, Calcining the impregnated product at a temperature of 450 C. for a period of 8 h to obtain the sulfur tolerant CO shift conversion catalyst F3.

Example 4

(50) The Example 4 provides a sulfur tolerant CO shift conversion catalyst, which is prepared by the following materials:

(51) Mg(OH).sub.2, 10.0 parts by weight;

(52) aluminum pseudoboehmite powder, when calculated in the form of MgO/Al.sub.2O.sub.3, a molar ratio of Mg(OH).sub.2 to the aluminum pseudoboehmite powder is 1.05;

(53) K.sub.2O, 1.5 parts by weight, with a particle size of 200 mesh in the Example 4;

(54) magnesia-alumina spinel powder, 3.2 parts by weight, with a particle size of 200 mesh and a specific surface area of 35 m.sup.2/g in the Example 4;

(55) CeO.sub.2, 3.0 parts by weight;

(56) CoO, 1.5 parts by weight;

(57) MoO.sub.3, 1.8 parts by weight; and

(58) citric acid solution of 6 mol/L, 37.8 parts by weight.

(59) The sulfur tolerant CO shift conversion catalyst is prepared by a method comprising the steps of:

(60) S1, weighting the Mg(OH).sub.2 and aluminum pseudoboehmite powder proportionally, and mixing them with 1.5 parts by weight of K.sub.2O, 3.2 parts by weight of magnesia-alumina spinel powder, and 3.0 parts by weight of CeO.sub.2, then adding 37.8 parts by weight of citric acid solution of 6 mol/L, followed by kneading to produce a mixture;

(61) S2, Extruding the mixture to obtain an extruded strip product;

(62) S3, Drying the extruded strip product at a temperature of 140 C. for a period of 5 hours to give a semi-finished product;

(63) S4, Calcining the semi-finished product at a temperature of 650 C. for a period of 6 hours to obtain a catalyst carrier T4;

(64) S5, Impregnating the catalyst carrier T4 with 1.5 parts by weight of CoO and 1.8 parts by weight of MoO.sub.3 by an incipient-wetness impregnation method to obtain an impregnated product; and

(65) S6, Calcining the impregnated product at a temperature of 300 C. for a period of 8 h to obtain the sulfur tolerant CO shift conversion catalyst F4.

Example 5

(66) The Example 5 provides a sulfur tolerant CO shift conversion catalyst, which is prepared by the following materials:

(67) basic magnesium carbonate, 12.2 parts by weight;

(68) aluminium nitrate, when calculated in the form of MgO/Al.sub.2O.sub.3, a molar ratio of the basic magnesium carbonate to the aluminium nitrate is 1.10;

(69) PbO, 0.9 parts by weight,

(70) CaO, 0.9 parts by weight;

(71) magnesia-alumina spinel powder, 1.8 parts by weight;

(72) Pr.sub.2O.sub.3, 1.2 parts by weight;

(73) CoO, 0.5 parts by weight;

(74) MoO.sub.3, 1.9 parts by weight;

(75) nitric acid solution of 0.5 mol/L, 30 parts by weight, and

(76) oxalic acid solution of 0.5 mol/L, 33.3 parts by weight.

(77) The sulfur tolerant carbon monoxide shift conversion catalyst is prepared by a method comprising the steps of:

(78) S1, Weighting the basic magnesium carbonate and aluminium nitrate proportionally, and mixing them with 0.9 parts by weight of PbO, 0.9 parts by weight of CaO, 1.8 parts by weight of magnesia-alumina spinel powder, and 1.2 parts by weight of Pr.sub.2O.sub.3, then adding 30 parts by weight of nitric acid solution of 0.5 mol/L and 33.3 parts by weight of oxalic acid solution of 0.5 mol/L, followed by kneading to produce a mixture;

(79) S2, Extruding the mixture to obtain an extruded strip product;

(80) S3, Drying the extruded strip product at a temperature of 130 C. for a period of 6 hours to give a semi-finished product;

(81) S4, Calcining the semi-finished product at a temperature of 600 C. for a period of 9 hours to obtain a catalyst carrier T5;

(82) S5, Impregnating the catalyst carrier T5 with 0.5 parts by weight of CoO and 1.9 parts by weight of MoO.sub.3 by an incipient-wetness impregnation method to obtain an impregnated product; and

(83) S6, Calcining the impregnated product at a temperature of 400 C. for a period of 5 h to obtain the sulfur tolerant CO shift conversion catalyst F5.

