RU2772281C2 - Composition capable of reducing co and nox emissions, its production method and use, and method for catalytic cracking in fluidized layer - Google Patents

Abstract

FIELD: catalytic cracking.

SUBSTANCE: present invention relates to the field of catalytic cracking, in particular to a composition capable of reducing CO and NOx emissions, a method for the production of a composition capable of reducing CO and NOx emissions, a composition capable of reducing CO and NOx emissions, produced by this method, the use of a composition capable of reducing CO and NOx emissions, and a method for catalytic cracking in a fluidized layer (FCC). A composition capable of reducing CO and NOx emissions is described, containing: an inorganic oxide-based carrier and the first element-metal applied to the inorganic oxide-based carrier. The first element-metal is selected from a group consisting of elements-base metals of group VIII. The first element-metal includes Fe and Co. The mass ratio of Fe to Co is 1:(0.1-10) per oxides. The composition also contains the second element-metal applied to the inorganic oxide-based carrier. The second metal is at least one metal selected from a group consisting of elements-metals of group IA and/or IIA. Per the total weight of the composition, the inorganic oxide-based carrier is present in the amount of 10-90 wt. %. Per oxides, the first element-metal is present in the amount of 0.5-50 wt. %, and the second element-metal is present in the amount of 0.5-20 wt. %.

EFFECT: development of an additive suitable for the reduction in contaminant emission in flue gas of a device with incomplete regeneration for the additional reduction in NOx emission in flue gas.

17 cl, 5 dwg, 18 tbl

Description

The field of technology to which the present invention relates

The present invention relates to the field of catalytic cracking, in particular to a composition capable of reducing CO and NOx emissions, a method for producing a composition capable of reducing CO and NOx emissions, a composition capable of reducing CO and NOx emissions obtained by this method, the use of a composition capable of reducing emissions CO and NOx, and the fluid catalytic cracking (FCC) process.

Background of the Invention

The continuous rise in the price of crude oil greatly increases the cost of processing at a refinery. On the one hand, a refinery can drive down costs by buying cheap low-grade oil; on the other hand, economic effects can be increased by deep processing of heavy oil. Catalytic cracking is an important means for processing heavy oil in a refinery and plays an important role in oil refining. It is not only the main tool for balancing heavy oil and obtaining clean fuels in the refinery, but also the key to saving energy and improving refinery efficiency. Catalytic cracking is a fast catalytic reaction system associated with the rapid deactivation of catalysts. Therefore, finding a solution for catalyst regeneration is always the main work in the development of catalytic cracking.

In a fluidized catalytic cracking (FCC) process, the crude oil and the regenerated catalyst are rapidly contacted in a riser to carry out a catalytic cracking reaction. The coke formed during the reaction is deposited on the catalyst and causes its deactivation. The catalyst deactivated by the formed coke is removed and then introduced into the regenerator where it is contacted with air or oxygen-enriched air for regeneration, which enters the regenerator from below to perform regeneration by burning the coke. The regenerated catalyst is fed back to the reactor for re-participation in the catalytic cracking reaction. Based on the excess oxygen content in the flue gas from the regeneration process or the oxidation state of CO, the catalytic cracking device can be divided into a complete regeneration device and a partial regeneration device.

In complete regeneration, the coke and nitrogen compounds in the coke form CO ₂ and N ₂ under the action of the regeneration air. At the same time, pollutants such as CO, NOx and the like are generated. The use of a catalytic additive is an important technical means for controlling CO and NOx emissions.

A promoter for reducing CO emissions in flue gas from regeneration is commonly referred to as a CO combustion promoter. For example, document CN 1022843 C discloses a noble metal carbon monoxide combustion promoter on a carrier, in which the active component is 1-1000 ppm platinum or 50-1000 ppm palladium, and the carrier consists of (1) 99.5- 50% microspheroidal cracking catalyst particles or matrix thereof and (2) 0.5-50% Al ₂ O ₃ , 0-20% RE ₂ O ₃ and 0-15% ZrO ₂ , wherein (2) is the outer coating of the particles (1 ).

A NOx reduction promoter in flue gas is commonly referred to as a NOx reduction additive or NOx reduction additive. For example, document CN 102371150 A discloses a base metal composition for reducing NOx emissions in flue gas from regeneration in a catalytic cracking unit, wherein the composition has a bulk density of not more than 0.65 g/ml and contains, in terms of oxide (1) 50 -99 wt. % carrier based on inorganic oxide, (2) 0.5-40 wt. % of one or more elements selected from the group consisting of non-noble metal elements of groups IIA, IIB, IVB and VIB, and (3) 0.5-30 wt. % rare earth element based on the weight of the composition. When used in an FCC, the composition can significantly reduce NOx emissions in flue gas from regeneration.

There is also a kind of promoter capable of simultaneously reducing CO and NOx emissions in flue gas from regeneration, which can both promote CO combustion and reduce NOx emissions. As environmental regulations become more and more stringent, the use of such a promoter becomes more frequent. For example, document CN 1688508 A discloses a composition for reducing NOx and CO emissions in flue gas from the FCC and its use, wherein the composition contains copper and/or cobalt and a carrier selected from the group consisting of hydrotalcite compounds, spinel, alumina, zinc titanate , zinc aluminate and zinc titanate/zinc aluminate. CN 102371165 A discloses a low bulk density composition for reducing CO and NOx emissions in flue gas from FCC regeneration, the composition comprising a rare earth element and one or more base metal elements, preferably on a Y-zeolite carrier. US 6,165,933 discloses a CO combustion-promoting composition (promoter) for reducing NOx emissions in a catalytic cracking process, comprising: (i) an acidic metal oxide substantially free of zeolite; (ii) an alkali metal, an alkaline earth metal, or a mixture thereof; (iii) an oxygen-containing component; and (iv) palladium, wherein the inorganic oxide support is preferably silica-alumina and the oxygen-containing transition metal oxide is preferably cerium dioxide. US 7,045,056 discloses a composition for simultaneously reducing CO and NOx emissions in flue gas from catalytic cracking, comprising: (i) an inorganic oxide carrier; (ii) cerium oxide; (iii) an oxide of a lanthanide other than cerium, wherein the weight ratio of (ii) to (iii) is at least 1.66:1; (iv) optionally a transition metal oxide from Group IB and IIB; and (v) at least one noble metal element. Document CN 105363444 A discloses a composition for reducing CO and NOx emissions in flue gas from FCC regeneration, containing in terms of oxide (1) 0.5-30 wt. % rare earth element, (2) 0.01-0.15 wt. % of a noble metal element, and (3) the remaining portion of the inorganic oxide-based carrier is substantially free of alkali metal and alkaline earth metal, and a method for producing the same, wherein the noble metal composition is treated with an alkaline solution before drying and/or calcination. When used in FCC, the disclosed composition can effectively avoid "after-burning" caused by high concentration of CO in flue gas from regeneration, effectively control flue gas CO and NOx emissions from regeneration, and significantly reduce flue gas NOx emissions, and essentially has no detrimental effect on distribution of FCC products.

In case of incomplete regeneration due to a small excess of oxygen and a high concentration of CO in the flue gas, the concentration of NOx in the flue gas at the outlet of the regenerator is very low, while the concentration of reduced nitrides such as NH ₃ , HCN and the like is high. These reduced nitrides flow downstream with the flue gas to a CO distiller for energy recovery, in which, if they are completely oxidized, NOx is formed, and if they are not completely oxidized, the remaining NH ₃ and the like can easily cause the ammonia-nitrogen standard to be exceeded. in the downstream scrubber effluent or react with SOx in the flue gas to form ammonium salt precipitates, which can cause salt deposits in the waste heat boiler or other flue gas post-treatment equipment (such as the SCR), affecting unit life. Thus, the catalyst additive is used in the regenerator in a partial regeneration process to catalyze the conversion of NH ₃ and the like, so that the emission of NOx in the flue gas can be reduced and the operation period of the device can be extended.

US 5,021,144 discloses a method for reducing NH ₃ emissions in flue gas from an FCC device with incomplete regeneration, wherein the CO combustion promoter is added to the regenerator in an excess amount that is 2-3 times the minimum amount necessary to prevent fluidized bed burnout. Although such a method can reduce the emission of NH ₃ in the flue gas from the incompletely regenerated FCC device, a large amount of CO is used, which has the disadvantage of high energy consumption and is not beneficial in terms of environmental protection.

US 4,755,282 discloses a process for reducing NH ₃ emissions in flue gas from an FCC device with partial regeneration or incomplete regeneration, wherein an ammonia decomposition catalyst with a particle size of 10-40 µm is added to the regenerator and maintained at some concentration in the fluidized bed to convert NH ₃ to N ₂ and water. The active component of the ammonia decomposition catalyst may be a noble metal dispersed on an inorganic oxide support.

CN 101024179 A discloses a NOx reduction composition for use in an FCC process comprising (i) an acidic metal oxide substantially free of zeolite, (ii) an alkali metal, an alkaline earth metal, or a mixture thereof, and (iii) an oxygen containing component. The noble metal impregnated composition is used to convert gaseous reduced nitrogen-containing substances in flue gas from a partial recovery catalytic cracker and thereby reduce NOx emissions in the flue gas.

Currently, there are few reports on the study and use of an additive to control NH ₃ and NOx emissions in flue gas from a device with incomplete regeneration. Due to the significant difference in the composition of the flue gas from the partial recovery device and the full recovery device, existing catalytic additives suitable for the full recovery device do not have an ideal effect when used in the partial recovery device. Although the additive compositions disclosed in the above documents can catalyze the conversion of reduced nitrides such as NH ₃ and the like in flue gas to some extent, the catalytic conversion activity of reduced nitrides such as NH ₃ and the like in flue gas still needs to be further improved. to reduce the effect of NH ₃ scale deposits and the like on equipment operation. Thus, there is a need to develop an additive suitable for reducing the emission of contaminants in the flue gas of a device with incomplete regeneration to further reduce the emission of NOx in the flue gas.

Brief summary of the present invention

In order to overcome the disadvantages of low catalytic conversion activity towards reduced nitrides such as NH ₃ and the like, in the regeneration process of the prior art, the present invention provides a new composition capable of reducing CO and NOx emissions, a method for producing a composition capable of reducing CO and NOx emissions, a composition capable of reducing CO and NOx emissions obtained by this method, and using a composition capable of reducing CO and NOx emissions in flue gas treatment, as well as a fluid catalytic cracking (FCC) method. The composition of the present invention capable of reducing CO and NOx emissions has a high catalytic conversion activity for reduced nitrides, is obtained in a simple manner, and when used in an FCC process, can effectively reduce CO and NOx emissions in flue gas from regeneration in the FCC process. The composition according to the present invention, which is capable of reducing CO and NOx emissions, is particularly suitable for treating flue gas from an incomplete regeneration operation.

The inventors of the present invention have found through research that by using Group VIII non-noble metal elements (referred to as "first metal"), which include Fe and Co as an active component, together with an inorganic oxide as a carrier, CO and NOx emissions in flue gas can be effectively reduced. gas from regeneration in the catalytic cracking process. Reasons are believed to include the following. The first metal includes Fe and Co in a specific amount, which leads to some synergistic effect and which is preferable for reducing the formation of oxidized nitrogen compounds and promoting the decomposition of reduced nitrogen compounds. The present inventors have also found that when the first metal is used in combination with at least one Group IA and/or IIA metal element (referred to as "second metal"), and/or at least one Group IB-base metal element- VIIB (referred to as "third metal"), and/or at least one noble metal element (referred to as "fourth metal"), wherein Fe and Co are used together as base metal elements and modified with a second metal and/or a third metal , and/or a fourth metal, can further reduce the formation of oxidized nitrogen compounds and further promote the decomposition of reduced nitrogen compounds.

Further research has found that preferably, after spray drying, by treating the solid materials obtained by spray drying in a carbonaceous atmosphere at a high temperature, CO and NOx emissions in flue gas from regeneration in a catalytic cracking process can be more effectively reduced. In the above preferred case, after the structure of the composition capable of reducing CO and NOx emissions can be further processed and stabilized, the composition capable of reducing CO and NOx emissions can have a significantly better catalytic conversion activity against reduced nitrides such as NH ₃ and the like, as well as better hydrothermal stability, and meet the requirements of the hydrothermal environment of the regenerator for a composition capable of reducing CO and NOx emissions.

Based on the above, in a first aspect, the present invention provides a composition capable of reducing CO and NOx emissions, comprising: an inorganic oxide carrier and a first metal element supported on the inorganic oxide carrier, the first metal element being selected from the group consisting of of Group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, and wherein the weight ratio of Fe and Co is 1:(0.1-10) in terms of oxides. Optionally, a second metal (which is at least one selected from the group consisting of metal elements from group IA and/or IIA) and/or a third metal (which is at least one selected from the group consisting of non-noble metal elements of groups IB-VIIB), and/or a fourth metal (which is at least one selected from the group consisting of noble metal elements).

In a second aspect, according to the present invention, there is provided a method for producing a composition capable of reducing CO and NOx emissions, comprising: obtaining a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor and water, spray drying the slurry, and then calcining to obtain a composition. When a second metal and/or a third metal is additionally supported on the carrier, the method comprises preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor, and/or a third metal precursor and water, spray drying the slurry, and then calcining with obtaining a composition. When a fourth metal is additionally applied to the carrier, the method further comprises: impregnating the composition obtained in the previous steps in an impregnating solution containing a precursor of the fourth metal to obtain a solid product, and then drying the solid product and/or performing a second calcination of the solid product.

In a third aspect, according to the present invention, there is provided a composition capable of reducing CO and NOx emissions obtained by the above production method.

In a fourth aspect, the present invention provides for the use of a composition capable of reducing CO and NOx emissions in flue gas treatment.

In a fifth aspect, the present invention provides for the use of a composition capable of reducing CO and NOx emissions in the treatment of flue gas from regeneration in a catalytic cracking process.

In the sixth aspect of the present invention, there is provided a fluidized catalytic cracking process comprising: contacting and reacting liquid petroleum products with a catalyst and regenerating the catalyst after contact and reaction, wherein the catalyst comprises a catalytic cracking catalyst and a composition capable of reducing CO and NOx emissions, and wherein a composition capable of reducing CO and NOx emissions is a composition capable of reducing CO and NOx emissions according to the present invention.

In particular, the present invention relates to the following objects.

1. A composition capable of reducing CO and NOx emissions, comprising: a carrier based on an inorganic oxide and a first metal element deposited on a carrier based on an inorganic oxide, the first metal element being selected from the group consisting of non-noble metal elements of group VIII, wherein the first metal element comprises Fe and Co, and wherein the weight ratio of Fe to Co is 1:(0.1-10) in terms of oxides.

2. A composition capable of reducing CO and NOx emissions, comprising: a carrier based on an inorganic oxide and a first metal element and a second metal element deposited on a carrier based on an inorganic oxide, the first metal element being selected from the group consisting of elements - non-noble metals of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.1-10) in terms of oxides, and the second metal is at least one selected from the group , consisting of metal elements of group IA and / or IIA.

3. A composition capable of reducing CO and NOx emissions, comprising: a carrier based on an inorganic oxide and a first metal element and a third metal element deposited on a carrier based on an inorganic oxide, the first metal element being selected from the group consisting of elements - non-noble metals of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.1-10) in terms of oxides, and the third metal is at least one selected from the group , consisting of base metal elements of groups IB-VIIB.

4. A composition capable of reducing CO and NOx emissions, comprising: a carrier based on an inorganic oxide and a first metal element and a fourth metal element deposited on a carrier based on an inorganic oxide, the first metal element being selected from the group consisting of elements - non-noble metals of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.05-20) in terms of oxides, and the fourth metal is at least one selected from the group , consisting of noble metal elements.

5. A composition capable of reducing CO and NOx emissions, comprising: a carrier based on an inorganic oxide and a first metal element, a second metal element and a third metal element supported on a carrier based on an inorganic oxide, the first metal element being selected from the group , consisting of non-noble metal elements of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.05-20) in terms of oxides, and the second metal is at least one , selected from the group consisting of metal elements of groups IA and/or IIA, and wherein the third metal is at least one selected from the group consisting of base metal elements of groups IB-VIIB.

6. A composition capable of reducing CO and NOx emissions, comprising: a carrier based on an inorganic oxide and a first metal element, a second metal element and a fourth metal element supported on a carrier based on an inorganic oxide, the first metal element being selected from the group , consisting of non-noble metal elements of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.05-20) in terms of oxides, and the second metal is at least one , selected from the group consisting of metal elements of group IA and/or IIA, and wherein the fourth metal is at least one selected from the group consisting of noble metal elements.

7. A composition capable of reducing CO and NOx emissions, comprising: a carrier based on an inorganic oxide and a first metal element, a third metal element and a fourth metal element deposited on a carrier based on an inorganic oxide, the first metal element being selected from the group , consisting of non-noble metal elements of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.05-20) in terms of oxides, the third metal is at least one, selected from the group consisting of non-noble metal elements of groups IB-VIIB, and wherein the fourth metal is at least one selected from the group consisting of noble metal elements.

8. A composition capable of reducing CO and NOx emissions, comprising: a carrier based on an inorganic oxide and a first metal element, a second metal element, a third metal element and a fourth metal element deposited on a carrier based on an inorganic oxide, the first element -metal is selected from the group consisting of group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the weight ratio of Fe to Co is 1:(0.05-20) in terms of oxides, the second metal being is at least one selected from the group consisting of metal elements of groups IA and/or IIA, wherein the third metal is at least one selected from the group consisting of base metal elements of groups IB-VIIB, and wherein the fourth the metal is at least one selected from the group consisting of noble metal elements.

