CN109201098B - Can reduce CO and NOxDischarged composition, preparation method and application thereof and fluidized catalytic cracking method - Google Patents

Abstract

The invention relates to the field of catalytic cracking, and discloses a composition capable of reducing CO and NOx emission, a preparation method and application thereof, and a fluidized catalytic cracking method, wherein the composition capable of reducing CO and NOx emission provided by the invention comprises the following components: the inorganic oxide carrier and a first metal element, a second metal element and a third metal element loaded on the inorganic oxide carrier, wherein the first metal element comprises Fe and Co, and the weight ratio of Fe to Co is 1: (0.05-20). The composition Fe and Co provided by the invention are jointly used as main metal elements, and the composition can be kept to have higher hydrothermal stability through further modification of at least one of group IA and/or IIA metal elements and at least one of precious metal elements, and has higher activity of reducing CO and NOx emission of regenerated flue gas.

Description

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

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, and a Group VIII non-precious metal element containing Fe and Co is mixed with at least one of the Group IA and/or IIA metal elements and the noble metal elements. At least one of them is used as an active component, which can effectively reduce CO and NOx emissions in the catalytic cracking regeneration flue gas. It is speculated that the reason may be due to: Fe and Co together as the main metal elements, through the further modification of at least one of the metal elements of Group IA and/or IIA and at least one of the noble metal elements, it is beneficial to reduce the nitrogen content in the oxidation state The formation of compounds, and can promote the decomposition of reduced nitrogen compounds.

Through further research, it is found that, in the preferred case, after spray drying and before impregnation with precious metal elements, the solid material obtained after spray drying is treated at high temperature in a carbon-containing atmosphere, which can more effectively reduce CO and NOx emissions from catalytic cracking regeneration flue gas ; In a further preferred case, the solid product obtained after the impregnation of the precious metal is subjected to alkali treatment, which can more effectively reduce the CO and NOx emissions of the catalytic cracking regeneration flue gas. In the above preferred case, the structure of the composition capable of reducing CO and NOx emissions is further modulated and stabilized, so that the composition capable of reducing CO and NOx emissions has obvious catalytic conversion activity to NH ₃ and other reduced nitrogen compounds It has better hydrothermal stability and meets the requirements of the regenerator hydrothermal environment for a composition capable of reducing CO and NOx emissions.

Based on this, according to a first aspect of the present invention, there is provided a composition capable of reducing CO and NOx emissions, the composition comprising: an inorganic oxide carrier and a first metal element and a second metal supported on the inorganic oxide carrier element and a third metal element, the first metal element is selected from the group VIII non-noble metal elements, and the first metal element includes Fe and Co, in terms of oxides, the weight ratio of Fe to Co is 1:(0.05 -20), the second metal element is selected from at least one of Group IA and/or IIA metal elements, and the third metal element is selected from at least one of noble metal elements.

According to a second aspect of the present invention, there is provided a method for preparing 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, the second metal element precursor and water to obtain a slurry, spray-drying the slurry, and then performing the first roasting to obtain a semi-finished product combination thing;

(2) using the solution containing the third metal element precursor as the dipping solution, impregnating the semi-finished product composition obtained in step (1) to obtain a solid product, and then drying and/or second roasting the solid product;

Wherein, the first metal element is selected from Group VIII non-noble metal elements, and the first metal element includes Fe and Co; the second metal element is selected from at least one of Group IA and/or IIA metal elements; the third The metal element is selected from at least one of precious 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 third 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 fourth 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 fifth aspect of the present invention, there is provided the application of the above-mentioned composition capable of reducing CO and NOx emissions in the treatment of catalytic cracking regeneration flue gas.

According to a sixth aspect of the present invention, a fluidized catalytic cracking method is provided, 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.

