CN109201080B - Compositions capable of reducing CO and NOx emissions, methods for their preparation and applications, and methods for fluid catalytic cracking - Google Patents

Abstract

The invention relates to the field of catalytic cracking, and discloses a composition capable of reducing CO and NOx emissions, a preparation method and application thereof, and a fluidized catalytic cracking method. The method comprises: (1) combining a precursor of an inorganic oxide carrier, a first metal The element precursor and water are mixed and beaten to obtain a slurry, the slurry is spray-dried, and then first roasted to obtain a semi-finished product composition; (2) with the solution containing the fourth metal element precursor as the dipping solution, step ( 1) The obtained semi-finished product composition is impregnated to obtain a solid product, and the solid product is subjected to alkali treatment, followed by drying and/or second roasting. The composition prepared by the method provided by the present invention has higher hydrothermal stability and higher activity of reducing CO and NOx emission of regeneration flue gas.

Description

Compositions capable of reducing CO and NOx emissions, methods of making and using the same, and streams chemical catalytic cracking process

technical field

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 preparing the composition capable of reducing CO and NOx emissions, and a composition capable of reducing CO and NOx emissions prepared by the method, and the above-mentioned compositions capable of reducing CO and NOx emissions. Use of a composition for reducing CO and NOx emissions and a fluid catalytic cracking process.

Background technique

The rising price of crude oil has greatly increased the processing cost of refineries. On the one hand, refineries reduce costs by purchasing low-priced and inferior oil; on the other hand, they increase economic benefits by in-depth processing of heavy oil. Catalytic cracking, as an important means of heavy oil processing in refineries, plays an important role in refineries. It is not only the main means of heavy oil balance and clean fuel production in refineries, but also the focus of energy conservation and efficiency enhancement in refineries. Catalytic cracking is a fast catalytic reaction system with rapid catalyst deactivation, and solving the problem of catalyst regeneration has always been the main line of catalytic cracking development.

In the process of fluid catalytic cracking (FCC), the feedstock oil and the regenerated catalyst are rapidly contacted in the riser to carry out the catalytic cracking reaction, and the coke generated by the reaction is deposited on the catalyst to cause its deactivation. A regenerator, which is in contact with the regeneration air or oxygen-enriched air entering the bottom of the regenerator for scorch regeneration. The regenerated catalyst is recycled back to the reactor to participate in the catalytic cracking reaction again. According to the level of excess oxygen content in the flue gas or the sufficient degree of CO oxidation during the regeneration process, the catalytic cracking unit can be divided into complete regeneration and incomplete regeneration operations.

During the complete regeneration process, the coke and the nitrogen-containing compounds in the coke generate CO ₂ and N ₂ under the action of the regeneration air, and also produce pollutants such as CO and NOx. The use of catalytic promoters is an important technical measure to control CO and NOx emission pollution.

The adjuvant used to reduce the CO emission of the regenerated flue gas is usually referred to as a CO combustion accelerant. For example, CN1022843C discloses a noble metal supported carbon monoxide combustion accelerant, the active component of which is 1-1000ppm platinum or 50-1000ppm palladium, and the carrier is composed of (1 ) 99.5-50% of cracking catalyst or microsphere particles of its matrix and (2) 0.5-50% Al ₂ O ₃ , 0-20% RE ₂ O ₃ and 0-15% ZrO ₂ composition, (2) is ( 1) The outer coating of the particles.

Adjuvants used to control flue gas NOx emissions are commonly referred to as NOx reduction aids or NOx reduction aids, for example CN102371150A discloses a non-precious metal composition for reducing NOx emissions from catalytic cracking regeneration flue gas, the composition The bulk ratio does not exceed 0.65 g/ml, based on the weight of the composition, and contains, in terms of oxide: (1) 50-99 wt % inorganic oxide carrier, (2) 0.5-40 wt % optional One or several non-noble metal elements from groups IIA, IIB, IVB and VIB, and (3) 0.5-30 wt% rare earth elements. The composition is used in fluid catalytic cracking and can significantly reduce NOx emissions from regeneration flue gas.

There is also a class of additives that can simultaneously reduce CO and NOx emissions from regenerated flue gas, and can take into account both CO combustion support and NOx emission reduction. With the increasingly strict environmental regulations, the application of such additives is becoming more and more common. For example, CN1688508A discloses a composition for reducing NOx and CO emissions from fluidized catalytic cracking flue gas and its application, the composition comprising copper and/or cobalt and a carrier selected from the group consisting of hydrotalcite compounds, sharp Spar, alumina, zinc titanate, zinc aluminate, zinc titanate/zinc aluminate. CN102371165A discloses a low stack ratio composition for reducing CO and NOx emissions from FCC regeneration flue gas, the composition contains rare earth elements and one or several non-precious metal elements, preferably the non-precious metals are supported on Y-type zeolite. US6165933 discloses a CO combustion-supporting composition (co-agent) for reducing NOx emissions from a catalytic cracking process, the composition comprising: (i) an acidic metal oxide substantially free of zeolite; (ii) an alkali metal, alkaline earth metal or is a mixture thereof; (iii) an oxygen storage component and (iv) palladium, the inorganic oxide support is preferably silica-alumina, and the oxygen storage transition metal oxide is preferably ceria. US7045056 discloses a composition for simultaneously reducing CO and NOx emissions from a catalytic cracking process flue gas, the composition comprising: (i) an inorganic oxide support; (ii) an oxide of cerium; (iii) a a lanthanide oxide other than cerium, wherein the weight ratio of (ii) to (iii) is at least 1.66:1; (iv) optionally a Group IB and IIB transition metal oxide, and (v) at least one a precious metal element. CN105363444A discloses a composition for reducing CO and NOx emissions from FCC regeneration flue gas and a preparation method thereof, the composition contains in terms of oxides: (1) 0.5-30 wt% rare earth elements, (2) 0.01 -0.15% by weight of precious metal elements, and (3) the balance of an inorganic oxide support that is substantially free of alkali metals and alkaline earth metals; in the preparation method, the composition after the introduction of precious metals is subjected to alkaline treatment before drying and/or calcination Solution treatment, the disclosed composition is used for fluidized catalytic cracking, which can effectively avoid "after-burning" caused by excessively high CO concentration in the regenerated flue gas, can effectively control the emission concentration of CO and NOx in the regenerated flue gas, and significantly reduce the smoke Gas NOx emissions, basically no adverse effect on the distribution of FCC products.

During the incomplete regeneration process, due to the low excess oxygen content and high CO concentration in the flue gas, the NOx concentration in the flue gas at the regenerator outlet is very low, while the concentration of reduced nitrogen compounds such as NH ₃ and HCN is high. These reduced nitrogens flow downstream with the flue gas. In the CO boiler used for energy recovery, if they are fully oxidized, NOx will be generated; if they are not fully oxidized, the remaining NH ₃ will easily cause downstream scrubber wastewater. Ammonia nitrogen exceeds the standard, or reacts with SO _x in the flue gas to form ammonium salts, which will cause salt formation in the residual boiler or other flue gas post-processing equipment (such as SCR), which will affect the long-term operation of the device. Therefore, the incomplete regeneration process uses catalytic promoters to catalytically convert NH ₃ and other substances in the regenerator, which can reduce the NOx emission in the flue gas and prolong the operation period of the device.

US5021144 discloses a method for reducing _NH3 emission in flue gas of incompletely regenerated FCC unit. The method is to add excess CO combustion-supporting agent in the regenerator, and the addition amount is the minimum addition amount that can prevent tail-burning in the dilute phase bed. 2-3 times. Although this method can reduce the _NH3 emission in the flue gas of the incompletely regenerated FCC unit, the amount of CO used is relatively large, which has the disadvantage of high energy consumption, and is not conducive to environmental protection.