9. The composition according to any one of the preceding paragraphs, in which, in terms of the total weight of the composition, the carrier based on inorganic oxide is in the amount of 60-95 wt. %, and the total amount of Fe and Co is 5-40 wt. % in terms of oxides,

preferably the carrier based on the inorganic oxide is in the amount of 75-92 wt. %, and the total amount of Fe and Co is 8-25 wt. % in terms of oxides,

preferably the carrier based on the inorganic oxide is in the amount of 84-90 wt. %, and the total amount of Fe and Co is 10-16 wt. % in terms of oxides.

10. The composition according to any one of the preceding paragraphs, in which, in terms of the total weight of the composition, the carrier based on inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, and the second metal element is in the amount of 1-20 wt. %,

preferably the carrier based on the inorganic oxide is in the amount of 60-90 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, and the second metal element is in the amount of 5-15 wt. %,

even more preferably, the inorganic oxide carrier is in the amount of 72-85 wt. %, and in terms of oxides, the first metal element is in the amount of 10-16 wt. %, and the second metal element is in the amount of 5-12 wt. %.

11. The composition according to any one of the preceding paragraphs, in which, in terms of the total weight of the composition, the carrier based on inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, and the third metal element is in the amount of 1-20 wt. %,

preferably the carrier based on the inorganic oxide is in the amount of 60-90 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, and the third metal element is in the amount of 2-15 wt. %,

even more preferably the carrier based on inorganic oxide is in the amount of 76-86 wt. %, and in terms of oxides, the first metal element is in the amount of 10-16 wt. %, and the third metal element is in the amount of 2-8 wt. %.

12. The composition according to any of the preceding paragraphs, in which, in terms of the total weight of the composition, the carrier based on inorganic oxide is in the amount of 59.9-94.995 wt. %, the first metal element is in the amount of 5-40 wt. % in terms of oxides, and the fourth metal element is in the amount of 0.005-0.1 wt. % in terms of elements,

preferably, the carrier based on the inorganic oxide is in the amount of 74.92-91.99 wt. %, the first metal element is in the amount of 8-25 wt. % in terms of oxides, and the fourth metal element is in the amount of 0.01-0.08 wt. % in terms of elements,

even more preferably, the inorganic oxide carrier is in the amount of 83.93-89.95 wt. %, the first metal element is in the amount of 10-16 wt. % in terms of oxides, and the fourth metal element is in the amount of 0.05-0.07 wt. % in terms of elements.

13. The composition according to any one of the preceding paragraphs, in which, in terms of the total weight of the composition, the carrier based on inorganic oxide is in the amount of 10-90 wt. %, and in terms of oxides, the first metal element is in the amount of 0.5-50 wt. %, the second metal element is in the amount of 0.5-20 wt. %, and the third metal element is in the amount of 0.5-20 wt. %,

preferably the carrier based on the inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, and the third metal element is in the amount of 1-10 wt. %,

even more preferably, the carrier based on the inorganic oxide is in the amount of 55-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, the second metal element is in the amount of 5-15 wt. %, and the third metal element is in the amount of 2-8 wt. %.

14. The composition according to any one of the preceding paragraphs, in which, in terms of the total weight of the composition, the carrier based on inorganic oxide is in the amount of 30-90 wt. %, and in terms of oxides, the first metal element is in the amount of 0.5-50 wt. %, the second metal element is in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.001-0.15 wt. %,

preferably the carrier based on the inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %,

even more preferably, the carrier based on inorganic oxide is in the amount of 60-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, the second metal element is in the amount of 2-15 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.01-0.08 wt. %.

15. The composition according to any one of the preceding paragraphs, in which, in terms of the total weight of the composition, the carrier based on inorganic oxide is in the amount of 30-90 wt. %, and in terms of oxides, the first metal element is in the amount of 0.5-50 wt. %, the third metal element is in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.001-0.15 wt. %,

preferably the carrier based on the inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the third metal element is in the amount of 1-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %,

even more preferably, the carrier based on inorganic oxide is in the amount of 60-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, the third metal element is in the amount of 2-15 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.01-0.08 wt. %.

16. The composition according to any one of the preceding paragraphs, in which, in terms of the total weight of the composition, the carrier based on inorganic oxide is in the amount of 10-90 wt. %, and in terms of oxides, the first metal element is in the amount of 0.5-50 wt. %, the second metal element is in the amount of 0.5-20 wt. %, the third metal element is in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.001-0.15 wt. %,

preferably the carrier based on the inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, the third metal element is in the amount of 1-10 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %,

even more preferably, the carrier based on the inorganic oxide is in the amount of 55-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, the second metal element is in the amount of 5-15 wt. %, the third metal element is in the amount of 2-8 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.01-0.08 wt. %.

17. The composition according to any one of the preceding claims, wherein the weight ratio of Fe to Co is 1:(0.1-10), preferably 1:(0.3-3) and more preferably 1:(0.5-2) in in terms of oxides.

18. A composition according to any one of the preceding claims, wherein,

at least part of the Fe in the composition is in the form of iron carbide and/or elemental iron;

at least a portion of the Co in the composition is in the form of cobalt monoxide and/or elemental cobalt;

preferably, at least part of the Fe in the composition is in the form of iron carbide;

at least a portion of the Co in the composition is in the form of elemental cobalt;

more preferably, the x-ray pattern of the composition contains diffraction peaks at 2θ 42.6°, 44.2° and 44.9°.

19. A composition according to any one of the preceding claims, wherein the inorganic oxide carrier is at least one selected from the group consisting of alumina, silica-alumina, zeolite, spinel, kaolin, diatomite, perlite and perovskite,

preferably at least one selected from the group consisting of alumina, spinel and perovskite,

and even more preferably alumina.

20. A composition according to any one of the preceding claims, wherein the second metal element is at least one selected from the group consisting of Na, K, Mg and Ca, preferably K and/or Mg, most preferably Mg;

the third metal element is at least one selected from the group consisting of Cu, Zn, Ti, Zr, V, Cr, Mo, W, Mn and rare earth elements, preferably at least one selected from the group consisting of Zr, V, W, Mn, Ce and La, most preferably Mn;

the fourth metal element is at least one selected from the group consisting of Pt, Ir, Pd, Ru and Rh, most preferably Ru.

21. A method for producing a composition capable of reducing CO and NOx emissions, comprising:

obtaining a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor and water, spray drying the slurry, and then calcining;

wherein the precursor of the first metal element comprises an Fe precursor and a Co precursor, wherein the Fe precursor and Co precursor are used in such amounts that the weight ratio of Fe to Co in the resulting composition is 1:(0.1-10) in terms of oxides.

22. A method for producing a composition capable of reducing CO and NOx emissions, comprising:

obtaining a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor and water, spray drying the slurry, and then calcining;

wherein the first metal element is selected from the group consisting of Group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the second metal is at least one selected from the group consisting of Group IA metal elements and /or IIA, and moreover, in the precursor of the first metal element, the Fe precursor and the Co precursor are used in such amounts that the mass ratio of Fe to Co in the resulting composition is 1: (0.1-10) in terms of oxides.

23. A method for producing a composition capable of reducing CO and NOx emissions, comprising:

obtaining a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a third metal precursor and water, spray-drying the slurry, and then calcining;

wherein the first metal element is selected from the group consisting of Group VIII base metal elements, wherein the first metal element comprises Fe and Co, wherein the third metal is at least one selected from the group consisting of Group IB base metal elements -VIIB, and moreover, in the precursor of the first metal element, the Fe precursor and the Co precursor are used in such amounts that the mass ratio of Fe to Co in the resulting composition is 1:(0.1-10) in terms of oxides.

24. A method for producing a composition capable of reducing CO and NOx emissions, comprising:

(1) preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, and water, spray drying the slurry, and performing a first calcination to obtain a semi-finished composition;

(2) impregnating the semi-finished composition obtained in step (1) in an impregnating solution containing a precursor of the fourth metal element to obtain a solid product, and then drying the solid product and/or performing a second calcination,

wherein the first metal element is selected from the group consisting of Group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the fourth metal is at least one selected from the group consisting of noble metal elements, and moreover, in the precursor of the first metal element, the Fe precursor and the Co precursor are used in such amounts that the mass ratio of Fe to Co in the resulting composition is 1:(0.05-20) in terms of oxides.

25. A method for producing a composition capable of reducing CO and NOx emissions, comprising:

obtaining a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor, a third metal precursor, and water, spray drying the slurry, and then calcining;

wherein the first metal element is selected from the group consisting of Group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the second metal is at least one selected from the group consisting of Group IA metal elements and / or IIA, wherein the third metal is at least one selected from the group consisting of non-noble metal elements of groups IB-VIIB, and wherein in the precursor of the first metal element, the Fe precursor and the Co precursor are used in such amounts that the mass ratio Fe to Co in the resulting composition was 1:(0.05-20) in terms of oxides.

26. A method for producing a composition capable of reducing CO and NOx emissions, comprising:

(1) preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor, and water, spray drying the slurry, and then performing a first calcination to obtain a semi-finished composition;

(2) impregnating the semi-finished composition obtained in step (1) in an impregnating solution containing a precursor of the fourth metal element to obtain a solid product, and then drying the solid product and/or performing a second calcination,

wherein the first metal element is selected from the group consisting of Group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the second metal is at least one selected from the group consisting of Group IA metal elements and / or IIA, wherein the fourth metal is at least one selected from the group consisting of noble metal elements, and wherein in the precursor of the first metal element, the Fe precursor and the Co precursor are used in such amounts that the weight ratio of Fe to Co in the resulting composition was 1:(0.05-20) in terms of oxides.

27. A method for producing a composition capable of reducing CO and NOx emissions, comprising:

(1) preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a third metal precursor, and water, spray drying the slurry, and then performing a first calcination to obtain a semi-finished composition;

(2) impregnating the semi-finished composition obtained in step (1) in an impregnating solution containing a precursor of the fourth metal element to obtain a solid product, and then drying the solid product and/or performing a second calcination,

wherein the first metal element is selected from the group consisting of Group VIII base metal elements, wherein the first metal element comprises Fe and Co, wherein the third metal is at least one selected from the group consisting of Group IB base metal elements -VIIB, wherein the fourth metal is at least one selected from the group consisting of noble metal elements, and wherein, in the precursor of the first metal element, the Fe precursor and the Co precursor are used in such amounts that the weight ratio of Fe to Co in the resulting composition was 1:(0.05-20) in terms of oxides.

28. A method for producing a composition capable of reducing CO and NOx emissions, comprising:

(1) preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor, a third metal precursor, and water, spray drying the slurry, and then performing a first calcination to obtain a semi-finished composition;

(2) impregnating the semi-finished composition obtained in step (1) in an impregnating solution containing a precursor of the fourth metal element to obtain a solid product, and then drying the solid product and/or performing a second calcination,

wherein the first metal element is selected from the group consisting of Group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the second metal is at least one selected from the group consisting of Group IA metal elements and /or IIA, wherein the third metal is at least one selected from the group consisting of non-noble metal elements of groups IB-VIIB, wherein the fourth metal is at least one selected from the group consisting of noble metal elements, and moreover, in the precursor of the first metal element, the Fe precursor and the Co precursor are used in such amounts that the mass ratio of Fe to Co in the resulting composition is 1:(0.05-20) in terms of oxides.

29. The method according to any one of the preceding claims, wherein the inorganic oxide carrier precursor and the first metal element precursor are used in such amounts that in the resulting composition, based on the total weight of the composition, the inorganic oxide carrier is in an amount of 60-95 wt. . %, and the total amount of Fe and Co was 5-40 wt. % in terms of oxides,

preferably the carrier based on the inorganic oxide is in the amount of 75-92 wt. %, and the total amount of Fe and Co is 8-25 wt. % in terms of oxides,

preferably the carrier based on the inorganic oxide is in the amount of 84-90 wt. %, and the total amount of Fe and Co is 10-16 wt. % in terms of oxides.

30. The method according to any one of the preceding claims, wherein the inorganic oxide carrier precursor, the first metal element precursor, and the second metal element precursor are used in such amounts that the resulting composition, based on the total weight of the composition, contains the inorganic oxide carrier. in the amount of 50-90 wt. %, and in terms of oxides, the first metal element was in the amount of 3-30 wt. %, and the second metal element was in the amount of 1-20 wt. %,

preferably the media based on the inorganic oxide was in the amount of 60-90 wt. %, and in terms of oxide, the first metal element was in the amount of 5-25 wt. %, and the second metal element was in the amount of 5-15 wt. %,

even more preferably the carrier based on the inorganic oxide was in the amount of 72-85 wt. %, and in terms of oxides, the first metal element was in the amount of 10-16 wt. %, and the second metal element was in the amount of 5-12 wt. %.

31. The method according to any one of the preceding claims, wherein the inorganic oxide carrier precursor, the first metal element precursor, and the third metal element precursor are used in such amounts that the resulting composition, based on the total weight of the composition, contains the inorganic oxide carrier. in the amount of 50-90 wt. %, and in terms of oxides, the first metal element was in the amount of 3-30 wt. %, and the third metal element was in the amount of 1-20 wt. %,

preferably the media based on the inorganic oxide was in the amount of 60-90 wt. %, and in terms of oxide, the first metal element was in the amount of 5-25 wt. %, and the third metal element was in the amount of 2-15 wt. %,

even more preferably, the inorganic oxide carrier was in the amount of 76-86 wt. %, and in terms of oxide, the first metal element was in the amount of 10-16 wt. %, and the third metal element was in the amount of 2-8 wt. %.

32. The method according to any one of the preceding claims, wherein the inorganic oxide carrier precursor, the first metal element precursor, and the fourth metal element precursor are used in such amounts that the resulting composition, based on the total weight of the composition, contains the inorganic oxide carrier. in the amount of 59.9-94.995 wt. %, the first metal element was in the amount of 5-40 wt. % in terms of oxides, and the fourth metal element was in the amount of 0.005-0.1 wt. % in terms of elements,

preferably, the carrier based on the inorganic oxide was in the amount of 74.92-91.99 wt. %, the first metal element was in the amount of 8-25 wt. % in terms of oxides, and the fourth metal element was in the amount of 0.01-0.08 wt. % in terms of elements,

even more preferably, the inorganic oxide carrier was in the amount of 83.93-89.95 wt. %, the first metal element was in the amount of 10-16 wt. % in terms of oxides, and the fourth metal element was in the amount of 0.05-0.07 wt. % in terms of elements.

33. The method according to any one of the preceding claims, wherein the inorganic oxide support precursor, the first metal element precursor, the second metal element precursor, and the third metal element precursor are used in such amounts that in the resulting composition, based on the total weight of the composition carrier based on inorganic oxide was in the amount of 10-90 wt. %, and in terms of oxides, the first metal element was in the amount of 0.5-50 wt. %, the second metal element was in the amount of 0.5-20 wt. %, and the third metal element was in the amount of 0.5-20 wt. %,

preferably the media based on the inorganic oxide was in the amount of 50-90 wt. %, and in terms of oxides, the first metal element was in the amount of 3-30 wt. %, the second metal element was in the amount of 1-20 wt. %, and the third metal element was in the amount of 1-10 wt. %,

even more preferably, the carrier based on the inorganic oxide was in the amount of 55-85 wt. %, and in terms of oxides, the first metal element was in the amount of 5-25 wt. %, the second metal element was in the amount of 5-15 wt. %, and the third metal element was in the amount of 2-8 wt. %.

34. The method according to any of the preceding claims, wherein the inorganic oxide support precursor, the first metal element precursor, the second metal element precursor, and the fourth metal element precursor are used in such amounts that in the resulting composition, based on the total weight of the composition carrier based on inorganic oxide was in the amount of 30-90 wt. %, and in terms of oxides, the first metal element was in the amount of 0.5-50 wt. %, the second metal element was in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.001-0.15 wt. %,

preferably the media based on the inorganic oxide was in the amount of 50-90 wt. %, and in terms of oxides, the first metal element was in the amount of 3-30 wt. %, the second metal element was in the amount of 1-20 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.005-0.1 wt. %,

even more preferably, the carrier based on the inorganic oxide was in the amount of 60-85 wt. %, and in terms of oxides, the first metal element was in the amount of 5-25 wt. %, the second metal element was in the amount of 2-15 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.01-0.08 wt. %.

35. The method according to any one of the preceding claims, wherein the inorganic oxide support precursor, the first metal element precursor, the third metal element precursor, and the fourth metal element precursor are used in such amounts that in the resulting composition, based on the total weight of the composition, carrier based on inorganic oxide was in the amount of 30-90 wt. %, and in terms of oxides, the first metal element was in the amount of 0.5-50 wt. %, the third metal element was in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.001-0.15 wt. %,

preferably the media based on the inorganic oxide was in the amount of 50-90 wt. %, and in terms of oxides, the first metal element was in the amount of 3-30 wt. %, the third metal element was in the amount of 1-20 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.005-0.1 wt. %,

even more preferably, the carrier based on the inorganic oxide was in the amount of 60-85 wt. %, and in terms of oxides, the first metal element was in the amount of 5-25 wt. %, the third metal element was in the amount of 2-15 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.01-0.08 wt. %.

36. A method according to any one of the preceding claims, wherein the inorganic oxide support precursor, the first metal element precursor, the second metal element precursor, the third metal element precursor, and the fourth metal element precursor are used in such amounts that in the resulting composition in terms of the total weight of the composition, the carrier based on the inorganic oxide was in the amount of 10-90 wt. %, and in terms of oxides, the first metal element was in the amount of 0.5-50 wt. %, the second metal element was in the amount of 0.5-20 wt. %, the third metal element was in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.001-0.15 wt. %,

preferably the media based on the inorganic oxide was in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element was in the amount of 1-20 wt. %, the third metal element is in the amount of 1-10 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.005-0.1 wt. %,

even more preferably, the carrier based on the inorganic oxide was in the amount of 55-85 wt. %, and in terms of oxides, the first metal element was in the amount of 5-25 wt. %, the second metal element was in the amount of 5-15 wt. %, the third metal element was in the amount of 2-8 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.01-0.08 wt. %.