The composition capable of reducing CO and NOx emissions provided by the invention can be used as a catalytic cracking aid, can maintain high hydrothermal stability in the hydrothermal environment of the regenerator, and has high reduction activity of regenerating flue gas CO and NOx emissions, In addition, 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 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 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 wt % of the total weight of the catalyst, and heated at 800° C. and 100% water. Catalytic cracking reaction-regeneration evaluation is carried out after aging in a steam atmosphere for 12 hours. Compared with the composition D-3 which can reduce CO and NOx emissions prepared by the active component saturated impregnation method in the prior art, the use of the composition provided by the present invention can reduce the CO and NOx emissions. The NOx emission concentration in the fully regenerated flue gas was reduced from 264 ppm to 51 ppm when combining CO and NOx emissions.

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

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the specification, and together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached image:

FIG. 1 is the XRD patterns of the compositions prepared in Example 1 and Example 5 capable of reducing CO and NOx emissions.

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

The present invention has a wide selection range for the content of the first metal element, the second metal element and the third metal element in the composition. Preferably, based on the total amount of the composition, the inorganic oxide carrier has a The content is 30-90% by weight, in terms of oxides, the content of the first metal element is 0.5-50% by weight, and the content of the second metal element is 0.5-20% by weight, in terms of elements, the content of the first metal element is 0.5-20% by weight. The content of the trimetal element is 0.001-0.15% by weight; further preferably, the content of the inorganic oxide carrier is 50-90% by weight, and the content of the first metal element is 3-30% by weight in terms of oxides , the content of the second metal element is 1-20% by weight, and the content of the third metal element is 0.005-0.1% by weight in terms of elements; more preferably, the content of the inorganic oxide carrier is 60% -85% by weight, based on oxides, the content of the first metal element is 5-25% by weight, and the content of the second metal element is 2-15% by weight, based on the element, the content of the third metal element The content of the metal element is 0.01-0.08% by weight; most preferably, the content of the inorganic oxide carrier is 72-85% by weight, and the content of the first metal element is 10-16% by weight in terms of oxides, the The content of the second metal element is 4.9-12% by weight, and the content of the third metal element is 0.05-0.07% by weight in terms of elements.

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

According to a most preferred embodiment of the present invention, the composition is composed of an inorganic oxide support and a first metal element, a second metal element and a third metal element supported on the inorganic oxide support, and the first metal element The elements are only Fe and Co.

In the present invention, as long as Fe and Co are contained in the first metal element, the catalytic conversion activity of the composition to reduced nitrides such as NH ₃ can be improved. , the weight ratio of Fe to Co is 1:(0.1-10), more preferably 1:(0.3-3), and even more preferably 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 a preferred embodiment of the present invention, Fe in the composition at least partially exists in the form of iron carbide, preferably, the iron carbide is Fe ₃ C and/or Fe ₇ C ₃ . The amount of iron carbide present is not particularly limited in the present invention, as long as a part of iron carbide 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, the Co in the composition is at least partially present in the form of elemental cobalt. The present invention has no particular limitation on the amount of elemental cobalt present, as long as a part of 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 compositions for reducing CO and NOx emissions, most of the metal elements in the compositions exist in an oxidized form. In the preparation process of the composition of the present invention, preferably before impregnating the precious metal, it is calcined in a carbon-containing atmosphere, so that part of FeO is converted into iron carbide, and part of CoO is converted into elemental cobalt.

The presence of iron carbide and/or elemental cobalt enables the composition to better promote the decomposition of reduced nitrogen-containing compounds, reduce the generation of nitrogen oxides, and promote the reduction of nitrogen oxides to a certain extent.

According to the composition provided by the present invention, preferably, in the XRD pattern of the composition, there are diffraction peaks at 2θ of 42.6°, 44.2° and 44.9°.

Specifically, the diffraction peaks of iron carbide at 2θ of 42.6° and 44.9° are the diffraction peaks of elemental cobalt at 2θ of 44.2°.

According to a preferred embodiment of the present invention, in the XRD pattern of the composition provided by the present invention, the diffraction peak at 2θ of 44.9° is stronger than the diffraction peak at 2θ of 42.6°.