Example 6

(84) The Example 6 provides a sulfur tolerant carbon monoxide shift conversion catalyst which is prepared by the following materials:

(85) light MgO, 5.9 parts by weight, Mg(OH).sub.2, 3 parts by weight;

(86) Al.sub.2O.sub.3.H.sub.2O, when calculated in the form of MgO/Al.sub.2O.sub.3, a molar ratio of the light MgO and Mg(OH).sub.2 to the Al.sub.2O.sub.3.H.sub.2O is 1.36;

(87) B.sub.2O.sub.3, 1.8 parts by weight,

(88) K.sub.2O, 0.5 parts by weight;

(89) magnesia-alumina spinel powder, 2.3 parts by weight;

(90) CeO.sub.2, 1.3 parts by weight,

(91) La.sub.2O.sub.3, 1.0 parts by weight;

(92) CoO, 0.9 parts by weight;

(93) MoO.sub.3, 2.2 parts by weight; and

(94) citric acid solution of 3 mol/L, 44.7 parts by weight.

(95) The sulfur tolerant carbon monoxide shift conversion catalyst is prepared by a method comprising the steps of:

(96) S1, Weighting the light MgO, Mg(OH).sub.2 and Al.sub.2O.sub.3.H.sub.2O proportionally, and mixing them with 1.8 parts by weight of B.sub.2O.sub.3, 0.5 parts by weight of K.sub.2O, 2.3 parts by weight of magnesia-alumina spinel powder, 1.3 parts by weight of CeO.sub.2, and 1.0 parts by weight of La.sub.2O.sub.3, then adding 44.7 parts by weight of citric acid solution of 3 mol/L, followed by kneading to produce a mixture;

(97) S2, Extruding the mixture to obtain an extruded strip product;

(98) S3, Drying the extruded strip product at a temperature of 140 C. for a period of 6 hours to give a semi-finished product;

(99) S4, Calcining the semi-finished product at a temperature of 550 C. for a period of 13 hours to obtain a catalyst carrier T6;

(100) S5, Impregnating the catalyst carrier T6 with 0.9 parts by weight of CoO and 2.2 parts by weight of MoO.sub.3 by an incipient-wetness impregnation method to obtain an impregnated product; and

(101) S6, Calcining the impregnated product at a temperature of 450 C. for a period of 5 h to obtain the sulfur tolerant carbon monoxide shift catalyst F6.

Example 7

(102) The Example 7 provides a sulfur tolerant carbon monoxide shift conversion catalyst, prepared by the following materials:

(103) light MgO, 8.9 parts by weight;

(104) Al.sub.2O.sub.3.H.sub.2O and Al.sub.2O.sub.3.3H.sub.2O, when calculated in the form of MgO/Al.sub.2O.sub.3, a molar ratio of the light MgO to Al.sub.2O.sub.3.H.sub.2O and Al.sub.2O.sub.3.3H.sub.2O is 1.25;

(105) PbO, 1.8 parts by weight,

(106) K.sub.2O, 0.5 parts by weight;

(107) magnesia-alumina spinel powder, 2.3 parts by weight;

(108) CeO.sub.2, 0.8 parts by weight,

(109) La.sub.2O.sub.3, 1.5 parts by weight;

(110) CoO, 0.9 parts by weight;

(111) MoO.sub.3, 2.2 parts by weight; and

(112) oxalic acid solution of 3 mol/L, 63.3 parts by weight.

(113) The sulfur tolerant carbon monoxide shift conversion catalyst is prepared by a method comprising the steps of:

(114) S1, Weighting the light MgO, Al.sub.2O.sub.3.H.sub.2O and Al.sub.2O.sub.3.3H.sub.2O proportionally, and mixing them with 1.8 parts by weight of PbO, 0.5 parts by weight of K.sub.2O, 2.3 parts by weight of magnesia-alumina spinel powder, 0.8 parts by weight of CeO.sub.2, 1.5 parts by weight of La.sub.2O.sub.3, then adding 63.3 parts by weight of oxalic acid solution of 3 mol/L, followed by kneading to produce a mixture;

(115) S2, Extruding the mixture to obtain an extruded strip product;

(116) S3, Drying the extruded strip product at a temperature of 130 C. for a period of 7 hours to give a semi-finished product;

(117) S4, Calcining the semi-finished product at a temperature of 620 C. for a period of 8 hours to obtain a catalyst carrier T7;

(118) S5, Impregnating the catalyst carrier T7 with 0.9 parts by weight of CoO and 2.2 parts by weight of MoO.sub.3 by an incipient-wetness impregnation method to obtain an impregnated product; and

(119) S6, Calcining the impregnated product at a temperature of 420 C. for a period of 6 h to obtain the sulfur tolerant carbon monoxide shift catalyst F7.