37. The method according to any one of the preceding claims, wherein the calcination in step (1) is carried out in a carbon-containing atmosphere at a temperature of 400-1000°C, preferably 450-650°C, for 0.1-10 hours, preferably 1-3 hours ;

preferably, the carbon-containing atmosphere is provided by an elemental carbon-containing gas, the elemental carbon-containing gas being at least one selected from the group consisting of CO, methane and ethane, preferably CO.

38. The method according to any one of the preceding claims, wherein the Fe precursor and Co precursor are used in such amounts that the weight ratio of Fe to Co in the resulting composition is 1:(0.3-3), preferably 1:(0.4-2 ), in terms of oxides.

39. The method according to any one of the preceding paragraphs, and the method further provides after the impregnation of stage (2) performing alkaline treatment of the solid product before drying and/or second calcination;

preferably the alkaline treatment comprises: obtaining a slurry by mixing the solid product and the alkaline solution, or washing the solid product with the alkaline solution;

preferably the alkaline solution is an alkaline solution of a non-metal element, preferably aqueous ammonia and/or an alkaline ammonium salt solution;

preferably the alkaline solution has a concentration of 0.01-10 mol/l, preferably 0.05-5 mol/l;

preferably the alkaline solution is used in an amount by volume of 1-10 times the pore volume of the solid product, preferably 1.5-5 times.

40. The method according to any one of the preceding claims, wherein the inorganic oxide carrier is at least one selected from the group consisting of alumina, silica-alumina, zeolite, spinel, kaolin, diatomite, perlite and perovskite, preferably at least one selected from the group consisting of alumina, spinel and perovskite, and particularly preferably alumina;

preferably the alumina precursor is treated with acid peptization before making the slurry, and particularly preferably the acid used in the acid peptization is hydrochloric acid and the acid peptization is carried out with an acid to alumina ratio of 0.12-0.22:1 for 20-40 minutes.

41. The method according to any of the preceding paragraphs, in which the second metal element is at least one selected from the group consisting of Na, K, Mg and Ca, preferably K and/or Mg, most preferably Mg;

the third metal element is at least one selected from the group consisting of Cu, Zn, Ti, Zr, V, Cr, Mo, W, Mn and rare earth elements, preferably at least one selected from the group consisting of Zr, V, W, Mn, Ce and La, most preferably Mn;

the fourth metal element is at least one selected from the group consisting of Pt, Ir, Pd, Ru and Rh, most preferably Ru,

the first metal element precursor, the second metal element precursor, the third metal element precursor, and the fourth metal element precursor are respectively selected from the groups consisting of water-soluble salts of the first metal element, water-soluble salts of the second metal element, water-soluble salts of the third metal element; and water-soluble salts of the fourth metal element.

42. Composition capable of reducing CO and NOx emissions, obtained by the method according to any one of the preceding paragraphs 21-41.

43. The use of a composition capable of reducing CO and NOx emissions according to any one of the preceding paragraphs 1-20 and 42 for flue gas treatment.

44. The use of a composition capable of reducing CO and NOx emissions according to any of the preceding claims 1-20 and 42 for treating flue gas from regeneration in a catalytic cracking process.

45. A method for catalytic cracking in a fluidized bed, comprising: contacting and reacting liquid petroleum products with a catalyst and regenerating the catalyst after contact and reaction, wherein the catalyst contains a catalytic cracking catalyst and a composition capable of reducing CO and NOx emissions, and moreover, a composition capable of reducing CO emissions and NOx, is a composition capable of reducing CO and NOx emissions according to any of the preceding paragraphs 1-20 and 42.

46. The method of catalytic cracking in a fluidized bed according to p. 45, in which the composition capable of reducing CO and NOx emissions is in an amount of 0.05-5 wt. %, preferably 0.1-3 wt. %, based on the total weight of the catalyst.

Preferably, the present invention relates to the following objects.

1. A composition capable of reducing CO and NOx emissions, comprising: a carrier based on an inorganic oxide and a first metal element deposited on a carrier based on an inorganic oxide, the first metal element being selected from the group consisting of non-noble metal elements of group VIII, wherein the first metal element comprises Fe and Co, and wherein the weight ratio of Fe to Co is 1:(0.1-10) in terms of oxides.

2. The composition according to claim 1, wherein the composition also comprises a second metal element supported on an inorganic oxide carrier, the second metal being at least one selected from the group consisting of metal elements from group IA and/or IIA, and moreover, in terms of the total weight of the composition, the carrier based on the inorganic oxide is in the amount of 10-90 wt. %, and in terms of oxides, the first metal element is in the amount of 0.5-50 wt. %, and the second metal element is in the amount of 0.5-20 wt. %.

3. The composition according to claim 1 or claim 2, wherein the composition also contains a third metal element supported on an inorganic oxide carrier, the third metal is at least one selected from the group consisting of base metal elements from the groups IB-VIIB, and in terms of the total weight of the composition, the third metal element is in the amount of 0.5-20 wt. % in terms of oxides.

4. The composition according to any one of the preceding claims 1-3, wherein the composition also comprises a fourth metal element deposited on an inorganic oxide carrier, the fourth metal being at least one selected from the group consisting of noble metal elements, and moreover, in terms of the total weight of the composition, the fourth metal element is in the amount of 0.001-0.15 wt. % in terms of elements.

5. A composition according to any of the preceding claims 1-4, wherein the composition comprises an inorganic oxide carrier and a first metal element, a second metal element, a third metal element, and a fourth metal element deposited on the inorganic oxide carrier, and moreover, in terms of the total weight of the composition, the carrier based on the inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, the third metal element is in the amount of 1-10 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %.

6. The composition according to any one of the preceding claims 1-5, wherein the weight ratio of Fe to Co is 1:(0.3-3) in terms of oxides.

7. A composition according to any one of the preceding claims 1-6, wherein,

at least part of the Fe in the composition is in the form of iron carbide; and

at least a portion of the Co in the composition is in the form of elemental cobalt.

8. Composition according to any of the preceding claims 1-7, wherein the inorganic oxide carrier is at least one selected from the group consisting of alumina, silica-alumina, zeolite, spinel, kaolin, diatomite, perlite and perovskite.

9. The composition according to any one of the preceding paragraphs 1-8, in which the second metal element is at least one selected from the group consisting of Na, K, Mg and Ca;

the third metal element is at least one selected from the group consisting of Cu, Zn, Ti, Zr, V, Cr, Mo, W, Mn and rare earth elements;

the fourth metal element is at least one selected from the group consisting of Pt, Ir, Pd, Ru and Rh.

10. A method for obtaining a composition according to claim 1, including:

(1) preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, and water, spray drying the slurry, and then calcining to obtain a composition.

11. The method according to p. 10, providing for:

(1) preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor, and water, spray drying the slurry, and then calcining to obtain a composition.

12. The method according to p. 10 or p. 11, providing:

(1) preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor, a third metal precursor, and water, spray drying the slurry, and then calcining to obtain a composition.

13. The method according to any of the preceding paragraphs 10-12, further comprising:

(2) impregnating the composition obtained in step (1) in an impregnating solution containing a precursor of the fourth metal element to obtain a solid product, and then drying the solid product and/or performing a second calcination.

14. The method according to any one of the preceding paragraphs 10-13, wherein the calcination in step (1) is carried out in a carbon-containing atmosphere at a temperature of 400-1000°C for 0.1-10 hours.

15. The method according to any one of the preceding paragraphs 10-14, in which the carrier based on the inorganic oxide is alumina; moreover, before obtaining a suspension, the alumina precursor is treated with acid peptization, moreover, the acid used in acid peptization is hydrochloric acid, and moreover, acid peptization is carried out with an acid to alumina ratio of 0.12-0.22: 1 for 20-40 minutes .

16. The method according to p. 13, and the method further provides after the impregnation of stage (2) performing alkaline treatment of the solid product before drying and/or second calcination; and

moreover, alkaline processing includes: obtaining a suspension by mixing a solid product with an alkaline solution or washing the solid product with an alkaline solution.

17. The use of a composition capable of reducing CO and NOx emissions according to any of the preceding claims 1 to 9 for flue gas treatment.

18. The use of a composition capable of reducing CO and NOx emissions according to any one of the preceding claims 1 to 9 for treating flue gas from regeneration in a catalytic cracking process.

19. A method for catalytic cracking in a fluidized bed, comprising: contacting and reacting liquid petroleum products with a catalyst and regenerating the catalyst after contact and reaction, wherein the catalyst contains a catalytic cracking catalyst and a composition capable of reducing CO and NOx emissions, and moreover, a composition capable of reducing CO emissions and NOx, is a composition capable of reducing CO and NOx emissions, according to any one of the preceding paragraphs 1-9.

20. The method of catalytic cracking in a fluidized bed according to p. 45, in which the composition capable of reducing CO and NOx emissions is in an amount of 0.05-5 wt. %, based on the total weight of the catalyst.

The present invention provides a composition capable of reducing CO and NOx emissions as a catalytic cracking additive that can maintain high hydrothermal stability in the hydrothermal environment of a regenerator and has a high CO and NOx reducing activity in regenerated flue gas. In addition, the method for producing the composition of the present invention capable of reducing CO and NOx emissions is easy to operate and has low production costs. Compared with the FCC process using an existing CO and NOx abatement additive, the FCC process using the composition of the present invention capable of reducing CO and NOx emissions uses less CO and NOx abatement composition and has greater activity. regarding the reduction of CO and NOx emissions.

Other features and advantages of the present invention will be described in more detail in the following section of the detailed description.

Brief description of the figures

The appended figures are included to provide a further understanding of the present invention and are part of this description, which together with the following detailed description of the technology, shows embodiments of the present invention, but is not intended to limit its scope. On the figures:

fig. 1 is X-ray diffraction patterns of compositions capable of reducing CO and NOx emissions obtained in Examples 1.1 and 1.5;

fig. 2 is X-ray diffraction patterns of compositions capable of reducing CO and NOx emissions obtained in Examples 2.1 and 2.5;

fig. 3 is X-ray diffraction patterns of compositions capable of reducing CO and NOx emissions obtained in Examples 3.1 and 3.5;

fig. 4 is X-ray diffraction patterns of compositions capable of reducing CO and NOx emissions obtained in Examples 4.1 and 4.5;

fig. 5 is X-ray diffraction patterns of compositions capable of reducing CO and NOx emissions obtained in Examples 5.1 and 5.5.

Detailed disclosure of the present invention

It should be understood that the endpoints and any values within the ranges disclosed herein are not limited to a precise range or value, but encompass values close to those ranges or values. For value ranges, you can combine the endpoints of each of the ranges, the endpoints of each of the ranges, and individual points and individual points to obtain one or more new value ranges, as if those value ranges were specifically disclosed herein.

The present invention provides a composition capable of reducing CO and NOx emissions, consisting of a carrier based on an inorganic oxide and Fe and Co supported on a carrier based on an inorganic oxide, and the mass ratio of Fe to Co is 1: (0.1-10) in terms of for oxides. In one embodiment, the present invention provides a composition capable of reducing CO and NOx emissions comprising: an inorganic oxide carrier and a first metal element and a second metal element supported on an inorganic oxide carrier, the first metal element being selected from the group , consisting of non-noble metal elements of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.1-10) in terms of oxides, and the second metal is at least one selected from the group consisting of group IA and/or IIA metal elements. In one embodiment, the present invention provides a composition capable of reducing CO and NOx emissions comprising: an inorganic oxide carrier and a first metal element and a third metal element supported on an inorganic oxide carrier, the first metal element being selected from the group , consisting of non-noble metal elements of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.1-10) in terms of oxides, and the third metal is at least one selected from the group consisting of non-noble metal elements of groups IB-VIIB. In one embodiment, the present invention provides a composition capable of reducing CO and NOx emissions comprising: an inorganic oxide carrier and a first metal element and a fourth metal element supported on an inorganic oxide carrier, the first metal element being selected from the group , consisting of non-noble metal elements of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.05-20) in terms of oxides, and the fourth metal is at least one selected from the group consisting of noble metal elements. In one embodiment, the present invention provides a composition capable of reducing CO and NOx emissions comprising: an inorganic oxide carrier and a first metal element, a second metal element and a third metal element supported on an inorganic oxide carrier, the first element -metal is selected from the group consisting of group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the weight ratio of Fe to Co is 1:(0.05-20) in terms of oxides, the second metal being is at least one selected from the group consisting of metal elements of groups IA and/or IIA, and wherein the third metal is at least one selected from the group consisting of base metal elements of groups IB-VIIB. In one embodiment, the present invention provides a composition capable of reducing CO and NOx emissions comprising: an inorganic oxide carrier and a first metal element, a second metal element and a fourth metal element supported on an inorganic oxide carrier, the first element -metal is selected from the group consisting of group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the weight ratio of Fe to Co is 1:(0.05-20) in terms of oxides, the second metal being is at least one selected from the group consisting of Group IA and/or IIA metal elements, and wherein the fourth metal is at least one selected from the group consisting of noble metal elements.

In one embodiment, the present invention provides a composition capable of reducing CO and NOx emissions comprising: an inorganic oxide carrier and a first metal element, a third metal element and a fourth metal element supported on an inorganic oxide carrier, the first element -metal is selected from the group consisting of base metal elements of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.05-20) in terms of oxides, and the third metal is is at least one selected from the group consisting of non-noble metal elements of groups IB-VIIB, and wherein the fourth metal is at least one selected from the group consisting of noble metal elements. In one embodiment, the present invention provides a composition capable of reducing CO and NOx emissions comprising: an inorganic oxide carrier and a first metal element, a second metal element, a third metal element, and a fourth metal element supported on an inorganic carrier. oxide, and the first metal element is selected from the group consisting of non-noble metal elements of group VIII, and the first metal element includes Fe and Co, and the mass ratio of Fe to Co is 1: (0.05-20) in terms of oxides , wherein the second metal is at least one selected from the group consisting of Group IA and/or IIA metal elements, wherein the third metal is at least one selected from the group consisting of Group IB- non-noble metal elements. VIIB, and wherein the fourth metal is at least one selected from the group consisting of noble metal elements.

In the composition of the present invention, the contents of the first metal element, the second metal element, the third metal element, and the fourth metal element can be selected within a wide range. In one embodiment, based on the total weight of the composition, the inorganic oxide carrier is in the amount of 60-95 wt. %, and the total amount of Fe and Co is 5-40 wt. % in terms of oxides; preferably the carrier based on the inorganic oxide is in the amount of 75-92 wt. %, and the total amount of Fe and Co is 8-25 wt. % in terms of oxides; and even more preferably, the inorganic oxide carrier is in the amount of 84-90 wt. %, and the total amount of Fe and Co is 10-16 wt. % in terms of oxides. In one embodiment, based on the total weight of the composition, the inorganic oxide carrier is in an amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, and the second metal element is in the amount of 1-20 wt. %; preferably the carrier based on the inorganic oxide is in the amount of 60-90 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, and the second metal element is in the amount of 5-15 wt. %; and even more preferably, the inorganic oxide carrier is in the amount of 72-85 wt. %, and in terms of oxides, the first metal element is in the amount of 10-16 wt. %, and the second metal element is in the amount of 5-12 wt. %. In one embodiment, based on the total weight of the composition, the inorganic oxide carrier is in an amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, and the third metal element is in the amount of 1-20 wt. %; preferably the carrier based on the inorganic oxide is in the amount of 60-90 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, and the third metal element is in the amount of 2-15 wt. %; and even more preferably, the inorganic oxide carrier is in the amount of 76-86 wt. %, and in terms of oxides, the first metal element is in the amount of 10-16 wt. %, and the third metal element is in the amount of 2-8 wt. %. In one embodiment, based on the total weight of the composition, the inorganic oxide carrier is in the amount of 59.9-94.995 wt. %, and in terms of oxides, the first metal element is in the amount of 5-40 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %; preferably, the carrier based on the inorganic oxide is in the amount of 74.92-91.99 wt. %, and in terms of oxides, the first metal element is in the amount of 8-25 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.01-0.08 wt. %; and even more preferably, the inorganic oxide carrier is in the amount of 83.93-89.95 wt. %, and in terms of oxides, the first metal element is in the amount of 10-16 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.05-0.07 wt. %. In one embodiment, based on the total weight of the composition, the inorganic oxide carrier is in an amount of 10-90 wt. %, and in terms of oxides, the first metal element is in the amount of 0.5-50 wt. %, the second metal element is in the amount of 0.5-20 wt. %, and the third metal element is in the amount of 0.5-20 wt. %; preferably the carrier based on the inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, and the third metal element is in the amount of 1-10 wt. %; and even more preferably, the inorganic oxide carrier is in the amount of 55-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, the second metal element is in the amount of 5-15 wt. %, and the third metal element is in the amount of 2-8 wt. %. In one embodiment, based on the total weight of the composition, the inorganic oxide carrier is in an amount of 30-90 wt. %, and in terms of oxides, the first metal element is in the amount of 0.5-50 wt. %, the second metal element is in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.001-0.15 wt. %; preferably the carrier based on the inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %; and even more preferably, the inorganic oxide carrier is in the amount of 60-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, the second metal element is in the amount of 2-15 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.01-0.08 wt. %. In one embodiment, based on the total weight of the composition, the inorganic oxide carrier is in an amount of 30-90 wt. %, and in terms of oxides, the first metal element is in the amount of 0.5-50 wt. %, the third metal element is in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.001-0.15 wt. %; preferably the carrier based on the inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the third metal element is in the amount of 1-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %; and even more preferably, the inorganic oxide carrier is in the amount of 60-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, the third metal element is in the amount of 2-15 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.01-0.08 wt. %. In one embodiment, based on the total weight of the composition, the inorganic oxide carrier is in an amount of 10-90 wt. %, and in terms of oxides, the first metal element is in the amount of 0.5-50 wt. %, the second metal element is in the amount of 0.5-20 wt. %, the third metal element is in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.001-0.15 wt. %; preferably the carrier based on the inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, the third metal element is in the amount of 1-10 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %; and even more preferably, the inorganic oxide carrier is in the amount of 55-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, the second metal element is in the amount of 5-15 wt. %, the third metal element is in the amount of 2-8 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.01-0.08 wt. %.