US4755282 discloses a method for reducing _NH3 emissions in the flue gas of a partially regenerated or incompletely regenerated FCC unit. This method converts _NH3 into _N2 and water by adding ammonia decomposition catalyst with a particle size of 10-40 μm into the regenerator to maintain a certain concentration in the dilute phase bed. The active component of the ammonia decomposition catalyst may be a noble metal dispersed on an inorganic oxide support.

CN101024179A discloses a NOx reducing composition for use in an FCC process comprising (i) an acidic metal oxide substantially free of zeolite, (ii) alkali metals, alkaline earth metals and mixtures thereof and (iii) Oxygen storage components. The prepared composition is impregnated with precious metal to convert gas-phase reduced nitrogen substances in flue gas of incomplete regeneration catalytic cracking unit, and reduce NOx emission of flue gas.

At present, there are relatively few reports on the research and application of adjuvant technology for controlling the emission of _NH3 and NOx in the flue gas of the incomplete regeneration device. Since the flue gas composition of the incomplete regeneration device is significantly different from that of the complete regeneration device, the existing ones are suitable for the complete regeneration device. The application effect of the incomplete regeneration device is not ideal. Although the adjuvant compositions disclosed in the above technologies can catalytically convert reduced nitrogen compounds such as NH _{3 in flue gas to a certain extent, the catalytic conversion activity of NH 3 and} other reduced nitrogen compounds in flue gas still needs to be improved to slow down. The impact of NH ₃ and other deposited salts on the operation of the equipment requires the development of flue gas pollutant emission reduction aids suitable for incomplete regeneration devices to further reduce flue gas NOx emissions.

SUMMARY OF THE INVENTION

Aiming at the defect of low catalytic conversion activity of _NH3 and other reduced nitrogen compounds in the regeneration process of the prior art, the present invention provides a new composition capable of reducing CO and NOx emissions, and a composition capable of reducing CO and NOx emissions A preparation method and a composition capable of reducing CO and NOx emissions prepared by the method, application of the above-mentioned composition capable of reducing CO and NOx emissions in flue gas treatment, and a fluidized catalytic cracking method. The composition capable of reducing CO and NOx emissions provided by the invention has high catalytic conversion activity to reduced nitrogen compounds, and the preparation method is simple, and can be used in the fluidized catalytic cracking process, and can effectively reduce CO and NOx in the catalytic cracking regeneration flue gas emission.

The inventors of the present invention found in the research process that an inorganic oxide is used as a carrier, a Group VIII non-precious metal element containing Fe and Co is used in combination with at least one of noble metal elements as an active component, and the composition is prepared during the preparation process. After impregnating the precious metal, the obtained solid product is subjected to alkali treatment, so that the precious metal element (the fourth metal element) and the first metal element can be closely combined, which is conducive to the synergistic effect of the two, which is conducive to improving the ability to reduce CO Catalytic conversion activity and hydrothermal stability of the composition for reducing nitrogen such as _NH3 and NOx emissions.

Through further research, it was found that, in the preferred case, the Group VIII non-noble metal element containing Fe and Co is compounded with a noble metal element and a second metal element (at least one of Group IA and/or IIA metal elements) and a third metal element. The use of at least one of the elements (at least one of the non-precious metal elements of Groups IB-VIIB) can more effectively reduce CO and NOx emissions in the catalytic cracking regeneration flue gas, and it is speculated that the reason may be due to the Or at least one of Group IIA metal elements, at least one of Group IB-VIIB non-precious metal elements and noble metal elements jointly modify the first metal element, which is more conducive to exerting the synergistic effect between metals and is conducive to reducing oxidation It can promote the formation of nitrogen-containing compounds in the reduced state, and can promote the decomposition of nitrogen-containing compounds in the reduced state.

Based on this, according to a first aspect of the present invention, there is provided a method for preparing a composition for reducing CO and NOx emissions, the method comprising:

(1) mixing and beating the precursor of the inorganic oxide carrier, the first metal element precursor and water to obtain a slurry, the slurry is spray-dried, and then first roasted to obtain a semi-finished product composition;

(2) Impregnating the semi-finished product composition obtained in step (1) with the solution containing the precursor of the fourth metal element as the impregnating liquid to obtain a solid product, subjecting the solid product to alkali treatment, and then drying and/or second roasting;

Wherein, the first metal element is selected from group VIII non-noble metal elements, and the first metal element includes Fe and Co; the fourth metal element is selected from at least one of noble metal elements;

Wherein, in the first metal element precursor, the amount of Fe precursor and Co precursor is such that in the obtained composition, in terms of oxide, the weight ratio of Fe to Co is 1:(0.05-20).

According to a second aspect of the present invention, there is provided a composition capable of reducing CO and NOx emissions prepared by the above preparation method.

According to a third aspect of the present invention, there is provided the use of the above-mentioned composition capable of reducing CO and NOx emissions in flue gas treatment.

According to a fourth aspect of the present invention, there is provided the use of the above-mentioned composition capable of reducing CO and NOx emissions in the treatment of catalytic cracking regeneration flue gas.

According to a fifth aspect of the present invention, there is provided a fluidized catalytic cracking method, the method comprising: contacting and reacting hydrocarbon oil with a catalyst, and then regenerating the catalyst after the contact reaction, the catalyst comprising a catalytic cracking catalyst and a catalyst capable of reducing CO and a composition for reducing CO and NOx emission, the composition capable of reducing CO and NOx emission is the above-mentioned composition capable of reducing CO and NOx emission of the present invention.

In the preparation method of the composition capable of reducing CO and NOx emissions provided by the present invention, the utilization rate of precious metals is high and the production cost is low; and the composition capable of reducing CO and NOx emissions provided by the present invention is used as fluidized catalytic cracking to reduce CO and NOx emission aids, resulting in lower coke and dry gas yields in FCC products. Compared with the FCC method using the existing CO and NOx emission reduction aids, the FCC method using the composition capable of reducing CO and NOx emission provided by the present invention, the amount of the composition capable of reducing CO and NOx emission is low, and the CO and higher NOx emission activity.

For example, the composition prepared by the method for preparing a composition capable of reducing CO and NOx emissions provided in Example 3 of the present invention is uniformly blended with the FCC main catalyst (Cat-A) in a proportion of 0.8% by weight of the total weight of the catalyst. , the catalytic cracking reaction-regeneration evaluation was carried out after aging at 800 ° C and 100% steam atmosphere for 12 hours. Compared with the composition D-3 which can reduce CO and NOx emissions prepared by the saturated impregnation method of active components in the prior art , when the composition capable of reducing CO and NOx emission prepared by the preparation method provided by the invention is used, the emission concentration of NOx in the completely regenerated flue gas is reduced from 264ppm to 36ppm.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Detailed ways

The endpoints of ranges and any values disclosed herein are not limited to the precise ranges or values, which are to be understood to encompass values proximate to those ranges or values. For ranges of values, the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein.

The present invention provides a preparation method of a composition capable of reducing CO and NOx emissions, the method comprising:

(1) mixing and beating the precursor of the inorganic oxide carrier, the first metal element precursor and water to obtain a slurry, the slurry is spray-dried, and then first roasted to obtain a semi-finished product composition;

(2) Impregnating the semi-finished product composition obtained in step (1) with the solution containing the precursor of the fourth metal element as the impregnating liquid to obtain a solid product, subjecting the solid product to alkali treatment, and then drying and/or second roasting;

Wherein, the first metal element is selected from group VIII non-noble metal elements, and the first metal element includes Fe and Co; the fourth metal element is selected from at least one of noble metal elements;

Wherein, in the first metal element precursor, the amount of Fe precursor and Co precursor is such that in the obtained composition, in terms of oxide, the weight ratio of Fe to Co is 1:(0.05-20).