According to the composition provided by the present invention, the inorganic oxide carrier can be various inorganic oxide carriers conventionally used in the art, such as selected from alumina, silica-alumina, zeolite, spinel, kaolin, diatom At least one of soil, perlite and perovskite. In the present invention, the spinel may be various commonly used spinels, for example, may be at least one of magnesium aluminum spinel, zinc aluminum spinel and titanium aluminum spinel.

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

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

The alumina can be derived 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. Preferably the alumina is derived from pseudoboehmite.

The above-mentioned inorganic oxide supports are commercially available, and can also be prepared by using existing methods.

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; the noble metal elements include At least one of Au, Ag, Pt, Os, Ir, Ru, Rh and Pd.

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

According to a most preferred embodiment of the present invention, the use of Fe, Co, Mg and Ru as active components can greatly improve the catalysis of the composition capable of reducing CO and NOx emissions to NH ₃ and other reduced nitrides conversion activity, and enables compositions capable of reducing CO and NOx emissions to have more excellent hydrothermal stability properties.

According to a specific embodiment of the present invention, the composition comprises: alumina and Fe, Co, Mg and Ru supported on the alumina, in terms of oxides, the weight ratio of Fe to Co is 1:(0.4-2 ), based on the total amount of the composition, the content of alumina is 72-85% by weight, the total content of Fe and Co is 10-16% by weight in terms of oxides, and the content of Mg is 4.9-12% by weight, The content of Ru 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). .

The present invention also provides a method for preparing 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, the second metal element precursor and water to obtain a slurry, spray-drying the slurry, and then performing the first roasting to obtain a semi-finished product combination thing;

(2) using the solution containing the third metal element precursor as the dipping solution, impregnating the semi-finished product composition obtained in step (1) to obtain a solid product, and then drying and/or second roasting the solid product;

Wherein, the first metal element is selected from Group VIII non-noble metal elements, and the first metal element includes Fe and Co; the second metal element is selected from at least one of Group IA and/or IIA metal elements; the third The metal element is selected from at least one of precious 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.

According to the preparation method provided by the present invention, the selection of the inorganic oxide carrier, the first metal element, the second metal element and the third metal element is as described above, and details are not repeated here.

In the present invention, the precursor of alumina 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 present invention, the first metal element precursor, the second metal element precursor and the third metal element precursor are respectively selected from water-soluble salts of the first metal element, the second metal element and the third metal element, such as nitric acid Salts, chlorides, chlorates or sulfates, etc., are not particularly limited in the present invention.

According to the preparation method of the present invention, the amount of the first metal element precursor, the second metal element precursor and the third metal element precursor can be selected in a wide range. The amount of the precursor, the first metal element precursor, the second metal element precursor and the third metal element precursor is such that, in the prepared composition, based on the total amount of the composition, the inorganic oxide support The content is 30-90% by weight, in terms of oxides, the content of the first metal element is 0.5-50% by weight, and the content of the second metal element is 0.5-20% by weight, in terms of elements, the content of the first metal element is 0.5-20% by weight. The content of the trimetal element is 0.001-0.15% by weight; further preferably, the content of the inorganic oxide carrier is 50-90% by weight, and the content of the first metal element is 3-30% by weight in terms of oxides , the content of the second metal element is 1-20% by weight, and the content of the third metal element is 0.005-0.1% by weight in terms of elements; more preferably, the content of the inorganic oxide carrier is 60% -85% by weight, based on oxides, the content of the first metal element is 5-25% by weight, and the content of the second metal element is 2-15% by weight, based on the element, the content of the third metal element The content of the metal element is 0.01-0.08% by weight; most preferably, the content of the inorganic oxide carrier is 72-85% by weight, and the content of the first metal element is 10-16% by weight in terms of oxides, the The content of the second metal element is 4.9-12% by weight, and the content of the third 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 , the amount and mass ratio of the second metal element precursor calculated as the metal element oxide of Group IA and/or IIA and the third metal element precursor calculated as the noble metal element is 30-90: 0.5-50: 0.5-20: 0.001-0.15; further, it can be 50-90: 3-30: 1-20: 0.005-0.1; further, it can be 60-85: 5-25: 2-15: 0.01-0.08, and it can also be 72-85:10-16:4.9-12:0.05-0.07. 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).