The first metal element of the present invention includes Fe and Co. However, the present invention does not exclude cases where the first metal element also includes an element other than Fe and Co from the group VIII non-noble metal elements such as Ni. According to one most preferred embodiment of the present invention, the composition comprises an inorganic oxide support and a first metal element and a second metal element supported on an inorganic oxide support, the first metal element comprising only Fe and Co.

In the present invention, since Fe and Co are included in the first metal element, it is possible to improve the catalytic conversion activity of the composition against reduced nitrides such as NH ₃ and the like. To further take advantage of the synergistic effect of Fe and Co, it is preferable that the weight ratio of Fe to Co is 1:(0.3-3) and even more preferably 1:(0.4-2) in terms of oxides.

In the present invention, unless specifically indicated, the term "in terms of oxides" refers to "in terms of Fe ₂ O ₃ "for Fe and to" in terms of Co ₂ O ₃ "for Co.

According to a preferred embodiment of the present invention, at least part of the Fe in the composition is in the form of iron carbide. Preferably the iron carbide is Fe ₇ C ₃ and/or Fe ₇ C ₃ . There is no particular limitation on the amount of iron carbide in the present invention. As long as the iron carbide is present, the performance of the composition capable of reducing CO and NOx emissions can be effectively improved. According to another preferred embodiment of the present invention, at least a portion of the Fe in the composition is in the form of elemental iron. There is no particular limitation on the amount of elemental iron in the present invention. As long as elemental iron is present, the performance of the composition capable of reducing CO and NOx emissions can be effectively improved.

According to a preferred embodiment of the present invention, at least part of the Co in the composition is in the form of cobalt monoxide. There is no particular limitation on the amount of cobalt monoxide in the present invention. As long as cobalt monoxide is present, the performance of the composition capable of reducing CO and NOx emissions can be effectively improved. According to another preferred embodiment of the present invention, at least a portion of the Co in the composition is in the form of elemental cobalt. There is no particular limitation on the amount of elemental cobalt in the present invention. As long as elemental cobalt is present, the performance of the composition capable of reducing CO and NOx emissions can be effectively improved.

It should be noted that in the existing composition for reducing CO and NOx emissions, most of the metal elements in the composition are in an oxidized state. In the process for preparing the composition of the present invention, the composition is preferably calcined in a carbon containing atmosphere so that part of the iron oxides is converted to iron carbide and/or elemental iron and part of the cobalt oxides is converted to cobalt monoxide and/or elemental cobalt.

The presence of iron carbide and/or elemental iron and cobalt monoxide and/or elemental cobalt can provide better promotion of the composition for the decomposition of reduced nitrogen compounds, reduction in the formation of nitrogen oxides and to some extent promotion of the reduction of nitrogen oxides.

Preferably, the x-ray pattern of the composition according to the present invention contains diffraction peaks at 2θ 42.6°, 44.2° and 44.9°.

In particular, the diffraction peak at 2θ 44.9° is the diffraction peak for iron carbide and/or elemental iron; the diffraction peaks at 2θ 42.6° and 44.2° are diffraction peaks for cobalt monoxide and/or elemental cobalt.

According to a preferred embodiment of the present invention, the x-ray pattern of the composition of the present invention has a stronger diffraction peak at 2θ 44.9° than at 2θ 42.6°.

In the composition of the present invention, the inorganic oxide carrier may be any inorganic oxide carrier commonly used in the art, for example, at least one selected from the group consisting of alumina, silica-alumina, zeolite, spinel, kaolin, diatomite, perlite and perovskite. In the present invention, the spinel may be any commonly used spinel, for example at least one selected from the group consisting of magnesium aluminum spinel, zinc aluminum spinel and titanium aluminum spinel.

According to a preferred embodiment of the present invention, the inorganic oxide carrier is at least one selected from the group consisting of alumina, spinel and perovskite, and even more preferably alumina.

In the present invention, the alumina may be at least one selected from the group consisting of γ-alumina, δ-alumina, η-alumina, ρ-alumina, κ-alumina, and χ-alumina. There is no particular limitation for it in the present invention.

Aluminum oxide can be obtained from any aluminum sol or gel or aluminum hydroxide. The aluminum hydroxide may be at least one selected from the group consisting of gibbsite, paraluminite, nuoshui aluminite, diaspore, boehmite, and pseudoboehmite. Preferably the alumina is obtained from pseudoboehmite.

The inorganic oxide support may be commercially available or prepared by an existing process.

In the present invention, the Group IA metal elements include, but are not limited to, Na and/or K. The Group IIA metal elements include, but are not limited to, at least one of Mg, Ca, Sr, and Ba. Groups IB-VIIB base metal elements refer to base metals in groups IB-VIIB of the Periodic Table of the Elements, including Group IB base metals, Group IIB metals, Group IIIB metals, Group IVB metals, Group VB metals, Group VIB metals, and Group VIIB metals . In particular, base metal elements of groups IB-VIIB include, but are not limited to, at least one of Cu, Zn, Cd, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Re, and rare earth elements. The rare earth elements include, but are not limited to, at least one of La, Ce, Pr, Nd, Pm, Sm, and Eu. The noble metal elements include Au, Ag, Pt, Os, Ir, Ru, Rh, and Pd.

Preferably, in the composition of the present invention, the second metal element is at least one selected from the group consisting of Na, K, Mg and Ca, preferably K and/or Mg, most preferably Mg.

Preferably, in the composition of the present invention, the third metal element is at least one selected from the group consisting of Cu, Zn, Ti, Zr, V, Cr, Mo, W, Mn and rare earth elements, preferably at least one selected from the group consisting of Zr, V, W, Mn, Ce and La, most preferably Mn.

Preferably, in the composition of the present invention, the fourth metal element is at least one selected from the group consisting of Pt, Ir, Pd, Ru and Rh, most preferably Ru.

According to a preferred embodiment of the present invention, where Fe, Co, and Mg are used in combination as metal elements, the catalytic conversion activity of the composition capable of reducing CO and NOx emissions can be significantly improved with respect to reduced nitrides such as NH ₃ and the like. In addition, a composition capable of reducing CO and NOx emissions may preferably have better hydrothermal stability.

According to an embodiment of the present invention, the composition comprises alumina and Fe, Co and Mg deposited on alumina, wherein the weight ratio of Fe to Co is 1:(0.4-2) in terms of oxides, and in terms of the total weight of the composition oxide aluminum is in the amount of 72-85 wt. %, and in terms of oxides, the total amount of Fe and Co is 10-16 wt. %, and Mg is in the amount of 5-12 wt. %.

According to another preferred embodiment of the present invention, where Fe, Co, Mg and Mn are used in combination as metal elements, the catalytic conversion activity of the composition capable of reducing CO and NOx emissions can be significantly increased in relation to reduced nitrides such as NH ₃ and similar. In addition, a composition capable of reducing CO and NOx emissions may preferably have better hydrothermal stability.

According to another embodiment of the present invention, the composition contains alumina and Fe, Co, Mg and Mn deposited on alumina, and the mass ratio of Fe to Co is 1: (0.5-2) in terms of oxides, and in terms of total the mass of the composition of aluminum oxide is in the amount of 66-85 wt. %, and in terms of oxides, the total amount of Fe and Co is 6-16 wt. %, Mg is in the amount of 5-12 wt. %, and Mn is in the amount of 3-8 wt. %.

According to another preferred embodiment of the present invention, where Fe, Co, Mg and Ru are used in combination as active components, the catalytic conversion activity of the composition capable of reducing CO and NOx emissions can be significantly improved with respect to reduced nitrides such as NH ₃ and the like. . In addition, a composition capable of reducing CO and NOx emissions may preferably have better hydrothermal stability.

According to another embodiment of the present invention, the composition comprises alumina and Fe, Co, Mg and Ru deposited on alumina, wherein the weight ratio of Fe to Co is 1:(0.4-2) in terms of oxides, and in terms of total the mass of the composition of aluminum oxide is in the amount of 72-85 wt. %, and in terms of oxides, the total amount of Fe and Co is 10-16 wt. %, Mg is in the amount of 4.9-12 wt. %, and in terms of elements Ru is in the amount of 0.05-0.07 wt. %.

According to another preferred embodiment of the present invention, where Fe, Co, Mg, Mn and Ru are used in combination as active components, the catalytic conversion activity of the composition capable of reducing CO and NOx emissions can be significantly increased in relation to reduced nitrides such as NH ₃ and the like. In addition, a composition capable of reducing CO and NOx emissions may preferably have better hydrothermal stability.

According to another embodiment of the present invention, the composition comprises alumina and Fe, Co, Mg, Mn and Ru deposited on alumina, wherein the mass ratio of Fe to Co is 1:(0.5-2) in terms of oxides, and in terms of on the total weight of the composition, aluminum oxide is in the amount of 66-85 wt. %, and in terms of oxides, the total amount of Fe and Co is 6-16 wt. %, Mg is in the amount of 5-12 wt. %, Mn is in the amount of 3-8 wt. %, and in terms of elements Ru is in the amount of 0.05-0.07 wt. %.

In the present invention, the amount of each component in a composition capable of reducing CO and NOx emissions is measured using X-ray fluorescence spectrometry (The Analytic Method of Petrochemicals (RIPP Experimental Method), Edited by Cuiding Yang, et. al., Science Press, 1990).

The present invention also provides a process for preparing a composition capable of reducing CO and NOx emissions, comprising:

obtaining a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor and water, spray drying the slurry, and then calcining;

wherein the precursor of the first metal element comprises an Fe precursor and a Co precursor, and wherein the Fe precursor and Co precursor are used in such amounts that the weight ratio of Fe to Co in the resulting composition is 1:(0.1-10) in terms of oxides.

The present invention also provides a process for preparing a composition capable of reducing CO and NOx emissions, comprising:

obtaining a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor and water, spray drying the slurry, and then calcining;

wherein the first metal element is selected from the group consisting of Group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the second metal is at least one selected from the group consisting of Group IA metal elements and /or IIA, and

moreover, the precursor of the first metal element, the precursor of Fe and the precursor of Co, are used in such quantities that the mass ratio of Fe to Co in the resulting composition was 1: (0.1-10) in terms of oxides.

The present invention also provides a process for preparing a composition capable of reducing CO and NOx emissions, comprising:

obtaining a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor, a third metal precursor, and water, spray drying the slurry, and then calcining;

wherein the first metal element is selected from the group consisting of Group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the second metal is at least one selected from the group consisting of Group IA metal elements and /or IIA, wherein the third metal is at least one selected from the group consisting of non-noble metal elements of groups IB-VIIB, and

moreover, the precursor of the first metal element, the precursor of Fe and the precursor of Co, are used in such quantities that the mass ratio of Fe to Co in the resulting composition was 1: (0.05-20) in terms of oxides.

The present invention also provides a process for preparing a composition capable of reducing CO and NOx emissions, comprising:

(1) preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor, and water, spray drying the slurry, and then performing a first calcination to obtain a semi-finished composition;

(2) impregnating the semi-finished composition obtained in step (1) in an impregnating solution containing a precursor of the fourth metal element to obtain a solid product, and then drying the solid product and/or performing a second calcination,

wherein the first metal element is selected from the group consisting of Group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the second metal is at least one selected from the group consisting of Group IA metal elements and/ or IIA, wherein the fourth metal is at least one selected from the group consisting of noble metal elements, and

moreover, the precursor of the first metal element, the precursor of Fe and the precursor of Co, are used in such quantities that the mass ratio of Fe to Co in the resulting composition was 1: (0.05-20) in terms of oxides.

The present invention also provides a process for preparing a composition capable of reducing CO and NOx emissions, comprising:

(1) preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor, a third metal precursor, and water, spray drying the slurry, and then performing a first calcination to obtain a semi-finished composition;

(2) impregnating the semi-finished composition obtained in step (1) in an impregnating solution containing a precursor of the fourth metal element to obtain a solid product, and then drying the solid product and/or performing a second calcination,

wherein the first metal element is selected from the group consisting of Group VIII non-noble metal elements, wherein the first metal element comprises Fe and Co, wherein the second metal is at least one selected from the group consisting of Group IA metal elements and /or IIA, wherein the third metal is at least one selected from the group consisting of non-noble metal elements of groups IB-VIIB, wherein the fourth metal is at least one selected from the group consisting of noble metal elements, and

moreover, the precursor of the first metal element, the precursor of Fe and the precursor of Co, are used in such quantities that the mass ratio of Fe to Co in the resulting composition was 1: (0.05-20) in terms of oxides.

In the present invention, the inorganic oxide carrier precursor may comprise any materials from which the inorganic oxide carrier is obtained by post-calcination. There is no particular limitation for it in the present invention.

In the production methods of the present invention, the inorganic oxide support, the first metal element, the second metal element, the third metal element, and the fourth metal element are selected as described above, which will not be described again hereinafter.

In the present invention, the alumina precursor can be selected from the group consisting of various sols or gels of aluminum and aluminum hydroxide. The aluminum hydroxide may be at least one selected from the group consisting of gibbsite, paraluminite, nuoshui aluminite, diaspore, boehmite, and pseudoboehmite. Most preferably, the alumina precursor is pseudoboehmite.

In the preparation methods of the present invention, the alumina precursor may be treated by acid peptization prior to making the slurry. Acid peptization can be carried out according to conventional methods in this field. Even more preferably, the acid used in the acid peptization is hydrochloric acid.

In the present invention, conditions for acid peptization can be selected over a wide range. Preferably, acid peptization can be carried out with an acid to alumina ratio of 0.12-0.22:1 for 20-40 minutes.

In the present invention, unless otherwise specifically indicated, the ratio of acid to alumina refers to the mass ratio of hydrochloric acid in terms of concentrated hydrochloric acid with a concentration of 36 wt. % to the precursor of aluminum oxide in terms of dry matter.

Acid peptization can be carried out by adding pseudoboehmite to water and dispersing to form a slurry, then adding hydrochloric acid to acidify for 30 minutes, with the ratio of acid to alumina being 0.18.

In the present invention, the first metal element precursor, the second metal element precursor, the third metal element precursor, and the fourth metal element precursor are respectively selected from the group consisting of water-soluble salts of the first metal element, the second metal element, the third metal element. a metal and a fourth metal element such as nitrates, chlorides, chlorates or sulfates and the like. There is no particular limitation for it in the present invention.

In the production method of the present invention, the amounts of the first metal element, the second metal element, the third metal element, and the fourth metal element can be selected from a wide range.

In one embodiment, the inorganic oxide carrier precursor and the first metal element precursor are used in such amounts that in the resulting composition, based on the total weight of the composition, the inorganic oxide carrier is present in an amount of 60-95 wt. %, and the total amount of Fe and Co was 5-40 wt. % in terms of oxides. Preferably, the inorganic oxide carrier is in the amount of 75-92 wt. %, and the total amount of Fe and Co is 8-25 wt. % in terms of oxides. Even more preferably, the inorganic oxide carrier is in the amount of 84-90 wt. %, and the total amount of Fe and Co is 10-16 wt. % in terms of oxides.

In one embodiment, the inorganic oxide carrier precursor, the first metal element precursor, and the second metal element precursor are used in such amounts that the resulting composition, based on the total weight of the composition, contains the inorganic oxide carrier in an amount of 50-90 wt. %, and in terms of oxides, the first metal element was in the amount of 3-30 wt. %, and the second metal element was in the amount of 1-20 wt. %. Preferably the carrier based on inorganic oxide is in the amount of 60-90 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, and the second metal element is in the amount of 5-15 wt. %. Even more preferably, the inorganic oxide carrier is in the amount of 72-85 wt. %, and in terms of oxides, the first metal element is in the amount of 10-16 wt. %, and the second metal element is in the amount of 5-12 wt. %.

In one embodiment, the inorganic oxide carrier precursor, the first metal element precursor, the second metal element precursor, and the third metal element precursor are used in such amounts that the resulting composition, based on the total weight of the composition, contains the inorganic oxide carrier in amount of 10-90 wt. %, and in terms of oxides, the first metal element was in the amount of 0.5-50 wt. %, the second metal element was in the amount of 0.5-20 wt. %, and the third metal element was in the amount of 0.5-20 wt. %. Preferably, the inorganic oxide carrier is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, and the third metal element is in the amount of 1-10 wt. %. Even more preferably, the inorganic oxide carrier is in an amount of 55-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, the second metal element is in the amount of 5-15 wt. %, and the third metal element is in the amount of 2-8 wt. %. In one embodiment, the inorganic oxide carrier precursor, the first metal element precursor, the second metal element precursor, and the fourth metal element precursor are used in such amounts that the resulting composition, based on the total weight of the composition, contains the inorganic oxide carrier in amount of 30-90 wt. %, and in terms of oxides, the first metal element was in the amount of 0.5-50 wt. %, the second metal element was in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.001-0.15 wt. %. Preferably, the inorganic oxide carrier is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %. Even more preferably, the inorganic oxide carrier is in an amount of 60-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. % in terms of oxides, the second metal element is in the amount of 2-15 wt. % in terms of oxides, and in terms of elements, the fourth metal element is in the amount of 0.01-0.08 wt. %.

In one embodiment, the inorganic oxide carrier precursor, the first metal element precursor, the second metal element precursor, the third metal element precursor, and the fourth metal element precursor are used in such amounts that, in the resulting composition, based on the total weight of the composition, the carrier based on inorganic oxide was in the amount of 10-90 wt. %, and in terms of oxides, the first metal element was in the amount of 0.5-50 wt. %, the second metal element was in the amount of 0.5-20 wt. %, the third metal element was in the amount of 0.5-20 wt. %, and in terms of elements, the fourth metal element was in the amount of 0.001-0.15 wt. %. Preferably, the inorganic oxide carrier is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, the third metal element is in the amount of 1-10 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %. Even more preferably, the inorganic oxide carrier is in an amount of 55-85 wt. %, and in terms of oxides, the first metal element is in the amount of 5-25 wt. %, the second metal element is in the amount of 5-15 wt. %, the third metal element is in the amount of 2-8 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.01-0.08 wt. %.