In the present invention, the precursor of the inorganic oxide carrier includes various substances that can obtain the inorganic oxide carrier through subsequent calcination treatment, which is not particularly limited in the present invention.

The inorganic oxide carrier of the present invention can be selected from at least one of alumina, silica-alumina, zeolite, spinel, kaolin, diatomite, perlite and perovskite; preferably, the inorganic oxide support The oxide support is selected from at least one of alumina, spinel and perovskite, more preferably alumina.

The alumina precursor can be selected from various sols or gels of aluminum, or aluminum hydroxide. The aluminum hydroxide may be selected from at least one of gibbsite, pyrenite, nordishite, diaspore, boehmite, and pseudo-boehmite. Most preferably, the alumina precursor is pseudoboehmite.

According to the preparation method provided by the present invention, preferably, before beating, the alumina precursor is subjected to acidification peptization treatment, and the acidification peptization treatment can be carried out according to conventional technical means in the art. Further preferably, the acidified glue The acid used for the dissolution treatment was hydrochloric acid.

The present invention has a wide selection range for the conditions of the acidified peptization treatment. Preferably, the conditions of the acidified peptization treatment include: the acid-aluminum ratio is 0.12-0.22:1, and the time is 20-40 min.

In the present invention, unless otherwise specified, the acid-aluminum ratio refers to the mass ratio of hydrochloric acid based on 36% by weight of concentrated hydrochloric acid to the precursor of alumina based on dry basis.

The specific embodiment of the acidified peptizing treatment may be as follows: adding pseudo-boehmite to water for beating and dispersion, then adding hydrochloric acid for acidification for 30 minutes, and the acid-aluminum ratio is 0.18.

According to the preparation method of the present invention, the selection range of the amount of the first metal element precursor and the fourth metal element precursor is wide, preferably, the precursor of the inorganic oxide carrier, the first metal element The amount of the precursor and the precursor of the fourth metal element is such that, in the prepared composition, based on the total amount of the composition, the content of the inorganic oxide carrier is 59.9-94.995% by weight, calculated as oxide, so The content of the first metal element is 5-40% by weight, and the content of the fourth metal element is 0.005-0.1% by weight in terms of elements; further preferably, the content of the inorganic oxide carrier is 74.92-91.99% by weight %, in terms of oxides, the content of the first metal element is 8-25% by weight, in terms of elements, the content of the fourth metal element is 0.01-0.08% by weight; more preferably, the inorganic oxide The content of the material carrier is 83.93-89.95% by weight, the content of the first metal element is 10-16% by weight in terms of oxide, and the content of the fourth metal element is 0.05-0.07% by weight in terms of elements.

For the preparation method of the composition capable of reducing CO and NOx emissions provided by the present invention, preferably, the precursor of the inorganic oxide carrier in terms of oxide, the first metal element precursor in terms of Group VIII non-noble metal element oxide And the amount-to-mass ratio of the fourth metal element precursor based on the noble metal element is 59.9-94.995:5-40:0.005-0.1; further, it can be 74.92-91.99:8-25:0.01-0.08; further, Can be 83.93-89.95:10-16:0.05-0.07.

The first metal element of the present invention includes Fe and Co, as long as Fe and Co are included. The present invention does not exclude that the first metal element also contains elements other than Fe and Co in the non-noble metal elements of Group VIII , such as Ni.

According to a most preferred embodiment of the present invention, the first metal elements are only Fe and Co.

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

According to a preferred embodiment of the present invention, in the precursor of the first metal element, the amount of the Fe precursor and the Co precursor is such that, in the obtained composition, in terms of oxides, the weight ratio of Fe to Co is preferably It is 1:(0.1-10), More preferably, it is 1:(0.3-3), More preferably, it is 1:(0.4-2).

In the present invention, unless otherwise specified, Fe is calculated as an oxide means that Fe is calculated as Fe ₂ O ₃ , and Co is calculated as an oxide means that Co is calculated as Co ₂ O ₃ .

According to the present invention, preferably, the solid content of the slurry in step (1) is 8-30% by weight.

According to the present invention, the first metal element precursor and the fourth metal element precursor are respectively selected from water-soluble salts of the first metal element and the fourth metal element, such as nitrate, chloride, chlorate or sulfate, etc. , which is not particularly limited in the present invention.

In the present invention, the noble metal element includes at least one of Au, Ag, Pt, Os, Ir, Ru, Rh and Pd.

According to the preparation method provided by the present invention, preferably the fourth metal element is selected from at least one of Pt, Ir, Pd, Ru and Rh, most preferably Ru.

According to the present invention, the method for mixing and beating the precursor of the inorganic oxide carrier, the precursor of the first metal element and water is not particularly limited, and the addition of the precursor of the inorganic oxide carrier and the precursor of the first metal element The sequence is also not limited, as long as the precursor of the inorganic oxide carrier, the precursor of the first metal element and water are contacted, and then slurried to obtain a slurry.

According to a preferred embodiment of the present invention, the method further comprises: introducing a second metal element precursor and/or a third metal element precursor during the mixing and beating process of step (1); the second metal element is selected From at least one of Group IA and/or IIA metal elements, the third metal element is selected from at least one of Group IB-VIIB non-noble metal elements.

Introducing the second metal precursor in the beating process can improve the performance of the composition, and introducing the third metal precursor in the beating process can also improve the performance of the composition, but at the same time introducing the second metal element precursor and the third metal element precursor It is more beneficial to further improve the performance of the composition.

Therefore, according to the preparation method of the present invention, in step (1), preferably, the precursor of the inorganic oxide carrier, the precursor of the first metal element, the precursor of the second metal element and water can be mixed and beaten, or the precursor of the inorganic oxide carrier can be mixed and beaten with water. The precursor of the inorganic oxide carrier, the precursor of the first metal element, the precursor of the third metal element and the water are mixed and slurried. In step (1) of the present invention, it is more preferable to mix the precursor of the inorganic oxide carrier, the precursor of the first metal element, The second metal element precursor, the third metal element precursor and water are mixed and beaten. This preferred embodiment is more conducive to exerting the synergistic effect of the first metal element, the second metal element, the third metal element and the fourth metal element, and is more conducive to improving the performance of the composition.

The present invention has a wide selection range for the amount of the second metal element precursor and the third metal element precursor.

According to a specific embodiment of the present invention, the method further includes: introducing the second metal element precursor and the third metal element precursor during the mixing and beating process of step (1), specifically, step (1) includes: Mixing and beating the precursor of the inorganic oxide carrier, the first metal element precursor, the second metal element precursor, the third metal element precursor and water to obtain a slurry, spray-drying the slurry, and then performing a first calcination , to obtain a semi-finished product composition.