Comparative Example 1

(120) The Comparative Example 1 provides a sulfur tolerant carbon monoxide shift conversion catalyst, prepared by the following materials:

(121) basic magnesium carbonate, 18.5 parts by weight;

(122) Al.sub.2O.sub.3, when calculated in the form of MgO/Al.sub.2O.sub.3, a molar ratio of the basic magnesium carbonate to Al.sub.2O.sub.3 is 0.92;

(123) CoO, 0.6 parts by weight;

(124) MoO.sub.3, 1.4 parts by weight; and

(125) nitric acid solution of 1 mol/L, 56 parts by weight.

(126) A process for preparing the sulfur tolerant carbon monoxide shift catalyst comprises the steps of:

(127) S1, Weighting the basic magnesium carbonate and Al.sub.2O.sub.3 proportionally, and then adding 56 parts by weight of nitric acid solution of 1 mol/L, followed by kneading to produce a mixture;

(128) S2, Extruding the mixture to obtain an extruded strip product;

(129) S3, Drying the extruded strip product at a temperature of 120 C. for a period of 5 hours to give a semi-finished product;

(130) S4, Calcining the semi-finished product at a temperature of 550 C. for a period of 6 hours to obtain a catalyst carrier T8;

(131) S5, Impregnating the catalyst carrier T8 with 0.6 parts by weight of CoO and 1.4 parts by weight of MoO.sub.3 by an incipient-wetness impregnation method to obtain an impregnated product; and;

(132) S6, Calcining the impregnated product at a temperature of 300 C. for a period of 2 h to obtain the sulfur tolerant carbon monoxide shift catalyst F8.

Comparative Example 2

(133) The Comparative Example 2 provides a sulfur tolerant carbon monoxide shift catalyst, prepared by the following materials:

(134) basic magnesium carbonate, 18.5 parts by weight;

(135) Al.sub.2O.sub.3, when calculated in the form of MgO/Al.sub.2O.sub.3, a molar ratio of the basic magnesium carbonate to Al.sub.2O.sub.3 is 0.92;

(136) PbO, 3.0 parts by weight, with a particle size of 200 mesh;

(137) CeO.sub.2, 1.5 parts by weight;

(138) CoO, 0.6 parts by weight;

(139) MoO.sub.3, 1.4 parts by weight; and

(140) nitric acid solution of 1 mol/L, 56 parts by weight.

(141) A process for preparing the sulfur tolerant carbon monoxide shift catalyst, comprising the steps of:

(142) S1, Weighting the basic magnesium carbonate and Al.sub.2O.sub.3 proportionally, and mixing them with 3.0 parts by weight of PbO, 1.5 parts by weight of CeO.sub.2, then adding 56 parts by weight of nitric acid solution of 1 mol/L, followed by kneading to produce a mixture;

(143) S2, Extruding the mixture to obtain an extruded strip product;

(144) S3, Drying the extruded strip product at a temperature of 120 C. for a period of 5 hours to give a semi-finished product;

(145) S4, Calcining the semi-finished product at a temperature of 550 C. for a period of 6 hours to obtain a catalyst carrier T9;

(146) S5, Impregnating the catalyst carrier T9 with 0.6 parts by weight of CoO and 1.4 parts by weight of MoO.sub.3 by an incipient-wetness impregnation method to obtain an impregnated product; and;

(147) S6, Calcining the impregnated product at a temperature of 300 C. for a period of 2 h to obtain the sulfur tolerant carbon monoxide shift catalyst F9.

Test Examples

(148) In order to demonstrate the technical effects of the sulfur-tolerant carbon monoxide shift conversion catalyst of the present invention, the following test examples are designed to measure the properties of the sulfur-tolerant carbon monoxide shift conversion catalyst of the above Examples 1-7 and Comparative Examples 1-2:

(149) 1. The Sulfur-Tolerant Carbon Monoxide Shift Catalysts Provided in the Examples 1-7 and Comparative Examples 1-2 are Tested for Measuring their Strength, Pore Volume, Average Pore Diameter and Specific Surface Area.