Preferably, in the method of the present invention for producing a composition capable of reducing CO and NOx emissions, the weight ratio of the amount of inorganic oxide carrier precursor in terms of oxides, the amount of precursor of the first metal element in terms of oxides of Group VIII non-noble metal elements, and the amount of precursor of the second metal element in terms of oxides of metal elements of group IA and/or IIA may be 50-90:3-30:1-20; preferably 60-90:5-25:5-15 and even more preferably 72-85:10-16:5-12. Preferably, the weight ratio of the amount of precursor of the inorganic oxide carrier in terms of oxides, the amount of precursor of the first metal element in terms of oxides of non-noble metal elements of group VIII, the amount of precursor of the second metal element in terms of oxides of metal elements of group IA and/or IIA and the amount of the precursor of the third metal element in terms of oxides of non-noble metal elements of groups IB-VIIB can be 10-90:0.5-50:0.5-20:0.5-20; preferably 50-90:3-30:1-20:1-10; even more preferably 55-85:5-25:5-15:2-8 and more preferably 66-85:6-16:5-12:3-8. Preferably, the weight ratio of the amount of precursor of the inorganic oxide carrier in terms of oxides, the amount of precursor of the first metal element in terms of oxides of non-noble metal elements of group VIII, the amount of precursor of the second metal element in terms of oxides of metal elements of group IA and/or IIA and the amount of the precursor of the fourth metal element in terms of noble elements can be 30-90:0.5-50:0.5-20:0.001-0.15; preferably 50-90:3-30:1-20:0.005-0.1; even more preferably 60-85:5-25:2-15:0.01-0.08 and more preferably 72-85:10-16:4.9-12:0.05-0.07. Preferably, the weight ratio of the amount of precursor of the inorganic oxide carrier in terms of oxides, the amount of precursor of the first metal element in terms of oxides of non-noble metal elements of group VIII, the amount of precursor of the second metal element in terms of oxides of metal elements of group IA and/or IIA, the amount of the precursor of the third metal element in terms of oxides of non-noble metal elements of groups IB-VIIB, and the amount of the precursor of the fourth metal element in terms of noble elements can be 10-90:0.5-50:0.5-20 :0.5-20:0.001-0.15, preferably 50-90:3-30:1-20:1-10:0.005-0.1; even more preferably 55-85:5-25:5-15:2-8:0.01-0.08 and more preferably 66-85:6-16:5-12:3-8:0.05-0 .07.

In the present invention, the first metal element precursor contains at least an Fe precursor and a Co precursor.

According to a preferred embodiment of the present invention, in the precursor of the first metal element, the Fe precursor and the Co precursor are used in such amounts that the weight ratio of Fe to Co in the resulting composition is 1:(0.3-3), preferably 1:(0.4- 2) in terms of oxides.

In the present invention, it is preferable that the solids content of the suspension is 8-30 wt. %.

In the present invention, there is no particular limitation to the method for producing a slurry by mixing an inorganic oxide carrier precursor, a first metal element precursor, a second metal element precursor, a third metal element precursor, and water. There is no particular restriction on the order of adding the inorganic oxide support precursor, the first metal element precursor, the second metal element precursor, and the third metal element precursor, since the inorganic oxide support precursor, the first metal element precursor, the second metal element precursor metal and the precursor of the third metal element are in contact with water. Preferably, the first metal element precursor and the third metal element precursor are dissolved in water to which the inorganic oxide support precursor (preferably the inorganic oxide support precursor is acidified) is added to form a first solution. The precursor of the second metal element is mixed with water to form a second solution. The first solution and the second solution are mixed to form a suspension.

In the present invention, spray drying can be carried out according to conventional methods in the art without any particular limitation. Preferably, the spray drying is carried out under conditions which permit the production of spray-dried particles with an average particle size of 60-75 µm and a base particle size of 20-100 µm. It is also preferred that the spray drying is carried out under conditions that allow more than 50% of spray-dried particles with a particle size of 40-80 µm to be obtained.

In the present invention, even by calcining with conventional techniques in the art, it is possible to increase the catalytic conversion activity of a composition capable of reducing CO and NOx emissions against reduced nitrides such as NH ₃ and the like. However, in order to further improve the catalytic conversion activity against reduced nitrides such as NH ₃ and the like, and the hydrothermal stability of the composition capable of reducing CO and NOx emissions, the calcination is preferably carried out in a carbonaceous atmosphere. The inventors of the present invention have unexpectedly found in research that calcination in a carbonaceous atmosphere can significantly increase the catalytic conversion activity of reduced nitrides such as NH ₃ and the like, and the hydrothermal stability of the composition capable of reducing CO and NOx emissions. In addition, calcination in a carbonaceous atmosphere is better suited to control the relationship between the active metal-containing components and the support. The increase in activity may be due to the conversion of active components from oxides to carbides in the reduced state, while the increase in hydrothermal stability may be due to the fact that treatment in a carbonaceous atmosphere at high temperature facilitates adhesion, condensation and crosslinking of the active components in the composition. It can be seen from a comparison of the X-ray spectra that there are obvious peaks of iron carbide and elemental cobalt after treatment.

In particular, as shown in FIG. 1, there is a diffraction peak at 45.5° for Al ₂ O ₃ and Co ₂ AlO ₄ in the X-ray spectrum of composition S-1.5, which was not subjected to treatment in a carbonaceous atmosphere. In the X-ray spectrum of composition S-1.1, which was subjected to treatment in a carbonaceous atmosphere, there is not only a diffraction peak at 45.5° for Al ₂ O ₃ and Co ₂ AlO ₄ , but also obvious diffraction peaks at approximately 42.6°, 44 .2° and 45.0°, which may be due to the fact that the composition S-1.1, subjected to treatment in a carbonaceous atmosphere, has a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-1.5, composition S-1.1 has diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

As shown in FIG. 2, there is a diffraction peak at approximately 43.9° for MgO and a diffraction peak at approximately 45.9° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ in the X-ray spectrum of composition S-2.5, which was not treated with carbonaceous atmosphere. In the X-ray spectrum of composition S-2.1, which was subjected to treatment in a carbonaceous atmosphere, not only is there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° are shifted to the left, and the diffraction peak at approximately 45.0° becomes stronger, which may be due to the fact that composition S-2.1, processed in a carbonaceous atmosphere, has a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-2.5, composition S-2.1 has diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

As shown in FIG. 3, there is a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ in the X-ray spectrum of composition S-3.5, which was not treated with carbonaceous atmosphere. In the X-ray spectrum of composition S-2.1, which was subjected to treatment in a carbonaceous atmosphere, not only is there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° become much stronger and shift to the left, which may be due to the fact that the composition S-3.1, subjected to treatment in a carbonaceous atmosphere, has a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-3.5, composition S-3.1 has diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

As shown in FIG. 4, there is a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ in the X-ray spectrum of composition S-4.5, which was not treated with carbonaceous atmosphere. In the X-ray spectrum of composition S-4.1, which was subjected to treatment in a carbonaceous atmosphere, not only is there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° become much stronger and shift to the left, which may be due to the fact that composition S-4.1, subjected to treatment in a carbonaceous atmosphere, has a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-4.5, composition S-4.1 has diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

As shown in FIG. 5, there is a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ , and MgAl ₂ O ₄ in the X-ray spectrum of composition S-5.5, which was not treated with carbonaceous atmosphere. In the X-ray spectrum of composition S-5.1, which was subjected to treatment in a carbonaceous atmosphere, not only is there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° become much stronger and shift to the left, which may be due to the fact that composition S-5.1, subjected to treatment in a carbonaceous atmosphere, has a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.1 has diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

It should be noted that FIG. 1-5 show only the x-ray spectrum in the range of 41-50°, which is mainly used to show the forms of Fe and Co present in the composition. In the ranges beyond 41-50° there are other diffraction peaks, for example, at 29 31°, 37°, 59° and 65° for spinel, Fe ₃ O ₄ , Co ₃ O ₄ and the like, which is not further explained in the present invention .

According to a preferred embodiment of the present invention, the calcination is carried out in a carbonaceous atmosphere at a temperature of 490-1000°C, preferably 450-659°C, for 9.1-10 hours, preferably 1-3 hours.

There is no particular limitation to the pressure used in calcination. The calcination can be carried out at normal pressure, for example 0.01-1 MPa (absolute pressure).

In the present invention, a carbonaceous atmosphere is provided by a gas containing elemental carbon. Preferably, the elemental carbon-containing gas is selected from the group consisting of elemental carbon-containing reductive gases, even more preferably at least one selected from the group consisting of CO, methane and ethane, most preferably CO.

In the present invention, the elemental carbon-containing gas may also contain a portion of air and/or an inert gas, and the inert gas may be various inert gases commonly used in the art. Preferably the inert gas is at least one selected from the group consisting of nitrogen, argon and helium, and even more preferably nitrogen.

According to a preferred embodiment of the present invention, the carbon-containing atmosphere is provided by a mixed gas containing CO and nitrogen, wherein the volume concentration of CO in the carbon-containing atmosphere is preferably 1-20%, even more preferably 4-19%. By using the preferred embodiment of the present invention, not only processing requirements can be better met, but the safety of operators can also be guaranteed.

In the present invention, the calcination may be carried out in a calciner, which may be a rotary calciner used in the preparation of catalytic cracking catalysts and promoters. The elemental carbon-containing gas is contacted with the solid material in a countercurrent calcination furnace.

In the production method of the present invention, there is no particular restriction on the impregnation in step (2) which can be carried out according to conventional methods in the art, and it may be saturation impregnation or over impregnation, preferably over impregnation.

According to an embodiment of the present invention, the semi-finished composition may first be added to water, followed by addition of the fourth metal element precursor solution and mixing.

In the present invention, the mixture obtained after impregnation can be filtered to obtain a solid product. Filtration can be carried out according to conventional methods in the art.

In the production process of the present invention, the process preferably also includes, after the impregnation of step (2), performing an alkaline treatment on the solid product before drying and/or a second calcination. In a preferred embodiment of the present invention, the alkaline treatment after impregnation with the noble metal element results in a more complete association of the noble metal element (i.e., the fourth metal element) with the first metal element, the second metal element, and the third metal element, which is more preferably for the synergistic effects of the four elements and for enhancing the catalytic activity towards reduced nitrides such as NH ₃ and the like and the hydrothermal stability of the composition capable of reducing CO and NOx emissions.

According to an embodiment of the present invention, the alkaline treatment includes: obtaining a slurry by mixing a solid product and an alkaline solution, or washing the solid product with an alkaline solution.

In the present invention, the alkaline solution can be selected from a wide range. Preferably the alkaline solution is an alkaline solution of a non-metal element, preferably aqueous ammonia and/or an alkaline ammonium salt solution. The alkaline ammonium salt solution may be at least one of an ammonium carbonate solution, an ammonium bicarbonate solution, and a diammonium hydrogen phosphate solution. In the present invention, most preferably the alkaline solution is aqueous ammonia.

In the present invention, the concentration and amount of the alkaline solution can be selected over a wide range. For example, the alkaline solution may have a concentration of 0.01-10 mol/l, preferably 0.05-5 mol/l, even more preferably 0.5-2 mol/l. The alkaline solution can be used in an amount by volume of 1-10 times, preferably 1.5-5 times, greater than the pore volume of the solid product.

Those skilled in the art can select the concentration and amount of alkaline solution according to the pore volume of the resulting solid product. For example, according to an embodiment of the present invention, when the pore volume of the obtained solid product is about 0.4-0.5 ml/g, and the amount of solid product to be processed is 100 g, 60-250 ml of 0.5- 2 mol/l aqueous ammonia solution.

In step (2) of the present invention, the solid product may be only dried, only re-calcined, or dried and then re-calcined. There is no particular limitation for it in the present invention. Preferably the solid product is dried and then re-calcined. There is no particular limitation to the drying and re-calcination conditions in the present invention. They can be carried out according to conventional methods in this field. For example, drying can be carried out at a temperature of 60-150°C for 2-10 hours.

There is no particular limitation to re-calcination in the present invention. The second calcination can be carried out in air or an inert atmosphere (such as nitrogen). There is no particular limitation for it in the present invention. For example, the second calcination can be carried out at a temperature of 300-550°C for 1-10 hours.

The present invention also provides a composition capable of reducing CO and NOx emissions obtained by the above method.

The composition capable of reducing CO and NOx emissions obtained by the above method comprises Fe, Co, and optionally at least one of a second metal element, a third metal element, and a fourth metal element. By using such metal elements in combination, the catalytic conversion activity of the composition capable of reducing CO and NOx emissions can be significantly improved with respect to reduced nitrides such as NH ₃ and the like. In addition, a composition capable of reducing CO and NOx emissions may have better hydrothermal stability.

The present invention also provides for the use of a composition capable of reducing CO and NOx emissions in flue gas treatment. The composition of the present invention can be used to treat any flue gas in which it is necessary to reduce CO and NOx emissions.

The present invention also provides for the use of a composition capable of reducing CO and NOx emissions in the treatment of flue gas from regeneration in a catalytic cracking process. The composition of the present invention, capable of reducing CO and NOx emissions, is particularly suitable for reducing CO and NOx emissions in flue gas from complete regeneration and partial regeneration. A composition of the present invention capable of reducing CO and NOx emissions is more suitable for reducing CO and NOx emissions in flue gas from incomplete regeneration. Thus, the present invention provides the use of the above composition capable of reducing CO and NOx emissions in the treatment of flue gas from incomplete regeneration in a catalytic cracking process.

The present invention also provides a fluid catalytic cracking process comprising: contacting and reacting liquid petroleum products with a catalyst and regenerating the catalyst after contact and reaction, wherein the catalyst comprises a catalytic cracking catalyst and a composition capable of reducing CO and NOx emissions, and wherein the composition is capable of reducing CO and NOx emissions is a composition of the present invention capable of reducing CO and NOx emissions as described above.

In the fluid catalytic cracking process of the present invention, preferably the composition capable of reducing CO and NOx emissions is in an amount of 0.05 to 5 wt. %, preferably 0.1-3 wt. %, even more preferably 0.5-2.5 wt. %, based on the total weight of the catalyst.

In the fluid catalytic cracking process of the present invention, preferably liquid oils are contacted and reacted with a catalyst, and then the catalyst is not completely regenerated after contact and reaction. Also preferably, the oxygen concentration in the flue gas generated during incomplete regeneration is not more than 0.5 vol. %.

There is no particular limitation regarding liquid petroleum products in the present invention. They can be any liquid petroleum products commonly handled in the field of catalytic cracking, such as vacuum gas oil, fuel oil, tar, deasphalted oil, coker gas oil or hydroprocessing oil.

There is no particular limitation of the catalytic cracking catalyst in the present invention. It may be any of the existing catalytic cracking catalysts, which may be commercially available or obtained according to existing methods.

The composition of the present invention capable of reducing CO and NOx emissions may be in the form of independent particles or as part of integral catalytic cracking catalyst particles. Preferably, the composition of the present invention capable of reducing CO and NOx emissions is used as independent particles in combination with catalytic cracking catalyst particles.

In the present invention, unless specifically stated otherwise, the terms "ppm" represent concentration by volume.

In the fluid catalytic cracking process of the present invention, there is no particular limitation on the catalyst regeneration method compared to the existing regeneration method, and the catalyst regeneration method may include partial regeneration, partial regeneration, and full regeneration modes. Regarding the regeneration method, please refer to "Catalytic cracking process and engineering)", Edited by Junwu Chen, Sinopec press, page 1234-1343, 2005. Preferably, the regeneration temperature is 650-730°C.

The implementation and beneficial effects of the present invention will be described in more detail by means of the following examples, which are intended to assist the reader in a better understanding of the essence of the present invention, but are not intended to limit the practicable scope of the present invention.

In the examples, the amount of each component in a composition capable of reducing CO and NOx emissions is measured using X-ray fluorescence spectrometry (XRF). Please refer to "The Analytic Method of Petrochemicals (RIPP Experimental Method", Edited by Cuiding Yang, et. al., Science Press, 1990). In the examples, the X-ray spectrum of the composition capable of reducing CO and NOx emissions was measured on an X-ray diffractometer (Siemens D5005) to determine the structure. His conditions included: Cu target, Kα radiation, solid detector, lamp voltage 40 kV, tube current 40 mA.

The raw materials used in the examples and comparative examples included: analytical grade cobalt nitrate [Co(NO ₃ ) ₂ ⋅6H ₂ O], analytical grade iron nitrate [Fe(NO ₃ ) ₃ ⋅9H ₂ O], potassium permanganate (KMnO ₄ ) analytical grade, analytical grade magnesium oxide [MgO], all available from Sinopharm Group Chemical Reagent Co., Ltd.; ruthenium chloride (RuCl ₃ ) analytical grade with Ru≥37%, available from GRIKIN Advanced Material Co., Ltd; pseudoboehmite, technical grade product with alumina content of 64 wt. % and a pore volume of 0.31 ml/g, manufactured by Shandong Company of Aluminum Corporation of China Limited; hydrochloric acid with a concentration of 36.5 wt. %, analytical grade, available from Beijing chemical works; aqueous ammonia at 25-28% concentration, analytical grade, available from Beijing chemical works, diluted before use; carbon monoxide with a concentration of 10 vol. %, with nitrogen as the rest gas, available from Beijing AP BAIF gas Industrial Co., Ltd.; catalytic cracking catalyst, industrial product (Cat-A, catalyst grade: CGP-1), with a Na ₂ O content of 0.24 wt. %, the content of Re ₂ O ₃ 3.2 wt. % and the content of Al ₂ O ₃ 48.0 wt. %, average particle size 67 µm, available from Sinopec Catalyst Co., Ltd.