According to a preferred embodiment of the present invention, the amount of the precursor of the inorganic oxide support, the precursor of the first metal element, the precursor of the second metal element, the precursor of the third metal element and the precursor of the fourth metal element is such that , in the prepared composition, based on the total amount of the composition, the content of the inorganic oxide carrier is 10-90% by weight, and in terms of oxide, the content of the first metal element is 0.5-50% by weight %, the content of the second metal element is 0.5-20% by weight, the content of the third metal element is 0.5-20% by weight, and the content of the fourth metal element is 0.001-0.15% by weight in terms of elements ; Further preferably, the content of the inorganic oxide carrier is 50-90% by weight, in terms of oxide, the content of the first metal element is 3-30% by weight, and the content of the second metal element is 1 -20% by weight, the content of the third metal element is 1-10% by weight, in terms of elements, the content of the fourth metal element is 0.005-0.1% by weight; more preferably, the inorganic oxide support The content of the first metal element is 55-85% by weight, based on the oxide, the content of the first metal element is 5-25% by weight, the content of the second metal element is 5-15% by weight, and the content of the third metal element is 5-15% by weight. The content of the fourth metal element is 0.01-0.08% by weight in terms of element; most preferably, the content of the inorganic oxide carrier is 66-85% by weight, in terms of oxide The content of the first metal element is 6-16% by weight, the content of the second metal element is 5-12% by weight, and the content of the third metal element is 3-8% by weight, calculated as elements , the content of the fourth metal element is 0.05-0.07% by weight.

In the present invention, the content of each component in the composition capable of reducing CO and NOx emissions is measured by X-ray fluorescence spectroscopic analysis method (Petrochemical Analysis Method (RIPP Experimental Method), edited by Yang Cuiding et al., published by Science Press in 1990). .

For the preparation method of the composition capable of reducing CO and NOx emissions provided by the present invention, preferably, the precursor of the inorganic oxide carrier in terms of oxide, the first metal element precursor in terms of Group VIII non-noble metal element oxide , a second metal element precursor calculated as a Group IA and/or IIA metal element oxide, a third metal element precursor calculated as a Group IB-VIIB non-noble metal element oxide, and a fourth metal element calculated as a noble metal element The mass ratio of the amount of the element precursor is 10-90: 0.5-50: 0.5-20: 0.5-20: 0.001-0.15; further, it can be 50-90: 3-30: 1-20: 1-10: 0.005 -0.1; further, it can be 55-85:5-25:5-15:2-8:0.01-0.08, and it can also be 66-85:6-16:5-12:3-8:0.05- 0.07.

In the present invention, the method for mixing and beating the precursor of the inorganic oxide carrier, the precursor of the first metal element, the precursor of the second metal element, the precursor of the third metal element and water is not particularly limited. The order of adding the precursor of the carrier, the precursor of the first metal element, the precursor of the second metal element and the precursor of the third metal element is also not limited, as long as the precursor of the inorganic oxide carrier, the precursor of the first metal element, the precursor of the third metal element are added. The two metal element precursors and the third metal element precursors and water can be in contact with each other. Preferably, the first metal element precursor and the third metal element precursor are first dissolved in water, and then the precursor of the inorganic oxide carrier ( It is preferably a precursor of an acidified inorganic oxide carrier) to obtain a first solution, the second metal element precursor is mixed with water to obtain a second solution, and finally the first solution and the second solution are mixed, and then beating to obtain a slurry .

In the present invention, Group IA metal elements include but are not limited to Na and/or K; Group IIA metal elements include but are not limited to at least one of Mg, Ca, Sr and Ba. In the present invention, the non-noble metal elements of Group IB-VIIB refer to the non-noble metals from Group IB to Group VIIB in the periodic table, including Group IB non-noble metals, Group IIB metals, Group IIIB metals, and Group IVB metal, Group VB metal, Group VIB metal and Group VIIB metal, specifically, the non-noble metal elements of Group IB-VIIB include but are not limited to Cu, Zn, Cd, Sc, Y, Ti, Zr, At least one of 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; all The noble metal element includes at least one of Au, Ag, Pt, Os, Ir, Ru, Rh, and Pd.

According to the preparation method provided by the present invention, preferably the second metal element is selected from at least one of Na, K, Mg and Ca, more preferably K and/or Mg, and most preferably Mg.

According to the preparation method provided by the present invention, preferably the third metal element is selected from at least one of Cu, Zn, Ti, Zr, V, Cr, Mo, W, Mn and rare earth elements, preferably Zr, V, W At least one of , Mn, Ce and La, most preferably Mn.

The second metal element precursor and the third metal element precursor are respectively selected from water-soluble salts of the second metal element and the third metal element, such as nitrate, chloride, chlorate or sulfate, etc. This is not particularly limited.

In the present invention, the spray drying can be performed according to conventional technical means in the field, which is not particularly limited in the present invention. The range is mainly 20-100 μm, and further preferably, the conditions of spray drying are such that among the particles obtained by spray drying, particles with a particle size of 40-80 μm account for more than 50%.

According to the present invention, the first roasting in step (1) can effectively improve the catalytic conversion activity of the composition capable of reducing CO and NOx emissions to NH ₃ and other reduced nitrogen compounds by using conventional technical means in the field. There is no particular limitation.

According to a preferred embodiment of the present invention, the conditions for the first roasting include: the temperature is 400-1000°C, preferably 450-650°C, more preferably 500-650°C, and the time is 0.1-10h, preferably 1 -3h.

In the present invention, the pressure of the first calcination is not particularly limited, and it can be carried out under normal pressure. For example, it can be carried out at 0.01-1 Mpa (absolute pressure).

In the present invention, the first roasting can be performed in a roasting furnace, and the roasting furnace can be a rotary roasting furnace used in the production of catalytic cracking catalysts and auxiliary agents.

According to the preparation method of the present invention, the impregnation in step (2) is not particularly limited, and can be carried out according to conventional technical means in the art, which can be saturated impregnation or excessive impregnation, preferably excessive impregnation.

According to a specific embodiment of the present invention, the semi-finished product composition can be added into water first, and then the solution of the precursor of the fourth metal element is added thereto, and stirred.

In the present invention, the solid product can be obtained by filtering the mixture obtained after impregnation. The filtration can be performed according to conventional technical means in the art.

According to the preparation method of the present invention, after the impregnation in step (2), the solid product is subjected to alkali treatment before drying and/or the second roasting. Alkali treatment is performed after the impregnation of the noble metal element, so that the noble metal element (the fourth metal element) and the first metal element and optionally the second metal element and the third metal element can be more closely combined, which is more conducive to the development of the metal elements. The synergistic effect is more conducive to improving the catalytic conversion activity and hydrothermal stability of the composition capable of reducing CO and NOx emissions for reduced nitrogen such as _NH3 .

According to a specific embodiment of the present invention, the alkali treatment method may include: mixing and beating the solid product with an alkaline solution, or rinsing the solid product with an alkaline solution.

The present invention has a wide selection range for the alkaline solution, preferably the alkaline solution is a non-metallic element alkaline solution, more preferably ammonia water and/or alkaline ammonium salt solution. The alkaline ammonium salt solution may be at least one of ammonium carbonate solution, ammonium bicarbonate solution and diammonium hydrogen phosphate solution. Most preferably, the alkaline solution in the present invention is ammonia water.

The present invention has a wide selection range for the concentration and dosage of the alkaline solution. For example, the concentration of the alkaline solution can be 0.01-10 mol/L, preferably 0.05-5 mol/L, and more preferably 0.5-2 mol/L. L; the volume dosage of the alkaline solution can be 1-10 times the pore volume of the solid product, preferably 1.5-5 times.

Those skilled in the art can select the concentration and dosage of the alkaline solution according to the pore volume of the solid product obtained. For example, according to a specific embodiment of the present invention, when the pore volume of the solid product obtained by the present invention is about 0.4-0.5 In the case of mL/g, when the amount of the treated solid product is 100 g, 60-250 mL of 0.5-2 mol/L ammonia solution can be selected.