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 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 and water is not particularly limited. The order of adding the precursor of a metal element and the precursor of the second metal element is also not limited, as long as the precursor of the inorganic oxide carrier, the precursor of the first metal element and the precursor of the second metal element and water are contacted, preferably , first dissolve the first metal element precursor in water, then add the precursor of the inorganic oxide carrier (preferably the precursor of the acidified inorganic oxide carrier) to obtain a first solution, mix the second metal element precursor with The water is mixed to obtain the second solution, and finally the first solution and the second solution are mixed, and then pulped to obtain a slurry.

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, but in order to further To improve the catalytic conversion activity and hydrothermal stability of the composition capable of reducing CO and NOx emissions to reduced nitrogen compounds such as NH ₃ , it is preferable that the first calcination is performed in a carbon-containing atmosphere. The inventors of the present invention have unexpectedly discovered during the research process that the first calcination is carried out in a carbon-containing atmosphere, which can make the composition capable of reducing CO and NOx emissions in terms of catalytic conversion activity and reduction of _NH3 and other reduced nitrogen compounds. The hydrothermal stability is obviously improved, and the semi-finished composition obtained by the first calcination in a carbon-containing atmosphere is more conducive to the subsequent loading of precious metal elements. The improvement of activity is related to the conversion of active components from oxides to carbides and the reduced state, while the improvement of hydrothermal stability may be related to the fact that high temperature treatment further promotes the bonding, fusion and cross-linking of active components in the composition. It can be seen from the XRD comparison spectrum that there are obvious peaks of iron carbide and elemental cobalt after treatment. Specifically, as shown in Figure 1, the XRD spectrum of composition S-5 without carbon-containing atmosphere treatment has a diffraction peak of MgO at about 43.0°, and Al ₂ O ₃ and Co ₂ at about 45.0° The diffraction peaks of AlO ₄ and MgAl ₂ O ₄ , and the XRD spectrum of the composition S-1 treated with carbon-containing atmosphere not only has the diffraction peak of MgO at about 43.0°, but also has the diffraction peak of Al ₂ O ₃ , The diffraction peaks of Co ₂ AlO ₄ and MgAl ₂ O ₄ , and the diffraction peaks at around 43.0° and around 45.0° were significantly stronger and shifted to the left, which was attributed to the composition S-1 treated with carbon-containing atmosphere, Diffraction peaks appear at 2θ of 42.6° and 44.9°, and the diffraction peaks at 2θ of 42.6° and 44.9° are diffraction peaks of FeC (Fe ₃ C and Fe ₇ C ₃ ). In addition, compared with composition S-5, composition S-1 has a diffraction peak at 44.2°, and the diffraction peak at 2θ of 44.2° is the diffraction peak of elemental cobalt.

It should be noted that FIG. 1 only lists the XRD patterns in the range of 41°-50°, which are mainly used to illustrate the existence forms of Fe and Co in the composition. Outside the range of 41°-50°, there are other diffraction peaks, such as those of FeO (at 37°, 65° and 59° in 2θ) and CoO (at 37°, 65° and 31° in 2θ) , the present invention does not further explain this.

According to a preferred embodiment of the present invention, the conditions for the first calcination include: in a carbon-containing atmosphere, the temperature is 400-1000°C, preferably 450-650°C, more preferably 500-650°C, and the time is 400-1000°C. 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 carbon-containing atmosphere is provided by a gas containing carbon-containing elements, and the carbon-containing element-containing gas is preferably selected from reducing carbon-containing element gases, more preferably containing CO, methane and ethane. At least one, most preferably CO.

According to the present invention, the carbon-containing gas may also contain a part of inert gas, and the inert gas may be various inert gases conventionally used in the field. Preferably, the inert gas is selected from nitrogen, argon and helium. At least one of them is 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, and the volume concentration of CO in the carbon-containing atmosphere is preferably 1-20%, more preferably 4-10%. By adopting the preferred embodiment of the present invention, not only the processing requirements can be better met, but also the safety of operators can be ensured.