Example 1.1

(1) 2.62 kg of pseudoboehmite was added to 14.2 kg of deionized water and dispersed to form a slurry. 238 ml of hydrochloric acid was added to the suspension for acidification for 15 minutes to obtain an alumina gel. In terms of metal oxides, 100 g of iron nitrate (calculated as Fe ₂ O ₃ , the same below) and 100 g of cobalt nitrate (calculated as Co ₂ O ₃ , the same below) were added to 3500 ml of water, stirred until complete dissolution , and then the alumina gel was added thereto, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of particles obtained by spray drying (average particle size was 65 µm, and particles with a size of 40-80 µm were in the amount of 60%, the same below) were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 600° C. for 1.5 hours to obtain composition S-1.1.

The test results regarding the content of each component in the composition S-1.1 are shown in table 1.1.

Composition S-1.1 was analyzed by X-ray diffraction and the X-ray spectrum is shown in FIG. 1. As shown in FIG. 1, there was a diffraction peak at 45.5° for Al ₂ O ₃ and Co ₂ AlO ₄ in the X-ray spectrum of composition S-1.5, which was not subjected to treatment in a carbonaceous atmosphere. In the X-ray spectrum of the Sl. 1, which was subjected to treatment in a carbonaceous atmosphere, there was not only a diffraction peak at 45.5° for Al ₂ O ₃ and Co ₂ AlO ₄ , but also obvious diffraction peaks at approximately 42.6° and approximately 45.0°, which could be due to the fact that composition S-1.1, subjected to treatment in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-2.5, composition S-2.1 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

It should be noted that the figures show the X-ray spectrum only in the range 41-50 (and were mainly used to show the forms of Fe and Co present in the composition. In the range beyond 41-50°, other diffraction peaks were present, for example, at 2θ 31° , 37°, 59° and 65° for spinel, Fe ₃ O ₄ , Co ₃ O ₄ and the like, which is not further explained in the present invention.

Example 1.2

(1) 2.56 kg of pseudoboehmite was added to 13.9 kg of deionized water and dispersed to form a slurry. 232 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 140 g of iron nitrate and 60 g of cobalt nitrate were added to 3500 ml of water, stirred until completely dissolved, and then alumina gel was added thereto, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 500° C. for 3 hours to obtain composition S-1.2.

The test results regarding the content of each component in the composition S-1.2 are shown in table 1.1. Composition S-1.2 had similar results to example 1.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-1.2, which was subjected to treatment in a carbonaceous atmosphere, there was not only a diffraction peak at approximately 45.5° for Al ₂ O ₃ and Co ₂ AlO ₄ , but also obvious diffraction peaks at approximately 42.6° and approximately 45.0°, which could be due to the fact that composition S-1.2, subjected to treatment in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron . In addition, compared to composition S-1.5, composition S-1.2 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 1.3

(1) 2.34 kg of pseudoboehmite was added to 12.7 kg of deionized water and dispersed to form a slurry. 212 ml of hydrochloric acid was added to the suspension for acidification for 15 minutes to obtain an alumina gel. In terms of metal oxides, 100 g of iron nitrate and 200 g of cobalt nitrate were added to 4000 ml of water, stirred until completely dissolved, and then aluminum oxide gel was added thereto, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 650°C for 1 hour to obtain composition S-1.3.

The test results regarding the content of each component in the composition S-1.3 are shown in table 1.1. Composition S-1.3 had similar results to example 1.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-1.3, which was subjected to treatment in a carbonaceous atmosphere, there was not only a diffraction peak at approximately 45.5° for Al ₂ O ₃ and Co ₂ AlO ₄ , but also obvious diffraction peaks at approximately 42.6° and approximately 45.0°, which could be due to the fact that composition S-1.3, subjected to treatment in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron . In addition, compared to composition S-1.5, composition S-1.3 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 1.4

(1) 2.25 kg of pseudoboehmite was added to 12.2 kg of deionized water and dispersed to form a slurry. 294 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 200 g of iron nitrate and 120 g of cobalt nitrate were added to 3500 ml of water, stirred until completely dissolved, and then alumina gel was added thereto, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 199 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 600° C. for 1.5 hours to obtain composition S-1.4.

The test results regarding the content of each component in the composition S-1.4 are shown in table 1.1. Composition S-1.4 had similar results to example 1.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-1.4, which was subjected to treatment in a carbonaceous atmosphere, there was not only a diffraction peak at approximately 45.5° for Al ₂ O ₃ and Co ₂ AlO ₄ , but also obvious diffraction peaks at approximately 42.6° and approximately 45.0°, which could be due to the fact that composition S-1.4, subjected to treatment in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron . In addition, compared to composition S-1.5, composition S-1.4 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 1.5

Example 1.1 was repeated, except that the mixed gas CO/N ₂ with a concentration of CO 10 vol. % was replaced with air to obtain a composition of 1.5.

The test results regarding the content of each component in the composition S-1.5 are shown in table 1.1. Composition S-1.5 was analyzed by X-ray diffraction. From the X-ray spectrum (as shown in Fig. 1) it can be seen that there were no obvious diffraction peaks at 2θ 42.6°, 44.2° and 44.9°, which showed that the entire amount of Fe and Co in the composition of S- 1.5 was presented as oxides.

Example 1.6

Example 1.1 was repeated, except that, in terms of metal oxides, iron nitrate was used in an amount of 50 g, and cobalt nitrate was used in an amount of 150 g, to obtain composition 1.6.

The test results regarding the content of each component in the composition S-1.6 are shown in table 1.1. Composition S-1.6 had the same test results as example 1.1 using x-ray diffraction. In the X-ray spectrum of composition S-1.6, which was subjected to treatment in a carbonaceous atmosphere, there was not only a diffraction peak at approximately 45.5° for Al ₂ O ₃ and Co ₂ AlO ₄ , but also obvious diffraction peaks at approximately 42.6° and approximately 45.0°, which could be due to the fact that composition S-1.6, subjected to treatment in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron . In addition, compared to composition S-1.5, composition S-1.6 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 1.7

Example 1.1 was repeated, except that, in terms of metal oxides, iron nitrate was used in an amount of 150 g, and cobalt nitrate was used in an amount of 50 g, to obtain composition 1.7.

The test results regarding the content of each component in the composition S-1.7 are shown in table 1.1. Composition S-1.7 had similar results to example 1.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-1.7, which was treated in a carbonaceous atmosphere, there was not only a diffraction peak at approximately 45.5° for Al ₂ O ₃ and Co ₂ AlO ₄ , but also obvious diffraction peaks at approximately 42.6° and approximately 45.0°, which could be due to the fact that composition S-1.7, subjected to treatment in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron . In addition, compared to composition S-1.5, composition S-1.7 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 1.8

Example 1.1 was repeated, except that the mixed gas CO/N ₂ with a concentration of CO 10 vol. % was replaced by a mixed gas of ethane/nitrogen with an ethane concentration of 10 vol. % to obtain composition 1.8.

The results of testing in relation to the content of each component in the composition S-1.8 are shown in table 1.1. Composition S-1.8 had the same test results as Example 1.1 using X-ray diffraction. In the X-ray spectrum of composition S-1.8, which was subjected to treatment in a carbonaceous atmosphere, there was not only a diffraction peak at approximately 45.5° for Al ₂ O ₃ and Co ₂ AlO ₄ , but also obvious diffraction peaks at approximately 42.6° and approximately 45.0°, which could be due to the fact that composition S-1.8, subjected to treatment in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron . In addition, compared to composition S-1.5, composition S-1.8 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Comparative example 1.1

Example 1.1 was repeated, except that, in terms of metal oxides, cobalt nitrate was replaced by iron nitrate in the same amount, obtaining composition D-1.1.

The test results regarding the content of each component in the composition D-1.1 are shown in table 1.1.

Comparative example 1.2

Example 1.1 was repeated, except that, in terms of metal oxides, iron nitrate was replaced by cobalt nitrate in the same amount, obtaining composition D-1.2.

The test results regarding the content of each component in composition D-1.2 are shown in table 1.1.

Comparative Example 3

A comparative composition was prepared according to the method described in US 6800586. 34.4 g of dried γ-alumina support microspheres were weighed, impregnated with a solution prepared from 10.09 g of cerium nitrate, 2.13 g of lanthanum nitrate and 18 ml of water, dried at 120°C and calcined at 600°C for 1 hour, impregnated again with a solution prepared from 2.7 g of copper nitrate and 18 ml of water, and dried at 120°C and calcined at 600°C for 1 hour to obtain compositions D-3. In terms of oxides composition D-3 contained RE ₂ O ₃ in the amount of 12 wt. % and CuO in the amount of 2.3 wt. % (where RE was a lanthanide metal) based on the total weight of composition D-3.

The content of each component is presented as a mass percentage in terms of oxides.

Example 2.1

(1) 2.62 kg of pseudoboehmite was added to 14.2 kg of deionized water and dispersed to form a slurry. 238 ml of hydrochloric acid was added to the suspension for acidification for 15 minutes to obtain an alumina gel. In terms of metal oxides, 100 g of iron nitrate (calculated as Fe ₂ O ₃ , the same below) and 100 g of cobalt nitrate (calculated as Co ₂ O ₃ , the same below) were added to 3500 ml of water, stirred until complete dissolution , and then the alumina gel was added thereto, stirred for another 15 minutes to obtain the first solution. 100 g of MgO was added to 360 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of particles obtained by spray drying (average particle size was 65 µm, and particles with a size of 40-80 µm were in the amount of 60%, the same below) were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 600° C. for 1.5 hours to obtain composition S-2.1.

The test results regarding the content of each component in the composition S-2.1 are shown in table 2.1.

Composition S-2.1 was analyzed by X-ray diffraction and the X-ray spectrum is shown in FIG. 2. As shown in FIG. 2, there was a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ , and MgAl ₂ O ₄ in the X-ray spectrum of composition S-2.5, which was not treated with carbonaceous atmosphere. In the X-ray spectrum of composition S-2.1, which was subjected to treatment in a carbonaceous atmosphere, there was not only a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° shifted to the left, and the diffraction peak at approximately 45.0° became much stronger, which could be due to the fact that the composition S- 2.1, treated in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-2.5, composition S-2.1 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 2.2

(1) 2.56 kg of pseudoboehmite was added to 13.9 kg of deionized water and dispersed to form a slurry. 232 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 140 g of iron nitrate and 60 g of cobalt nitrate were added to 3500 ml of water, stirred until completely dissolved, and then alumina gel was added thereto, stirred for another 15 minutes to obtain a first solution. 160 g of MgO was added to 480 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. Received composition S-2.2.

The test results regarding the content of each component in the composition S-2.2 are shown in table 2.1. Composition S-2.2 had similar results to example 2.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-2.2, which was subjected to treatment in a carbonaceous atmosphere, there were not only a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° shifted to the left, and the diffraction peak at approximately 45.0° became much stronger, which could be due to the fact that the composition S- 2.2 treated in a carbonaceous atmosphere had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-2.5, composition S-2.2 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 2.3

(1) 2.34 kg of pseudoboehmite was added to 12.7 kg of deionized water and dispersed to form a slurry. 212 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 100 g of iron nitrate and 200 g of cobalt nitrate were added to 4000 ml of water, stirred until completely dissolved, and then aluminum oxide gel was added thereto, stirred for another 15 minutes to obtain a first solution. 200 g of MgO was added to 600 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 650°C for 1 hour to obtain composition S-2.3.

The test results regarding the content of each component in the composition S-2.3 are shown in table 2.1. Composition S-2.3 had the same test results as Example 2.1 using X-ray diffraction. In the X-ray spectrum of composition S-2.3, which was subjected to treatment in a carbonaceous atmosphere, there were not only a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° shifted to the left, and the diffraction peak at approximately 45.0° became much stronger, which could be due to the fact that the composition S- 2.3, treated in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-2.5, composition S-2.3 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 2.4

(1) 2.25 kg of pseudoboehmite was added to 12.2 kg of deionized water and dispersed to form a slurry. 204 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 200 g of iron nitrate and 120 g of cobalt nitrate were added to 3500 ml of water, stirred until completely dissolved, and then alumina gel was added thereto, stirred for another 15 minutes to obtain a first solution. 240 g of MgO was added to 720 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 600° C. for 1.5 hours to obtain composition S-2.4.

The test results regarding the content of each component in the composition S-2.4 are shown in table 2.1. Composition S-2.4 had similar results to example 2.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-2.4, which was subjected to treatment in a carbonaceous atmosphere, there were not only a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° shifted to the left, and the diffraction peak at approximately 45.0° became much stronger, which could be due to the fact that the composition S- 2.4, treated in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-2.5, composition S-2.4 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt. Example 2.5

Example 2.1 was repeated, except that the mixed gas CO/N ₂ with a CO concentration of 10 vol. % was replaced with air to obtain composition 2.5.

The test results regarding the content of each component in the composition S-2.5 are shown in table 2.1. Composition S-2.5 was analyzed by X-ray diffraction. From the X-ray spectrum (as shown in Fig. 2) it can be seen that there were no obvious diffraction peaks at 2θ 42.6°, 44.2° and 44.9°, which showed that the entire amount of Fe and Co in the composition of S- 2.5 was presented as oxides.

Example 2.6

Example 2.1 was repeated, except that MgO was replaced by CaO in the same amount in terms of metal oxides, to obtain composition S-2.6.

The test results regarding the content of each component in the composition S-2.6 are shown in table 2.1. Composition S-2.6 had similar results to example 2.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-2.6, which was subjected to treatment in a carbonaceous atmosphere, there were not only a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° shifted to the left, and the diffraction peak at approximately 45.0° became much stronger, which could be due to the fact that the composition S- 2.6 treated in a carbonaceous atmosphere had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-2.5, composition S-2.6 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 2.7

Example 2.1 was repeated, except that, in terms of metal oxides, iron nitrate was used in an amount of 50 g, and cobalt nitrate was used in an amount of 150 g, to obtain composition S-2.7.

The test results regarding the content of each component in the composition S-2.7 are shown in table 2.1. Composition S-2.7 had similar results to example 2.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-2.7, which was subjected to treatment in a carbonaceous atmosphere, there were not only a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° shifted to the left, and the diffraction peak at approximately 45.0° became much stronger, which could be due to the fact that the composition S- 2.7 treated in a carbonaceous atmosphere had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-2.5, composition S-2.7 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 2.8

Example 2.1 was repeated, except that, in terms of metal oxides, iron nitrate was used in an amount of 150 g, and cobalt nitrate was used in an amount of 50 g, to obtain composition S-2.8.

The test results regarding the content of each component in the composition S-2.8 are shown in table 2.1. Composition S-2.8 had similar results to example 2.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-2.8, which was subjected to treatment in a carbonaceous atmosphere, there were not only a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° shifted to the left, and the diffraction peak at approximately 45.0° became much stronger, which could be due to the fact that the composition S- 2.8 treated in a carbonaceous atmosphere had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-2.5, composition S-2.8 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 2.9

Example 2.1 was repeated, except that the mixed gas CO/N ₂ with a CO concentration of 10 vol. % was replaced by a mixed gas of ethane/nitrogen with an ethane concentration of 10 vol. % to obtain composition 2.9.

The test results regarding the content of each component in the composition S-2.9 are shown in table 2.1. Composition S-2.9 had similar results to example 2.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-2.8, which was subjected to treatment in a carbonaceous atmosphere, there were not only a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , CO ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° shifted to the left, and the diffraction peak at approximately 45.0° became much stronger, which could be due to the fact that the composition S- 2.9, treated in a carbonaceous atmosphere, had a diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-2.5, composition S-2.9 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Comparative example 2.1

Example 2.1 was repeated, except that, in terms of metal oxides, the cobalt nitrate was replaced by iron nitrate in the same amount, to obtain composition D-2.1.

The test results regarding the content of each component in composition D-2.1 are shown in table 2.1.

Comparative example 2.2

Example 2.1 was repeated, except that, in terms of metal oxides, iron nitrate was replaced by cobalt nitrate in the same amount, obtaining composition D-2.2.

The test results regarding the content of each component in composition D-2.2 are shown in table 2.1.

The content of each component is presented as a mass percentage in terms of oxides.

Example 3.1

2.62 kg of pseudoboehmite was added to 14.2 kg of deionized water and dispersed to form a slurry. 238 ml of hydrochloric acid was added to the suspension for acidification for 15 minutes to obtain an alumina gel. In terms of metal oxides 60 g of iron nitrate (calculated as Fe ₂ O ₃ , the same below), 60 g of cobalt nitrate (calculated as Co ₂ O ₃ , the same below) and 100 g of KMnO ₄ (calculated as MnO, the same below) was added to 3500 ml of water, stirred until completely dissolved, and then the alumina gel was added thereto, stirred for another 15 minutes to obtain the first solution. 100 g of MgO was added to 300 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of particles obtained by spray drying (average particle size was 65 µm, and particles with a size of 40-80 µm were in the amount of 60%, the same below) were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 600° C. for 1.5 hours to obtain composition S-3.1.

The test results regarding the content of each component in the composition S-3.1 are shown in table 3.1.

Composition S-3.1 was analyzed by X-ray diffraction and the X-ray spectrum is shown in FIG. 3. As shown in FIG. 3, there was a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ , and MgAl ₂ O ₄ in the X-ray spectrum of composition S-3.5, which was not treated with carbonaceous atmosphere. In the X-ray spectrum of composition S-4.1, which was treated in a carbonaceous atmosphere, not only was a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at about 43.0° and at about 45.0° became much stronger and shifted to the left, which could be due to the fact that composition S-3.1, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and F ₇ C ₃ ) and elemental iron. In addition, compared to composition S-3.5, composition S-3.1 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 3.2

(1) 2.53 kg of pseudoboehmite was added to 13.7 kg of deionized water and dispersed to form a slurry. 229 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 100 g of iron nitrate, 60 g of cobalt nitrate and 100 g of KMnO ₄ (calculated as MnO) were added to 3500 ml of water, stirred until completely dissolved, and then the alumina gel was added thereto, stirred for another 15 minutes to obtain the first solution. 160 g of MgO was added to 480 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 500° C. for 3 hours to obtain composition S-3.2.