In the step (2) of the present invention, only the solid product may be dried, or only the solid product may be subjected to the second roasting, and the solid product may also be dried and then subjected to the second roasting, which is not particularly limited in the present invention, The second calcination is preferably performed after drying the solid product. The conditions of the drying and the second calcination are not particularly limited in the present invention, and can be performed according to conventional technical means in the art. For example, the drying conditions may include: a temperature of 60-150° C. and a time of 2-10 h.

The present invention has no particular limitation on the conditions of the second calcination. The second calcination can be performed in air or in an inert atmosphere (eg, nitrogen), which is not particularly limited in the present invention, and the conditions of the second calcination can be Including: the temperature is 300-550℃, and the time is 1-10h.

According to a most preferred embodiment of the present invention, the use of Fe, Co, Mg, Mn and Ru as active components can greatly improve the effect of the composition capable of reducing CO and NOx emissions on reduced nitrides such as NH ₃ . high catalytic conversion activity, and the composition capable of reducing CO and NOx emissions has more excellent hydrothermal stability performance.

According to a specific embodiment of the present invention, the method includes:

(1) A precursor of alumina, a precursor of Fe, a precursor of Co, a precursor of Mg, a precursor of Mn and water are mixed and slurried to obtain a slurry, the slurry is spray-dried, and then the first calcination is performed , to obtain a semi-finished product composition;

(2) using the solution of the precursor containing Ru as the dipping solution, impregnating the semi-finished product composition obtained in step (1) to obtain a solid product, and performing alkali treatment on the solid product, and then drying and/or the second roasting;

Among them, the amount of the precursor of alumina, the precursor of Fe, the precursor of Co, the precursor of Mg, the precursor of Mn and the precursor of Ru is such that, in the obtained composition, in terms of oxide, Fe and The weight ratio of Co is 1:(0.4-2), based on the total amount of the composition, the content of alumina is 66-85% by weight, and the total content of Fe and Co is 6-16% by weight in terms of oxides , the content of Mg is 5-12% by weight, the content of Mn is 3-8% by weight, and the content of Ru is 0.05-0.07% by weight in terms of elements.

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

The composition capable of reducing CO and NOx emissions prepared by the above preparation method contains at least one of Fe and Co and noble metal elements, preferably also contains at least one of Group IA and/or IIA metal elements and/or At least one of the non-precious metal elements of Groups IB-VIIB, the above-mentioned metal elements are used in combination, so that the catalytic conversion activity of the composition capable of reducing CO and NOx emissions to NH ₃ and other reduced nitrides is significantly improved, and it is possible to reduce CO and NOx emission compositions have better hydrothermal stability.

The present invention also provides the application of the above-mentioned composition capable of reducing CO and NOx emissions in flue gas treatment. The compositions provided by the present invention can be used to treat any flue gas that needs to reduce CO and NOx emissions.

The present invention also provides the application of the above-mentioned composition capable of reducing CO and NOx emissions in the treatment of catalytic cracking regeneration flue gas. The above-described compositions capable of reducing CO and NOx emissions are particularly suitable for reducing CO and NOx emissions in fully regenerated flue gas and incompletely regenerated flue gas.

The present invention also provides a fluidized catalytic cracking method, which comprises: contacting and reacting hydrocarbon oil with a catalyst, and then regenerating the catalyst after the contact reaction, the catalyst comprising a catalytic cracking catalyst and a catalyst capable of reducing CO and NOx emissions The composition, the composition capable of reducing CO and NOx emission is the above-mentioned composition capable of reducing CO and NOx emission of the present invention.

According to the fluidized catalytic cracking method provided by the present invention, preferably, based on the total amount of catalyst, the content of the composition capable of reducing CO and NOx emissions is 0.05-5 wt %, more preferably 0.1-3 wt % , more preferably 0.5-2.5% by weight.

The hydrocarbon oil is not particularly limited in the present invention, and can be various hydrocarbon oils conventionally treated in the field of catalytic cracking, such as vacuum gas oil, atmospheric residual oil, vacuum residual oil, deasphalted oil, coking wax oil or added oil. Hydrogen treated oil.

The catalytic cracking catalyst is not particularly limited in the present invention, and can be one or more of the existing catalytic cracking catalysts, which can be purchased commercially or prepared according to existing methods.

The compositions provided by the present invention capable of reducing CO and NOx emissions may be a separate particle, or may be an integral part of the catalytic cracking catalyst particle. Preferably, the composition for reducing CO and NOx emissions provided by the present invention is used as a separate particle in combination with catalytic cracking catalyst particles.

In the present invention, unless otherwise specified, the ppm refers to volume concentration.

In the fluid catalytic cracking method of the present invention, the catalyst regeneration method has no special requirements compared with the existing regeneration methods, including partial regeneration, incomplete regeneration and complete regeneration operation modes. For the regeneration method, please refer to pages 1234-1343 of Catalytic Cracking Technology and Engineering, edited by Chen Junwu and published by China Petrochemical Press in 2005. The preferred regeneration temperature is 650°C to 730°C.

The implementation process and the beneficial effects of the present invention are described in detail below through specific examples, which are intended to help readers understand the spirit and essence of the present invention more clearly, but cannot constitute any limitation on the implementation scope of the present invention.

In the following examples, the content of the components in the compositions capable of reducing CO and NOx emissions were all determined by X-ray fluorescence spectroscopy (XRF) method. For details, please refer to the analysis method of petrochemical industry (RIPP experimental method), edited by Yang Cuiding et al., Science Press, 1990 publishing. The compositions capable of reducing CO and NOx emissions in the examples were obtained by using an X-ray diffractometer (Siemens D5005 model) to obtain XRD patterns for structure determination, Cu target, Kα radiation, solid state detector, tube voltage 40kV, tube current 40mA.

The raw materials used in the examples and comparative examples: cobalt nitrate [Co(NO ₃ ) ₂ ·6H ₂ O] is analytically pure, ferric nitrate [Fe(NO ₃ ) ₃ ·9H ₂ O] is analytically pure, potassium permanganate [ KMnO ₄ ] is analytically pure, magnesium oxide [MgO] is analytically pure, and both are produced by Sinopharm Chemical Reagent Co., Ltd.; ruthenium chloride (RuCl ₃ ) is analytically pure, with Ru content ≥ 37%. Co., Ltd.; pseudo-boehmite is an industrial-grade product, with an alumina content of 64% by weight and a pore volume of 0.31 ml/g, produced by Shandong Aluminum Company; hydrochloric acid, with a concentration of 36.5% by weight, analytically pure, produced by Beijing Chemical Plant Ammonia, the concentration is 25-28%, analytically pure, produced by Beijing Chemical Plant, used after dilution; Catalytic cracking catalyst industrial product (Cat-A, catalyst brand CGP-1), Na ₂ O content 0.24% by weight, RE ₂ O The content of ₃ is 3.2% by weight, the content of Al ₂ O ₃ is 48.0% by weight, and the average particle size is 67 microns, produced by Sinopec Catalyst Co., Ltd.