(150) Strength measurement is carried out in accordance with the standard of HG 2782-1996-T, measurement of anti-crushing force of fertilizer catalyst particle. The measurement of pore volume, average pore diameter and specific surface area is carried out with a gas adsorption pore diameter measuring instrument (Ominisorp 100cx type, Micrometrics company, US). Weighing 0.10 g of dried samples, vacuumizing at a temperature of 200 C. for a period of 2 h till the pressure is less than 10.sup.5 Torr, measuring a adsorption-desorption curve with N.sub.2 as adsorbate, at a liquid nitrogen temperature of 196 C. The specific surface area is calculated out according to the adsorption branch of the adsorption-desorption curve by using BET method. The pore volume and pore distribution are calculated out according to the desorption branch of the adsorption-desorption curve by using BJH method. The results shown in Table 1:

(151) TABLE-US-00001 TABLE 1 Structure parameters Average specific Pore pore surface Strength volume diameter area N .Math. cm.sup.1 (ml .Math. g.sup.1) (nm) (m.sup.2 .Math. g.sup.1) Carrier T1 203 0.49 5.8 168 Carrier T2 223 0.45 6.2 156 Carrier T3 193 0.49 5.5 173 Carrier T4 185 0.43 5.8 157 Carrier T5 186 0.42 5.5 162 Carrier T6 190 0.43 5.6 160 Carrier T7 180 0.44 5.7 158 Carrier T8 158 0.23 8.6 108 Carrier T9 162 0.28 7.9 125

(152) 2. Testing the Activities of the Sulfur-Tolerant Carbon Monoxide Shift Conversion Catalysts F1-F9

(153) The conditions for measuring the activities of the sulfur-tolerant carbon monoxide shift conversion catalyst are as follows: a reaction pressure of 4 Mpa, a gas space velocity of 3000 h.sup.1, a reaction temperature of 250-400 C., a molar ratio of steam to gas at 1.0, and the composition of the raw material gas in mass percentage is: 46 wt % of CO; 5 wt % of CO.sub.2; 1 wt % of H.sub.2S, the balance being H.sub.2. The activity of the catalyst is expressed as the conversion rate of CO, with the results shown in Table 2:

(154) TABLE-US-00002 TABLE 2 250 300 350 400 Conversion Conversion Conversion Conversion rate of rate of rate of rate of CO (%) CO (%) CO (%) CO (%) Catalyst F1 86.2 92.6 93.8 85.6 Catalyst F2 81.5 86.5 89.3 81.6 Catalyst F3 83.3 90.2 91.1 83.3 Catalyst F4 78.0 84.9 87.9 80.2 Catalyst F5 78.2 85.5 88.4 80.8 Catalyst F6 85.0 90.2 89.7 84.4 Catalyst F7 81.7 87.3 88.1 79.8 Catalyst F8 63.1 75.0 79.3 74.6 Catalyst F9 65.3 76.2 80.7 76.5

(155) 3. TEM Image of the Sulfur-Tolerant Carbon Monoxide Shift Conversion Catalyst in Example 1

(156) The CoO and MoO.sub.3 constitute the active component of the catalyst, and the main phase of the active component is MoS.sub.2, as shown in FIG. 1, the MoS.sub.2 phase has a size of about 5 nm. The lattice fringes bent significantly, the lattice spacing is 0.62 nm which is largely consistent with the interplanar spacing (002) of MoS.sub.2, indicating that the sheet-like MoS.sub.2 grows with its (002) plane perpendicular to the carrier. In general, the coordinatively unsaturated position at the sheet-edge of the MoS.sub.2 is the active site of the catalyst, so more active sites can be exposed when the sheet-like active phase grows perpendicularly to the surface of the carrier, thus greatly improving the utilization and performance of the active component of the catalyst.

(157) As can be seen from the above results, the catalyst carriers prepared by the present invention have high strength, high specific surface area, large pore volume, and small pore diameter. The relatively high mechanical strength give the catalyst carriers a good stability. The active phase of the catalyst has a nano-structure, and can expose more active sites. The sulfur-tolerant carbon monoxide shift catalysts provided in the present invention have a higher catalytic activity when compared with that of the Comparative Examples at 250 C., 300 C., 350 C., and 400 C., and shows the optimal activity at 350 C.

(158) Obviously, the above examples are merely illustrations clearly made, and not limited to the embodiments. For those skilled in the art, based on the above description, changes or alterations may be made in other different forms. All embodiments do not need to or cannot be exhaustive hereof. Obvious changes or alterations that is introduced thereof is still within the scope of the invention.