The test results regarding the content of each component in the composition S-3.2 are shown in table 3.1. Composition S-3.2 had similar results to example 3.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-4.2, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-3.2, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-3.5, composition S-3.2 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 3.3

(1) 2.09 kg of pseudoboehmite was added to 11.3 kg of deionized water and dispersed to form a slurry. 190 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 100 g of iron nitrate, 200 g of cobalt nitrate and 160 g of KMnO ₄ (calculated as MnO) were added to 4000 ml of water, stirred until completely dissolved, and then the alumina gel was added thereto, stirred for another 15 minutes to obtain the first solution. 200 g of MgO was added to 600 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 650°C for 1 hour to obtain composition S-3.3.

The test results regarding the content of each component in the composition S-3.3 are shown in table 3.1. Composition S-3.3 had similar results to example 3.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-3.3, which was subjected to treatment in a carbon-containing atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-3.3, subjected to treatment in a carbonaceous atmosphere, had diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-3.5, composition S-3.3 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 3.4

(1) 2.09 kg of pseudoboehmite was added to 11.3 kg of deionized water and dispersed to form a slurry. 190 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 200 g of iron nitrate, 120 g of cobalt nitrate and 100 g of KMnO ₄ (calculated as MnO) were added to 3500 ml of water, stirred until completely dissolved, and then the alumina gel was added there, stirred for another 15 minutes to obtain the first solution. 240 g of MgO was added to 720 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 100 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 600° C. for 1.5 hours to obtain composition S-3.4.

The test results regarding the content of each component in composition S-3.4 are shown in table 3.1. Composition S-3.4 had similar results to example 3.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-3.4, which was subjected to treatment in a carbon-containing atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-3.4, subjected to treatment in a carbonaceous atmosphere, had diffraction peak at 2θ 44.9°, where a diffraction peak at 2θ 44.9° was present for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-3.5, composition S-3.4 had diffraction peaks at 42.6° and 44.2°, where the diffraction peaks at 29°, 42.6° and 44.2° were for cobalt monoxide and elemental cobalt.

Example 3.5

Example 3.1 was repeated, except that the mixed gas CO/N ₂ with a concentration of CO 10 vol. % was replaced with air to obtain composition 3.5.

The test results regarding the content of each component in the composition S-3.5 are shown in table 3.1. Composition S-3.5 was analyzed by X-ray diffraction. From the X-ray spectrum (as shown in Fig. 3) it can be seen that there were no obvious diffraction peaks at 2θ 42.6°, 44.2° and 44.9°, which showed that all the Fe and Co in the composition S- 3.5 was presented as oxides.

Example 3.6

Example 3.1 was repeated, except that, in terms of metal oxides, MgO was replaced by CaO in the same amount, obtaining composition S-3.6.

The test results regarding the content of each component in the composition S-3.6 are shown in table 3.1. Composition S-3.6 had the same test results as example 3.1 using x-ray diffraction. In the X-ray spectrum of composition S-3.6, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-3.6, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-3.5, composition S-3.6 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 3.7

Example 3.1 was repeated, except that, in terms of metal oxides, KMnO ₄ was replaced by CeCl ₂ in the same amount, obtaining composition S-3.7.

The test results regarding the content of each component in the composition S-3.7 are shown in table 3.1. Composition S-3.7 had similar results to example 3.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-3.7, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-3.7, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-3.5, composition S-3.7 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 3.8

Example 3.1 was repeated, except that, in terms of metal oxides, iron nitrate was used in an amount of 30 g, and cobalt nitrate was used in an amount of 90 g, to obtain composition S-3.8.

The test results regarding the content of each component in the composition S-3.8 are shown in table 3.1. Composition S-3.8 had similar results to example 3.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-3.8, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-3.8, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-3.5, composition S-3.8 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 3.9

Example 3.1 was repeated, except that, in terms of metal oxides, iron nitrate was used in an amount of 90 g, and cobalt nitrate was used in an amount of 30 g, to obtain composition S-3.9.

The test results regarding the content of each component in the composition S-3.9 are shown in table 3.1. Composition S-3.9 had similar results to example 3.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-3.9, which was treated in a carbonaceous atmosphere, not only was a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that the composition S-3.9, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-3.5, composition S-3.9 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 3.10

Example 3.1 was repeated, except that the mixed gas CO/N ₂ with a concentration of CO 10 vol. % was replaced by a mixed gas of ethane/nitrogen with an ethane concentration of 10 vol. % to obtain composition 3.10.

The test results regarding the content of each component in the composition S-3.10 are shown in table 3.1. Composition S-3.10 had the same test results as Example 3.1 using X-ray diffraction. In the X-ray spectrum of composition S-3.10, which was subjected to treatment in a carbon-containing atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-3.10, subjected to treatment in a carbonaceous atmosphere, had diffraction peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-3.5, composition S-3.10 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Comparative example 3.1

Example 3.1 was repeated, except that, in terms of metal oxides, the cobalt nitrate was replaced by iron nitrate in the same amount, to obtain composition D-3.1.

The test results regarding the content of each component in composition D-3.1 are shown in table 3.1.

Comparative example 3.2

Example 3.1 was repeated, except that in terms of metal oxides, iron nitrate was replaced by cobalt nitrate in the same amount, to obtain composition D-3.2.

The test results regarding the content of each component in composition D-3.2 are shown in table 3.1.

The content of each component is presented as a mass percentage in terms of oxides.

Example 4.1

(1) 2.62 kg of pseudoboehmite was added to 14.2 kg of deionized water and dispersed to form a slurry. 238 ml of hydrochloric acid was added to the suspension for acidification for 15 minutes to obtain an alumina gel. In terms of metal oxides, 100 g of iron nitrate (calculated as Fe ₂ O ₃ , the same below) and 100 g of cobalt nitrate (calculated as Co ₂ O ₃ , the same below) were added to 3500 ml of water, stirred until complete dissolution , and then the alumina gel was added thereto, stirred for another 15 minutes to obtain the first solution. 100 g of MgO was added to 360 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 150 g of particles obtained by spray drying (average particle size was 65 µm, and particles with a size of 40-80 µm were in the amount of 60%, the same below) were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 600°C for 1.5 hours to obtain a semi-finished composition.

(2) 100 g of the semi-finished composition was weighed and added to 700 ml of water, then 4.8 ml of a solution of RuCl ₃ with a mass content of 12.5 g/l in terms of metal elements was added thereto, stirred for 20 minutes and filtered to obtain solid product. The solid product was washed with 80 ml of aqueous ammonia at a concentration of 2 mol/l and dried at 100°C for 4 hours, and then calcined at 400°C for 2 hours to obtain composition S-4.1.

The test results regarding the content of each component in the composition S-4.1 are shown in table 4.1.

Composition S-4.1 was analyzed by X-ray diffraction and the X-ray spectrum is shown in FIG. 4. As shown in FIG. 4, there was a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ in the X-ray spectrum of composition S-4.5, which was not treated with carbonaceous atmosphere. In the X-ray spectrum of composition S-4.1, which was treated in a carbonaceous atmosphere, not only was a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that the composition S-4.1, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-4.5, composition S-4.1 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 4.2

(1) 2.56 kg of pseudoboehmite was added to 13.9 kg of deionized water and dispersed to form a slurry. 232 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 140 g of iron nitrate and 60 g of cobalt nitrate were added to 3500 ml of water, stirred until completely dissolved, and then alumina gel was added thereto, stirred for another 15 minutes to obtain a first solution. 160 g of MgO was added to 480 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 150 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 500°C for 3 hours to obtain a semi-finished composition.

(2) 100 g of the semi-finished composition was weighed and added to 700 ml of water, then 4.4 ml of a solution of RuCl ₃ with a mass content of 12.5 g/l in terms of metal elements was added thereto, stirred for 20 minutes and filtered to obtain solid product. The solid product was washed with 100 ml of aqueous ammonia at a concentration of 2 mol/l and dried at 100°C for 4 hours, and then calcined at 400°C for 2 hours to obtain composition S-4.2.

The test results regarding the content of each component in the composition S-4.2 are shown in table 4.1. Composition S-4.2 had similar results to example 4.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-4.2, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that the composition S-4.2, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-4.5, composition S-4.2 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 4.3

(1) 2.34 kg of pseudoboehmite was added to 12.7 kg of deionized water and dispersed to form a slurry. 212 ml of hydrochloric acid was added to the suspension for acidification for 15 minutes to obtain an alumina gel. In terms of metal oxides, 100 g of iron nitrate and 200 g of cobalt nitrate were added to 4000 ml of water, stirred until completely dissolved, and then alumina gel was added thereto, stirred for another 15 minutes to obtain a first solution. 200 g of MgO was added to 600 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 150 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. Processing was carried out at 650°C for 1 hour to obtain a semi-finished composition.

(2) 100 g of the semi-finished composition was weighed and added to 700 ml of water, then 4 ml of a solution of RuCl ₃ with a mass content of 12.5 g/l in terms of metal elements was added thereto, stirred for 20 minutes and filtered to obtain a solid product . The solid product was washed with 80 ml of aqueous ammonia at a concentration of 2 mol/l and dried at 100°C for 4 hours, and then calcined at 400°C for 2 hours to obtain composition S-4.3.

The test results regarding the content of each component in the composition S-4.3 are shown in table 4.1. Composition S-4.3 had the same results as example 4.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-4.3, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-4.3, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-4.5, composition S-4.3 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 4.4

(1) 2.25 kg of pseudoboehmite was added to 12.2 kg of deionized water and dispersed to form a slurry. 204 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 200 g of iron nitrate and 120 g of cobalt nitrate were added to 3500 ml of water, stirred until completely dissolved, and then aluminum oxide gel was added thereto, stirred for another 15 minutes to obtain a first solution. 240 g of MgO was added to 720 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 150 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 600°C for 1.5 hours to obtain a semi-finished composition.

(2) 100 g of the semi-finished composition was weighed and added to 700 ml of water, then 5.2 ml of a solution of RuCl ₃ with a mass content of 12.5 g/l in terms of metal elements was added thereto, stirred for 20 minutes and filtered to obtain solid product. The solid product was washed with 80 ml of aqueous ammonia at a concentration of 2 mol/l and dried at 100°C for 4 hours, and then calcined at 400°C for 2 hours to obtain composition S-4.4.

The test results regarding the content of each component in the composition S-4.4 are shown in table 4.1. Composition S-4.4 had the same results as example 4.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-4.4, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that the composition S-4.4, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-4.5, composition S-4.4 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 4.5

Example 4.1 was repeated, except that the mixed gas CO/N ₂ with a concentration of CO 10 vol. % was replaced with air to obtain composition 4.5.

The test results regarding the content of each component in the composition S-4.5 are shown in table 4.1. Composition S-4.5 was analyzed by X-ray diffraction. From the X-ray spectrum (as shown in Fig. 4) it can be seen that there were no obvious diffraction peaks at 2θ 42.6°, 44.2° and 44.9°, indicating that all of the Fe and Co in the composition S- 4.5 was presented as oxides.

Example 4.6

Example 4.1 was repeated except that step (2) did not include washing the solid with 80 ml of 2 mol/L aqueous ammonia. Instead, the solid product was directly dried and then calcined to give composition S-4.6.

The test results regarding the content of each component in the composition S-4.6 are shown in table 4.1. Composition S-4.6 had similar results to example 4.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-4.6, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-4.6, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-4.5, composition S-4.6 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 4.7

Example 4.1 was repeated, except that, in terms of metal oxides, MgO was replaced by CaO in the same amount, to obtain composition S-4.6.

The test results for the content of each component in composition S-4.7 are shown in Table 4.1. Composition S-4.7 had similar results to example 4.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-4.7, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-4.7, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-4.5, composition S-4.7 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 4.8

Example 4.1 was repeated, except that, in terms of metal oxides, iron nitrate was used in an amount of 50 g, and cobalt nitrate was used in an amount of 150 g, to obtain composition S-4.8.

The test results regarding the content of each component in the composition S-4.8 are shown in table 4.1. Composition S-4.8 had similar results to example 4.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-4.8, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-4.8, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-4.5, composition S-4.8 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 4.9

Example 4.1 was repeated except that, in terms of metal oxides, iron nitrate was used in an amount of 150 g and cobalt nitrate was used in an amount of 50 g, to obtain composition S-4.9.

The test results regarding the content of each component in the composition S-4.9 are shown in table 4.1. Composition S-4.9 had similar results to example 4.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-4.9, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that the composition S-4.9, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-4.5, composition S-4.9 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 4.10

Example 4.1 was repeated, except that the mixed gas CO/N ₂ with a concentration of CO 10 vol. % was replaced by a mixed gas of ethane/nitrogen with an ethane concentration of 19 vol. % to obtain composition 4.10.

The test results regarding the content of each component in the composition S-4.10 are shown in table 4.1. Composition S-4.10 had the same test results as in example 4.1 using x-ray diffraction. In the X-ray spectrum of composition S-4.10, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-4.10, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-4.5, composition S-4.10 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Comparative example 4.1

Example 4.1 was repeated, except that, in terms of metal oxides, cobalt nitrate was replaced by iron nitrate in the same amount, obtaining composition D-4.1.

The test results regarding the content of each component in composition D-4.1 are shown in table 4.1.

Comparative example 4.2

Example 4.1 was repeated, except that in terms of metal oxides, iron nitrate was replaced by cobalt nitrate in the same amount, to obtain composition D-4.2.

The test results regarding the content of each component in composition D-4.2 are shown in table 4.1.

The contents of the first metal element and the second metal element were presented in mass percent in terms of oxides. The content of the fourth element, metal, was presented in mass percent in terms of elements.

Example 5.1

(1) 2.62 kg of pseudoboehmite was added to 14.2 kg of deionized water and dispersed to form a slurry. 238 ml of hydrochloric acid was added to the suspension for acidification for 15 minutes to obtain an alumina gel. In terms of metal oxides 60 g of iron nitrate (calculated as Fe ₂ O ₃ , the same below), 60 g of cobalt nitrate (calculated as Co ₂ O ₃ , the same below) and 100 g of KMnO ₄ (calculated as MnO, the same below) was added to 3500 ml of water, stirred until completely dissolved, and then the alumina gel was added thereto, stirred for another 15 minutes to obtain the first solution. 100 g of MgO was added to 300 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 150 g of particles obtained by spray drying (average particle size was 65 µm, and particles with a size of 40-80 µm were in the amount of 60%, the same below) were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 600°C for 1.5 hours to obtain a semi-finished composition.

(2) 100 g of the semi-finished composition was weighed and added to 700 ml of water, then 4.8 ml of a solution of RuCl ₃ with a mass content of 12.5 g/l in terms of metal elements was added thereto, stirred for 20 minutes and filtered to obtain solid product. The solid product was washed with 80 ml of aqueous ammonia at a concentration of 2 mol/l and dried at 100°C for 4 hours, and then calcined at 400°C for 2 hours to obtain composition S-5.1.

The test results regarding the content of each component in the composition S-5.1 are shown in table 5.1.

Composition S-5.1 was analyzed by X-ray diffraction and the X-ray spectrum is shown in FIG. 5. As shown in FIG. 5, there was a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ , and MgAl ₂ O ₄ in the X-ray spectrum of composition S-5.5, which was not treated with carbonaceous atmosphere. In the X-ray spectrum of composition S-5.1, which was subjected to treatment in a carbonaceous atmosphere, not only were there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-5.1, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.1 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 5.2

(1) 2.53 kg of pseudoboehmite was added to 13.7 kg of deionized water and dispersed to form a slurry. 229 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 100 g of iron nitrate, 60 g of cobalt nitrate and 60 g of KMnO ₄ (calculated as MnO) were added to 3500 ml of water, stirred until completely dissolved, and then the alumina gel was added thereto, stirred for another 15 minutes to obtain the first solution. 160 g of MgO was added to 480 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 150 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 500°C for 3 hours to obtain a semi-finished composition.

(2) 100 g of the semi-finished composition was weighed and added to 700 ml of water, then 4.4 ml of a solution of RuCl ₃ with a mass content of 12.5 g/l in terms of metal elements was added thereto, stirred for 20 minutes and filtered to obtain solid product. The solid product was washed with 100 ml of aqueous ammonia at a concentration of 2 mol/l and dried at 100°C for 4 hours, and then calcined at 400°C for 2 hours to obtain composition S-5.2.

The test results regarding the content of each component in the composition S-5.2 are shown in table 5.1. Composition S-5.2 had similar results to example 5.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-5.2, which was subjected to treatment in a carbonaceous atmosphere, not only was a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became much stronger and shifted to the left, which could be due to the fact that composition S-5.2, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.2 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 5.3

(1) 2.09 kg of pseudoboehmite was added to 11.3 kg of deionized water and dispersed to form a slurry. 190 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 100 g of iron nitrate, 200 g of cobalt nitrate and 160 g of KMnO ₄ (calculated as MnO) were added to 4000 ml of water, stirred until completely dissolved, and then the alumina gel was added thereto, stirred for another 15 minutes to obtain the first solution. 200 g of MgO was added to 600 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 150 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. Processing was carried out at 650°C for 1 hour to obtain a semi-finished composition.

(2) 100 g of the semi-finished composition was weighed and added to 700 ml of water, then 4 ml of a solution of RuCl ₃ with a mass content of 12.5 g/l in terms of metal elements was added thereto, stirred for 20 minutes and filtered to obtain a solid product . The solid product was washed with 80 ml of aqueous ammonia at a concentration of 2 mol/l and dried at 100°C for 4 hours, and then calcined at 400°C for 2 hours to obtain composition S-5.3.