Example 1

(1) 2.62kg of pseudo-boehmite was added to 14.2kg of deionized water for beating and dispersion, then 238mL of hydrochloric acid was added for acidification 15min to obtain bauxite colloid, the iron nitrate (in Fe ₂ O ₃ in terms of metal oxides, The same below) 60g, cobalt nitrate (in Co ₂ O ₃ , the same below) 60g, KMnO ₄ (in MnO, the same below) 100g were added into 3500 mL of water and stirred until fully dissolved, the bauxite colloid was added therein, and stirred for 15min to obtain The first solution; 100g of MgO was added to 300g of water, added to the first solution after stirring for 10min, and after stirring for 20min, a slurry was obtained, the slurry was spray-dried, and 150g of particles obtained by spray-drying (average particle size was 65 μm, The particles with a particle size of 40-80 μm accounted for 60%, the same below) transferred to a tube furnace, air was introduced at a flow rate of 100 mL/min, and treated at 600 ° C for 1.5 h to obtain a semi-finished product composition;

(2) take by weighing 100g above-mentioned semi-finished product composition and join in 700mL water, then add the RuCl solution _4.8mL that the mass content in terms of metal element is 12.5g/L, stir 20min, carry out filtration to obtain solid product, with concentration be 2mol/ The solid product was rinsed with 80 mL of L ammonia solution, dried (100° C., 4 h), and calcined (400° C., 2 h) to obtain composition S-1.

Table 1 shows the measurement results of the content of each component in composition S-1.

Example 2

(1) 2.53kg of pseudo-boehmite was added to 13.7kg of deionized water for beating and dispersion, then 229mL of hydrochloric acid was added for acidification for 15min to obtain bauxite colloid, 100g of iron nitrate, 60g of cobalt nitrate, KMnO ₄ (in terms of MnO) 60g was added into 3500mL of water and stirred until fully dissolved, bauxite colloid was added therein, stirred for 15min to obtain the first solution; 160g of MgO was added to 480g of water, added to the first solution after stirring for 10min, and after stirring for 20min , obtain a slurry, spray-dry the slurry, transfer 150 g of the particles obtained by spray-drying to a tube furnace, introduce air at a flow rate of 100 mL/min, and treat at 500 ° C for 3 hours to obtain a semi-finished product composition;

(2) take by weighing 100g above-mentioned semi-finished product composition and join in 700mL water, then add the RuCl solution _4.4mL that the mass content in terms of metal element is 12.5g/L, stir 20min, carry out filtration to obtain solid product, use concentration is 2mol/ The solid product was rinsed with 100 mL of L ammonia solution, dried (100° C., 4 h), and calcined (400° C., 2 h) to obtain composition S-2.

Table 1 shows the measurement results of the content of each component in composition S-2.

Example 3

(1) 2.09kg of pseudo-boehmite was added to 11.3kg of deionized water for slurring and dispersion, then 190mL of hydrochloric acid was added for acidification for 15min to obtain bauxite colloid, 100g of iron nitrate, 200g of cobalt nitrate, KMnO ₄ (in terms of MnO) 160g was added into 4000mL of water and stirred until fully dissolved, bauxite colloid was added to it, stirred for 15min to obtain the first solution; 200g of MgO was added to 600g of water, added to the first solution after stirring for 10min, and after stirring for 20min , obtain a slurry, spray-dry the slurry, transfer 150 g of the particles obtained by spray-drying to a tube furnace, introduce air at a flow rate of 100 mL/min, and treat at 650 ° C for 1 h to obtain a semi-finished product composition;

(2) take by weighing 100g above-mentioned semi-finished product composition and join in 700mL water, then add the RuCl that the mass content in terms of metal element is 12.5g/ _L Solution 4mL, stir 20min, carry out filtration to obtain solid product, with concentration be 2mol/L The solid product was rinsed with 80 mL of aqueous ammonia solution, dried (100° C., 4 h), and calcined (400° C., 2 h) to obtain composition S-3.

The results of the content determination of each component in composition S-3 are listed in Table 1.

Example 4

(1) 2.09kg of pseudo-boehmite was added to 11.3kg of deionized water for beating and dispersion, then 190mL of hydrochloric acid was added for acidification for 15min to obtain bauxite colloid, 200g of iron nitrate, 120g of cobalt nitrate, KMnO ₄ (in terms of MnO) 100g was added into 3500mL of water and stirred until fully dissolved, the bauxite colloid was added into it, and stirred for 15min to obtain the first solution; Obtaining a slurry, spray-drying the slurry, taking 150 g of the particles obtained by spray-drying and transferring it to a tube furnace, introducing air at a flow rate of 100 mL/min, and treating at 600 ° C for 1.5 hours to obtain a semi-finished product composition;

(2) take by weighing 100g above-mentioned semi-finished product composition and join in 700mL water, then add the RuCl solution _5.2mL that the mass content in terms of metal element is 12.5g/L, stir 20min, carry out filtration to obtain solid product, with concentration be 2mol/ The solid product was rinsed with 80 mL of L ammonia solution, dried (100° C., 4 h), and calcined (400° C., 2 h) to obtain composition S-4.

Table 1 shows the measurement results of the content of each component in composition S-4.

Example 5

(1) 2.62kg of pseudo-boehmite was added to 14.2kg of deionized water for slurrying and dispersion, then 238mL of hydrochloric acid was added for acidification for 15min to obtain bauxite colloid, and 100g of iron nitrate and 100g of cobalt nitrate in terms of metal oxide were added to 3500mL of water Stir until fully dissolved, add bauxite colloid into it, stir for 15 min to obtain the first solution; add 100 g of MgO to 360 g of water, add it to the first solution after stirring for 10 min, and stir for 20 min to obtain a slurry, which is subjected to Spray drying, take 150g of the particles obtained by spray drying (the average particle size is 65 μm, and the particles with a particle size of 40-80 μm account for 60%, the same below) and transfer them to a tube furnace, and pass air at a flow rate of 100 mL/min. Treated at 600°C for 1.5h to obtain a semi-finished product composition;

(2) take by weighing 100g above-mentioned semi-finished product composition and join in 700mL water, then add the RuCl solution _4.8mL that the mass content in terms of metal element is 12.5g/L, stir 20min, carry out filtration to obtain solid product, with concentration be 2mol/ The solid product was rinsed with 80 mL of L ammonia solution, dried (100° C., 4 h), and calcined (400° C., 2 h) to obtain composition S-5.

The content determination results of each component in composition S-5 are listed in Table 1.

Example 6

(1) 2.62kg of pseudo-boehmite was added to 14.2kg of deionized water for beating and dispersion, then 238mL of hydrochloric acid was added for acidification for 15min to obtain bauxite colloid, 100g of iron nitrate, 100g of cobalt nitrate, KMnO ₄ (in terms of MnO, the same below) 100 g was added into 3500 mL of water and stirred until fully dissolved, bauxite colloid was added therein, and after stirring for 20 min, a slurry was obtained, the slurry was spray-dried, and 150 g of particles (average particle size) obtained by spray drying were obtained. 65 μm, 60% of particles with a particle size of 40-80 μm, the same below) is transferred to a tube furnace, air is introduced at a flow rate of 100 mL/min, and treated at 600 ° C for 1.5 h to obtain a semi-finished product composition;

(2) take by weighing 100g above-mentioned semi-finished product composition and join in 700mL water, then add the RuCl solution _4.8mL that the mass content in terms of metal element is 12.5g/L, stir 20min, carry out filtration to obtain solid product, with concentration be 2mol/ The solid product was rinsed with 80 mL of L ammonia solution, dried (100° C., 4 h), and calcined (400° C., 2 h) to obtain composition S-6.

Table 1 shows the measurement results of the content of each component in composition S-6.

Example 7

(1) 2.62kg of pseudo-boehmite was added to 14.2kg of deionized water for slurrying and dispersion, then 238mL of hydrochloric acid was added for acidification for 15min to obtain bauxite colloid, and 100g of iron nitrate and 100g of cobalt nitrate in terms of metal oxide were added to 3500mL of water Stir until fully dissolved, add bauxite colloid into it, stir for 20min to obtain a slurry, carry out spray drying on the slurry, take 150g of the particles obtained by spray drying (average particle size is 65 μm, particle size is 40-80 μm) %, the same below) was transferred to a tube furnace, air was introduced at a flow rate of 100 mL/min, and treated at 600 ° C for 1.5 h to obtain a semi-finished product composition;

(2) take by weighing 100g above-mentioned semi-finished product composition and join in 700mL water, then add the RuCl solution _4.8mL that the mass content in terms of metal element is 12.5g/L, stir 20min, carry out filtration to obtain solid product, with concentration be 2mol/ The solid product was rinsed with 80 mL of L ammonia solution, dried (100° C., 4 h), and calcined (400° C., 2 h) to obtain composition S-7.

Table 1 shows the results of content determination of each component in composition S-7.

Example 8

According to the method of Example 1, the difference is that the amount of ferric nitrate calculated as metal oxide is 30 g, and the amount of cobalt nitrate is 90 g to obtain composition S-8.

Table 1 shows the results of determination of the content of each component in composition S-8.

Example 9

According to the method of Example 1, the difference is that the amount of ferric nitrate calculated as metal oxide is 90 g, and the amount of cobalt nitrate is 30 g to obtain composition S-9.

The content determination results of each component in composition S-9 are listed in Table 1.

Comparative Example 1

According to the method of Example 1, the difference is that the same mass of iron nitrate is used to replace the cobalt nitrate in terms of metal oxide to obtain the composition D-1.

Table 1 shows the measurement results of the content of each component in composition D-1.

Comparative Example 2

According to the method of Example 1, the difference is that the same mass of cobalt nitrate was used to replace the iron nitrate in terms of metal oxide to obtain the composition D-2.

Table 1 shows the measurement results of the content of each component in composition D-2.

Comparative Example 3

Comparative compositions were prepared according to the method described in US6800586. Take 34.4 grams of dried γ-alumina microsphere carrier, impregnate the alumina microspheres with a solution of 10.09g cerium nitrate, 2.13g lanthanum nitrate and 18mL water, dry at 120°C and bake at 600°C for 1 hour after dipping After that, it was impregnated with a solution prepared by 2.7 g of copper nitrate and 18 mL of water, dried at 120° C. and calcined at 600° C. for 1 hour to obtain composition D-3. In composition D-3, based on the total amount of composition D-3, in terms of oxides, the content of RE ₂ O ₃ is 12 wt %, and the content of CuO is 2.3 wt % (RE represents a lanthanoid metal element).

Table 1

Note: The content of the first metal element, the second metal element and the third metal element are calculated as oxides, and the unit is % by weight, and the content of the fourth metal element is calculated as the element, and the unit is % by weight.

Test Example 1

This test example is used to reduce the CO and NOx emissions in the fully regenerated flue gas and the effect on the FCC product distribution of the compositions provided in the above examples and comparative examples.

The composition capable of reducing CO and NOx emissions and the catalytic cracking catalyst (Cat-A) were uniformly blended (the composition capable of reducing CO and NOx emissions accounted for 0.8 of the total amount of the composition capable of reducing CO and NOx emissions and the catalytic cracking catalyst). % by weight), the catalytic cracking reaction-regeneration evaluation was carried out after aging at 800°C and 100% steam atmosphere for 12 h.

The catalytic cracking reaction-regeneration evaluation was carried out on a small fixed fluidized bed device. The aging catalyst loading was 9 g, the reaction temperature was 500°C, and the catalyst oil weight ratio was 6. The properties of the feedstock oil are shown in Table 2. The gaseous products were analyzed by online chromatography to obtain the cracked gas composition; the liquid products were analyzed by offline chromatography to obtain the yields of gasoline, diesel and heavy oil. After the reaction, it was stripped with N ₂ for 10 min, and the in-situ scorched regeneration was carried out. The regeneration air flow was 200 mL/min, the regeneration time was 15 min, and the initial regeneration temperature was the same as the reaction temperature. The flue gas in the regeneration process is collected, and the coke yield is calculated according to the CO ₂ infrared analyzer integral after the regeneration, and the FCC product distribution is obtained after the normalization of all product yields. The sum of the yields of liquefied gas, gasoline and coke. Testo350Pro flue gas analyzer was used to measure the concentrations of NOx and CO in the flue gas. The results are shown in Table 4.

Table 2

table 3

product distribution Example 1 Example 5 Example 6 Example 7 Comparative Example 3 Dry gas, wt% 1.70 1.71 1.71 1.71 1.73 Liquefied gas, wt% 19.29 19.24 19.27 19.26 19.20 Coke, wt% 7.20 7.19 7.18 7.19 7.29 Gasoline, wt% 49.66 49.68 49.55 49.58 49.44 Diesel, wt% 15.08 15.14 15.21 15.22 15.27 Heavy oil, wt% 7.07 7.03 7.09 7.03 7.06 Conversion rate,% 77.87 77.83 77.70 77.74 77.66

As can be seen from Table 3, the composition capable of reducing CO and NOx emissions provided by the present invention is used in combination with a catalytic cracking catalyst, so that the yields of coke and dry gas in the FCC product are low.

Table 4

As can be seen from the data in Table 4, the use of the composition capable of reducing CO and NOx emission provided by the present invention for catalytic cracking process has better reduction of CO and NOx than the composition capable of reducing CO and NOx emission provided by the comparative example. Emission performance, and the aged composition capable of reducing CO and NOx emissions was used in the evaluation process, and the aged composition capable of reducing CO and NOx emissions could still effectively reduce CO and NOx emissions, therefore, the present invention The provided compositions capable of reducing CO and NOx emissions have better hydrothermal stability.

Test Example 2

This test example is used for reducing CO and NOx emissions in incompletely regenerated flue gas of the compositions provided in the above examples and comparative examples that can reduce CO and NOx emissions.

The composition capable of reducing CO and NOx emissions is uniformly blended with the catalytic cracking catalyst (Cat-A) described above (the composition capable of reducing CO and NOx emissions accounts for 3% of the total amount of the composition capable of reducing CO and NOx emissions and the catalytic cracking catalyst). 2.2 wt%) after aging at 800° C. and 100% steam atmosphere for 12 hours, the catalytic cracking reaction-regeneration evaluation was carried out.

The catalytic cracking reaction-regeneration evaluation was carried out on a small fixed-bed simulated flue gas NOx reduction device, the aged catalyst loading was 10 g, the reaction temperature was 650°C, and the volume flow of feed gas was 1500 mL/min. The feed gas contained 3.7 vol% CO, 0.5 vol% oxygen, 800 ppm _NH3 , and the balance was _N2 . The gas products were analyzed by an on-line infrared analyzer to obtain the concentrations of NH ₃ , NOx and CO after the reaction, and the results are listed in Table 5.

table 5

Numbering NOx concentration, ppm NH₃ concentration, ppm CO concentration, vol% Example 1 S-1 62 63 2.87 Comparative Example 1 D-1 118 154 2.86 Comparative Example 2 D-2 110 151 2.91 Comparative Example 3 D-3 109 321 3.15 Example 2 S-2 55 60 2.80 Example 3 S-3 39 5 2.70 Example 4 S-4 30 8 2.70 Example 5 S-5 54 75 2.77 Example 6 S-6 72 91 2.75 Example 7 S-7 74 55 2.71 Example 8 S-8 61 65 2.90 Example 9 S-9 65 66 2.87

As can be seen from the data in Table 5, using the composition capable of reducing CO and NOx emissions provided by the present invention in the incomplete regeneration process of the catalytic cracking process has better performance than the composition capable of reducing CO and NOx emissions provided by the comparative example. CO, NH ₃ and NOx emission reduction performance, and the aged CO and NOx emission reduction compositions were used in the evaluation process, and the aged CO and NOx emission reduction compositions removed CO, NH ₃ and The NOx activity is still relatively high, therefore, the composition capable of reducing CO and NOx emissions provided by the present invention has better hydrothermal stability.