The test results regarding the content of each component in the composition S-5.3 are shown in table 5.1. Composition S-5.3 had similar results to example 5.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-5.3, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-5.3, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.3 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 5.4

(1) 2.99 kg of pseudoboehmite was added to 11.3 kg of deionized water and dispersed to form a slurry. 190 ml of hydrochloric acid was added to the suspension to acidify for 15 minutes to obtain an alumina gel. In terms of metal oxides, 200 g of iron nitrate, 120 g of cobalt nitrate and 100 g of KMnO ₄ (calculated as MnO) were added to 3500 ml of water, stirred until completely dissolved, and then the alumina gel was added thereto, stirred for another 15 minutes to obtain the first solution. 240 g of MgO was added to 720 g of water, stirred for 10 minutes, and then added to the first solution, stirred for another 20 minutes to obtain a suspension. The suspension was spray dried. 150 g of spray-dried particles were weighed and transferred to a tube furnace. Mixed gas CO / N ₂ with a concentration of CO 10 vol. % was introduced into a tube furnace at a rate of 100 ml/minute. The treatment was carried out at 600°C for 1.5 hours to obtain a semi-finished composition.

(2) 100 g of the semi-finished composition was weighed and added to 700 ml of water, then 5.2 ml of a solution of RuCl ₃ with a mass content of 12.5 g/l in terms of metal elements was added thereto, stirred for 20 minutes and filtered to obtain solid product. The solid product was washed with 80 ml of aqueous ammonia at a concentration of 2 mol/l and dried at 100°C for 4 hours, and then calcined at 400°C for 2 hours to obtain composition S-5.4.

The test results regarding the content of each component in the composition S-5.4 are shown in table 5.1. Composition S-5.4 had the same test results as Example 5.1 using X-ray diffraction. In the X-ray spectrum of composition S-5.4, which was subjected to treatment in a carbonaceous atmosphere, not only was a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-5.4, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.4 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 5.5

Example 5.1 was repeated, except that the mixed gas CO/N ₂ with a CO concentration of 10 vol. % was replaced with air to obtain composition 5.5.

The test results for the content of each component in composition S-5.5 are shown in Table 5.1. Composition S-5.5 was analyzed by X-ray diffraction. From the X-ray spectrum (as shown in Fig. 5) it can be seen that there were no obvious diffraction peaks at 2θ 42.6°, 44.2° and 44.9°, which showed that all the Fe and Co in the composition S- 5.5 was presented as oxides.

Example 5.6

Example 5.1 was repeated except that step (2) did not include washing the solid with 80 ml of 2 mol/L aqueous ammonia. Instead, the solid product was directly dried and then calcined to give composition S-5.6.

The test results regarding the content of each component in the composition S-5.6 are shown in table 5.1. Composition S-5.6 had the same results of testing using x-ray diffraction as in example 5.1. In the X-ray spectrum of composition S-5.6, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that the composition S-5.6, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.6 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 5.7

Example 5.1 was repeated, except that, in terms of metal oxides, MgO was replaced by CaO in the same amount, to obtain composition S-5.7.

The test results regarding the content of each component in the composition S-5.7 are shown in table 5.1. Composition S-5.7 had similar results to example 5.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-5.7, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-5.7, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.7 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 5.8

Example 5.1 was repeated, except that, in terms of metal oxides, KMnO ₄ was replaced by CeCl ₂ in the same amount, obtaining composition S-5.8.

The results of testing the content of each component in composition S-5.8 are shown in table 5.1. Composition S-5.8 had the same results of testing using x-ray diffraction as in example 5.1. In the X-ray spectrum of composition S-5.8, which was subjected to treatment in a carbonaceous atmosphere, not only was a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-5.8, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.8 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 5.9

Example 5.1 was repeated, except that, in terms of metal oxides, iron nitrate was used in an amount of 30 g, and cobalt nitrate was used in an amount of 90 g, to obtain composition S-5.9.

The test results regarding the content of each component in the composition S-5.9 are shown in table 5.1. Composition S-5.9 had similar results to example 5.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-5.9, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.0° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that the composition S-5.9, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.9 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 5.10

Example 5.1 was repeated, except that, in terms of metal oxides, iron nitrate was used in an amount of 99 g, and cobalt nitrate was used in an amount of 39 g, to obtain composition S-5.19.

The test results regarding the content of each component in the composition S-5.10 are shown in table 5.1. Composition S-5.19 had the same test results as Example 5.1 using X-ray diffraction. In the X-ray spectrum of composition S-5.19, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.9° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.9° became significantly stronger and shifted to the left, which could be due to the fact that the composition S-5.19, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.10 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Example 5.11

Example 5.1 was repeated, except that the mixed gas CO/N ₂ with a CO concentration of 10 vol. % was replaced by a mixed gas of ethane/nitrogen with an ethane concentration of 19 vol. % to obtain composition 5.11.

The test results regarding the content of each component in the composition S-5.11 are shown in table 5.1. Composition S-5.11 had similar results to example 5.1 testing using x-ray diffraction. In the X-ray spectrum of composition S-5.11, which was subjected to treatment in a carbonaceous atmosphere, not only was there a diffraction peak at approximately 43.9° for MgO and a diffraction peak at approximately 45.0° for Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ , but also the diffraction peaks at approximately 43.0° and at approximately 45.0° became significantly stronger and shifted to the left, which could be due to the fact that composition S-5.11, subjected to treatment in a carbonaceous atmosphere, had a diffractive peak at 2θ 44.9° for FeC (Fe ₃ C and Fe ₇ C ₃ ) and elemental iron. In addition, compared to composition S-5.5, composition S-5.11 had diffraction peaks at 2θ of 42.6° and 44.2° for cobalt monoxide and elemental cobalt.

Comparative example 5.1

Example 5.1 was repeated, except that, in terms of metal oxides, the cobalt nitrate was replaced by iron nitrate in the same amount, to obtain composition D-5.1.

The test results regarding the content of each component in composition D-5.1 are shown in table 5.1.

Comparative example 5.2

Example 5.1 was repeated, except that, in terms of metal oxides, iron nitrate was replaced by cobalt nitrate in the same amount, obtaining composition D-5.2.

The test results regarding the content of each component in composition D-5.2 are shown in table 5.1.

The content of the first metal element, the second metal element, and the third metal element were presented in mass percent in terms of oxides. The content of the fourth element, metal, was presented in mass percent in terms of elements.

Test Example 1

This test example was used to show the effects of the CO and NOx abatement compositions shown in the Examples and Comparative Examples on CO and NOx abatement in incomplete flue gas regeneration under aerobic conditions.

Compositions capable of reducing CO and NOx emissions were mixed with the above catalyst for catalytic cracking (Cat-A), and compositions capable of reducing CO and NOx emissions were in an amount of 2.2 wt. % based on the total weight of the compositions capable of reducing CO and NOx emissions and catalytic cracking catalyst, and aged at 800°C in an atmosphere of 100% steam for 12 hours. They were then subjected to evaluation of the catalytic cracking-regeneration reaction.

The evaluation of the catalytic cracking-regeneration reaction was carried out in a small fixed bed device simulating the reduction of NOx in the flue gas, with an aged catalyst load of 10 g, a reaction temperature of 650° C., and a feed gas volumetric flow rate of 1500 ml/minute. The feed gas contained 3.7 vol. % CO, 0.5 vol. % oxygen, 800 ppm NH ₃ and the rest is N ₂ . The gaseous products were analyzed using an infrared analyzer in real time to obtain the concentrations of NH ₃ , NOx and CO after the reaction. The results are shown in tables 1.2-5.2.

Based on the data in the above tables, it can be seen that when used in a catalytic cracking partial regeneration process (under aerobic conditions), the compositions of the present invention capable of reducing CO and NOx emissions had better CO, NH ₃ and NOx emission reduction characteristics compared to compositions capable of reducing CO and NOx emissions shown in the comparative example. In addition, the evaluation used an aged composition capable of reducing CO and NOx emissions. The aged composition capable of reducing CO and NOx emissions still provided high CO, NH ₃ and NOx removal activity. Thus, the composition of the present invention capable of reducing CO and NOx emissions had good hydrothermal stability.

Test Example 2

This test example was used to show the effects of the CO and NOx abatement compositions shown in the Examples and Comparative Examples on CO and NOx abatement in incomplete anaerobic flue gas regeneration.

Test Example 1 was repeated except that the feed gas contained 3.7 vol. % CO, 800 ppm NH ₃ and the rest is N ₂ . Received the concentration of NH ₃ , NOx and CO after the reaction, and the results are shown in tables 1.3-3.3.

From the above tables, it can be seen that even when used in the treatment of incompletely recovered catalytic cracking flue gas under anaerobic conditions, the compositions of the present invention capable of reducing CO and NOx emissions had better CO and NH ₃ emission reduction characteristics compared to compositions capable of reducing emissions of CO and NOx presented in the comparative example. In addition, the evaluation used an aged composition capable of reducing CO and NOx emissions. The aged composition capable of reducing CO and NOx emissions still provided high CO and NH ₃ removal activity. Thus, the composition of the present invention capable of reducing CO and NOx emissions had good hydrothermal stability.

Based on the data in the above tables, it can be seen that the compositions of the present invention capable of reducing CO and NOx emissions are suitable for partial regeneration under both aerobic and anaerobic conditions and have better hydrothermal stability. In particular, by introducing preferential calcination in a carbonaceous atmosphere, the performance of compositions capable of reducing CO and NOx emissions could be further improved; by introducing preferred metal elements, it was possible to further improve the performance of compositions capable of reducing CO and NOx emissions; and by implementing a preferred weight ratio of Fe to Co, it was possible to further improve the performance of compositions capable of reducing CO and NOx emissions.

Test Example 3

This test example was used to show the effects of the CO and NOx abatement compositions shown in the Examples and Comparative Examples on CO and NOx reduction in full flue gas recovery and their effects on the distribution of the resulting FCC products.

Compositions capable of reducing CO and NOx emissions were mixed with a catalytic cracking catalyst (Cat-A), with compositions capable of reducing CO and NOx emissions being in an amount of 0.8 wt. % based on the total weight of the compositions capable of reducing CO and NOx emissions and catalytic cracking catalyst, and aged at 800°C in an atmosphere of 100% steam for 12 hours. They were then subjected to evaluation of the catalytic cracking-regeneration reaction.

The evaluation of the catalytic cracking-regeneration reaction was carried out in a small fixed bed apparatus, with an aged catalyst load of 10 g, a reaction temperature of 500° C., and a catalyst to oil ratio of 6. The characteristics of the feed oil are given in Table 4. Gaseous products were analyzed by real-time chromatography. time to obtain the composition of the cracking gases. Liquid products were analyzed by offline chromatography to give yields of gasoline, diesel and fuel oil.

After the reaction, after stripping for 10 minutes with N ₂ , regeneration was carried out by in-situ combustion of coke with a regeneration air flow rate of 200 ml/minute, a regeneration time of 15 minutes, and an initial regeneration temperature the same as the reaction temperature. The flue gas during the regeneration process was collected. After regeneration, the coke yield was calculated according to the accumulated data of an infrared CO ₂ analyzer. The distribution of FCC products was obtained by normalizing the yields of all products, as shown in tables 4.5-5.5, where the conversion was related to the sum of the yields of dry gas, liquefied gas, gasoline and coke. NOx and CO concentrations in the flue gas were measured using a Flue Gas Analyzer Testo350pro and the results are shown in Tables 4.6-5.6.

From the above tables, it can be seen that the use of compositions of the present invention capable of reducing CO and NOx emissions in combination with a catalytic cracking catalyst resulted in low yields of coke and dry gas in the FCC products.

Based on the data in the above tables, it can be seen that when used in a catalytic cracking process, the compositions of the present invention capable of reducing CO and NOx emissions had better CO and NOx emission reduction characteristics compared to the compositions capable of reducing CO and NOx emissions presented in comparative example. In addition, the evaluation used an aged composition capable of reducing CO and NOx emissions. The aged composition capable of reducing CO and NOx emissions still provided high CO and NH ₃ removal activity. Thus, the composition of the present invention capable of reducing CO and NOx emissions had good hydrothermal stability.

Preferred embodiments of the present invention have been described in detail. However, the present invention is not limited to the specific details of the above embodiments. Various simple modifications can be made to the embodiments of the present invention within the scope of the technical idea of the present invention. Such simple modifications are within the protection scope of the present invention.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the present invention. The present invention is not described in detail for possible combinations to avoid unnecessary repetition.

In addition, any combination of embodiments of the present invention is also possible, as long as it does not deviate from the essence of the present invention, which should be considered as a disclosure of the present invention.

Claims (24)

1. A composition capable of reducing CO and NOx emissions, comprising: a carrier based on an inorganic oxide and a first metal element deposited on a carrier based on an inorganic oxide, the first metal element being selected from the group consisting of non-noble metal elements of group VIII, moreover, the first metal element includes Fe and Co, and moreover, the mass ratio of Fe to Co is 1: (0.1-10) in terms of oxides, and the composition also contains a second metal element deposited on a carrier based on an inorganic oxide, and the second metal is at least one selected from the group consisting of metal elements from group IA and/or IIA, and moreover, in terms of the total weight of the composition, the carrier based on inorganic oxide is in the amount of 10-90 wt. %, and in terms of oxides, the first metal element is in the amount of 0.5-50 wt. %, and the second metal element is in the amount of 0.5-20 wt. %. 2. The composition according to claim 1, wherein the composition also comprises a third metal element deposited on an inorganic oxide carrier, the third metal being at least one selected from the group consisting of non-noble metal elements from groups IB-VIIB , and moreover, in terms of the total weight of the composition, the third metal element is in the amount of 0.5-20 wt. % in terms of oxides. 3. The composition according to any of the preceding paragraphs. 1-2, wherein the composition also comprises a fourth metal element deposited on an inorganic oxide carrier, the fourth metal being at least one selected from the group consisting of noble metal elements, and moreover, in terms of the total weight of the composition, the fourth the metal element is in the amount of 0.001-0.15 wt. % in terms of elements. 4. Composition according to any of the preceding paragraphs. 1-3, and the composition contains a carrier based on an inorganic oxide and a first metal element, a second metal element, a third metal element and a fourth metal element deposited on a carrier based on an inorganic oxide, and moreover, in terms of the total weight of the composition, the carrier based on inorganic oxide is in the amount of 50-90 wt. %, and in terms of oxides, the first metal element is in the amount of 3-30 wt. %, the second metal element is in the amount of 1-20 wt. %, the third metal element is in the amount of 1-10 wt. %, and in terms of elements, the fourth metal element is in the amount of 0.005-0.1 wt. %. 5. Composition according to any one of the preceding paragraphs. 1-4, in which the mass ratio of Fe to Co is 1:(0.3-3) in terms of oxides. 6. Composition according to any one of the preceding paragraphs. 1-5, in which the x-ray pattern of the composition contains diffraction peaks at 2θ 42.6°, 44.2° and 44.9°. 7. Composition according to any one of the preceding paragraphs. 1-6, wherein the inorganic oxide carrier is at least one selected from the group consisting of alumina, silica-alumina, zeolite, spinel, kaolin, diatomite, perlite, and perovskite. 8. Composition according to any one of the preceding paragraphs. 1-7, wherein the second metal element is at least one selected from the group consisting of Na, K, Mg and Ca; the third metal element is at least one selected from the group consisting of Cu, Zn, Ti, Zr, V, Cr, Mo, W, Mn and rare earth elements; the fourth metal element is at least one selected from the group consisting of Pt, Ir, Pd, Ru and Rh. 9. A method for obtaining a composition according to claim 1, including: (1) preparing a slurry by mixing an inorganic oxide carrier precursor, a first metal precursor, a second metal precursor, and water, spray drying the slurry, and then calcining to obtain a composition, in which the calcination in stage (1) is performed in a carbon-containing atmosphere at a temperature of 400-1000°C for 0.1-10 hours. 10. The method according to p. 9, providing for: (1) preparing a slurry by mixing an inorganic oxide support precursor, a first metal precursor, a second metal precursor, a third metal precursor, and water, spray drying the slurry, and then calcining to obtain a composition. 11. The method according to any of the preceding paragraphs. 9-10, additionally providing: (2) impregnating the composition obtained in step (1) in an impregnating solution containing a fourth metal element precursor to obtain a solid product, and then drying the solid product and/or performing a second calcination. 12. The method according to any of the preceding paragraphs. 9-11, wherein the inorganic oxide support is alumina; and moreover, before obtaining a suspension, the alumina precursor is treated with acid peptization, and the acid used in the acid peptization is hydrochloric acid, and the acid peptization is carried out with an acid to alumina ratio of 0.12-0.22: 1 for 20-40 minutes . 13. The method according to p. 11, and the method further provides after the impregnation of stage (2) performing alkaline treatment of the solid product before drying and/or second calcination; and moreover, alkaline processing includes: obtaining a suspension by mixing a solid product and an alkaline solution, or washing a solid product with an alkaline solution. 14. The use of a composition capable of reducing CO and NOx emissions, according to any one of the preceding paragraphs. 1-8 for flue gas treatment. 15. The use of a composition capable of reducing CO and NOx emissions, according to any one of the preceding paragraphs. 1-8 for treating flue gas from regeneration in a catalytic cracking process. 16. The method of catalytic cracking in a fluidized bed, which includes: contact and reaction of liquid petroleum products with a catalyst and regeneration of the catalyst after contact and reaction, wherein the catalyst contains a catalytic cracking catalyst and a composition capable of reducing CO and NOx emissions, and moreover, a composition capable of reducing CO emissions and NOx, is a composition capable of reducing CO and NOx emissions, according to any one of the preceding paragraphs. 1-8. 17. The method of catalytic cracking in a fluidized bed according to p. 16, in which the composition capable of reducing CO and NOx emissions is in an amount of 0.05-5 wt. %, based on the total weight of the catalyst.

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