It can be seen from the data in Tables 4 and 5 that the composition capable of reducing CO and NOx emissions provided by the present invention is suitable for both complete regeneration and incomplete regeneration, and has better regeneration flue gas treatment capacity. Particularly,

From the comparison between Examples 1-4 and 5-7, it can be seen that the use of the preferred metal elements of the present invention as active components can further improve the performance of the composition capable of reducing CO and NOx emissions; It can be seen from the comparison of Example 8 and Example 9 that the preferred Fe to Co mass ratio of the present invention further improves the performance of the composition capable of reducing CO and NOx emissions; it can be seen from the comparison between Example 1 and Comparative Examples 1-3 It is found that the present invention greatly improves the performance of the composition capable of reducing CO and NOx emissions by using Fe and Co in combination.

The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details of the above-mentioned embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that each specific technical feature described in the above-mentioned specific implementation manner may be combined in any suitable manner under the circumstance that there is no contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

In addition, the various embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the spirit of the present invention, they should also be regarded as the contents disclosed in the present invention.

Claims (28)

1. a preparation method of a composition capable of reducing CO and NOx emissions, is characterized in that, the method comprises: (1) mixing and beating the precursor of the inorganic oxide carrier, the first metal element precursor and water to obtain a slurry, the slurry is spray-dried, and then first roasted to obtain a semi-finished product composition; (2) Impregnating the semi-finished product composition obtained in step (1) with the solution containing the precursor of the fourth metal element as the impregnating liquid to obtain a solid product, subjecting the solid product to alkali treatment, and then drying and/or second roasting; Wherein, the first metal element is selected from group VIII non-noble metal elements, and the first metal element includes Fe and Co; the fourth metal element is selected from at least one of noble metal elements; Wherein, in the first metal element precursor, the amount of Fe precursor and Co precursor is such that, in the obtained composition, in terms of oxide, the weight ratio of Fe to Co is 1:(0.05-20); The second metal element precursor and the third metal element precursor are introduced in the mixing and beating process of step (1); the second metal element is selected from at least one of the metal elements of Group IA and/or IIA, so The third metal element is selected from at least one of Cu, Zn, Ti, Zr, V, Cr, Mo, W and Mn; The alkali treatment method comprises: mixing and beating the solid product with an alkaline solution, or rinsing the solid product with an alkaline solution; The amount of the precursor of the inorganic oxide carrier, the precursor of the first metal element, the precursor of the second metal element, the precursor of the third metal element and the precursor of the fourth metal element is such that, in the prepared composition, in the combination The content of the inorganic oxide carrier is 10-90% by weight, based on the total amount of the oxide, the content of the first metal element is 0.5-50% by weight, and the content of the second metal element is 0.5-50% by weight. The content of the third metal element is 0.5-20% by weight, and the content of the fourth metal element is 0.001-0.15% by weight in terms of elements. 2 . The preparation method according to claim 1 , wherein the alkaline solution is a non-metallic element alkaline solution. 3 . 3. The preparation method according to claim 2, wherein the alkaline solution is ammonia water and/or alkaline ammonium salt solution. 4. The preparation method according to claim 1, wherein the concentration of the alkaline solution is 0.01-10 mol/L. 5. The preparation method according to claim 4, wherein the concentration of the alkaline solution is 0.05-5 mol/L. 6. The preparation method according to claim 1, wherein the volume dosage of the alkaline solution is 1-10 times the pore volume of the solid product. 7. The preparation method according to claim 6, wherein the volume dosage of the alkaline solution is 1.5-5 times the pore volume of the solid product. 8. The preparation method according to any one of claims 1-7, wherein the amount of the Fe precursor and the Co precursor is such that, in the obtained composition, in terms of oxides, the weight of Fe and Co The ratio is 1:(0.1-10). 9. preparation method according to claim 8, wherein, the consumption of the precursor of Fe and the precursor of Co is such that, in the obtained composition, in terms of oxide, the weight ratio of Fe to Co is 1:0.3 -3). 10. The preparation method according to claim 9, wherein the amount of the Fe precursor and the Co precursor is such that, in the obtained composition, in terms of oxides, the weight ratio of Fe to Co is 1:(0.4 -2). 11. The preparation method according to any one of claims 1-7, wherein the first metal element precursor and the fourth metal element precursor are respectively selected from the water-soluble water-soluble of the first metal element and the fourth metal element Salt. 12. The preparation method according to any one of claims 1-7, wherein the fourth metal element is selected from at least one of Pt, Ir, Pd, Ru and Rh. 13. The preparation method according to claim 12, wherein the fourth metal element is Ru. 14. The preparation method according to any one of claims 1-7, wherein the content of the inorganic oxide carrier is 50-90% by weight, and the content of the first metal element is 3% in terms of oxide. -30% by weight, the content of the second metal element is 1-20% by weight, the content of the third metal element is 1-10% by weight, in terms of elements, the content of the fourth metal element is 0.005- 0.1% by weight. 15. The preparation method according to claim 14, wherein the content of the inorganic oxide carrier is 55-85% by weight, and the content of the first metal element is 5-25% by weight in terms of oxide, so The content of the second metal element is 5-15% by weight, the content of the third metal element is 2-8% by weight, and the content of the fourth metal element is 0.01-0.08% by weight in terms of elements. 16. The preparation method according to claim 1, wherein the second metal element is selected from at least one of Na, K, Mg and Ca. 17. The preparation method according to claim 16, wherein the second metal element is K and/or Mg. 18. The preparation method according to claim 17, wherein the second metal element is Mg; The third metal element is selected from at least one of Zr, V, W and Mn; The second metal element precursor and the third metal element precursor are selected from water-soluble salts of the second metal element and the third metal element, respectively. 19. The preparation method according to claim 18, wherein the third metal element is Mn. 20. The preparation method according to any one of claims 1-7, wherein the inorganic oxide carrier is selected from alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, pearl At least one of rock and perovskite precursors. 21. The preparation method according to claim 20, wherein the inorganic oxide support is selected from at least one of alumina, spinel and perovskite. 22. The preparation method according to claim 21, wherein the inorganic oxide carrier is alumina. 23. The preparation method according to claim 22, wherein, before beating, acidizing and peptizing the alumina precursor is performed. 24. The preparation method according to claim 23, wherein the acid used in the acidified peptization treatment is hydrochloric acid, and the conditions of the acidified peptization treatment include: the acid-aluminum ratio is 0.12-0.22:1, and the time is 20- 40min. 25. A composition capable of reducing CO and NOx emissions prepared by the preparation method of any one of claims 1-24. 26. The use of the composition capable of reducing CO and NOx emissions according to claim 25 in flue gas treatment. 27. The use of the composition capable of reducing CO and NOx emissions according to claim 25 in catalytic cracking regeneration flue gas treatment. 28. A fluid catalytic cracking method comprising: contacting a hydrocarbon oil with a catalyst, and then regenerating the contact-reacted catalyst, the catalyst comprising a catalytic cracking catalyst and a composition capable of reducing CO and NOx emissions, It is characterized in that the composition capable of reducing CO and NOx emissions is the composition capable of reducing CO and NOx emissions according to claim 25 .