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. The carbon-containing gas is brought into countercurrent contact with the solid material in the roaster in the roaster.

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 composition can be added to water first, and then the solution of the precursor of the third 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, preferably, the method further comprises: after the impregnation in step (2), before drying and/or the second roasting, performing an alkali treatment on the solid product. According to the preferred embodiment of the present invention, alkali treatment is performed after impregnation of the noble metal element, so that the noble metal element (the third metal element), the first metal element and the second metal element can be more closely combined, which is more conducive to the synergy of the three It is more beneficial to improve the catalytic conversion activity and hydrothermal stability of the composition capable of reducing CO and NOx emissions to _NH3 and other reduced nitrogen compounds.

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.

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 Fe and Co, at least one of Group IA and/or IIA metal elements, and at least one of noble metal elements, and the above 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 nitrogen compounds is significantly improved, and the composition capable of reducing CO and NOx emissions has 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.

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, magnesium oxide [MgO] It is analytically pure and produced by Sinopharm Chemical Reagent Co., Ltd.; ruthenium chloride (RuCl ₃ ) is analytically pure, with Ru content ≥37%, produced by Yanyijin New Materials Co., Ltd.; pseudo-boehmite is industrial grade Product, alumina content of 64% by weight, pore volume of 0.31 ml/g, produced by Shandong Aluminum Company; hydrochloric acid, concentration of 36.5% by weight, analytically pure, produced by Beijing Chemical Plant; ammonia water, concentration of 25-28%, analytically pure , produced by Beijing Chemical Plant, used after dilution; carbon monoxide, concentration of 10% by volume, nitrogen as balance gas, produced by Beijing Helium Pubei Gas Industry Co., Ltd.; catalytic cracking catalyst industrial product (Cat-A, catalyst brand CGP-1) , Na ₂ O content 0.24 wt %, RE ₂ O ₃ content 3.2 wt %, Al ₂ O ₃ content 48.0 wt %, average particle size 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) 100g, cobalt nitrate ₍ calculated as Co ₂ O , the same below) 100g are added into 3500mL water and stirred until fully dissolved, the bauxite colloid is added to it, and stirred for 15min to obtain the first solution; 100g MgO is added to 360g water, After stirring for 10min, it was added to the first solution, and after stirring for 20min, a slurry was obtained, the slurry was spray-dried, and 150 g of the particles obtained by spray-drying (average particle size was 65 μm, particle size was 40-80 μm) accounted for 60% , the same below) is transferred to a tube furnace, and a _CO /N mixed gas with a CO concentration of 10% by volume 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-1.

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

The composition S-1 was subjected to XRD analysis, and the XRD spectrum was shown in Figure 1. It can be seen from Figure 1 that,

The XRD spectrum of composition S-5 without carbon-containing atmosphere treatment has the diffraction peak of MgO at about 43.0°, and the diffraction peak of Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ at about 45.0° However, in the XRD spectrum of composition S-1 treated with carbon-containing atmosphere, there are not only MgO diffraction peaks at about 43.0°, but also Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ at about 45.0° The diffraction peaks at around 43.0° and around 45.0° were significantly stronger and shifted to the left, which was attributed to the composition S-1 treated with carbon-containing atmosphere, at 2θ of 42.6° and 44.9°. Diffraction peaks appeared, and the diffraction peaks at 2θ of 42.6° and 44.9° were those of FeC (Fe ₃ C and Fe ₇ C ₃ ). In addition, compared with composition S-5, composition S-1 has a diffraction peak at 44.2°, and the diffraction peak at 2θ of 44.2° is the diffraction peak of elemental cobalt.

It should be noted that FIG. 1 only lists the XRD patterns in the range of 41°-50°, which are mainly used to illustrate the existence forms of Fe and Co in the composition. Outside the range of 41°-50°, there are other diffraction peaks, such as those of FeO (at 37°, 65° and 59° in 2θ) and CoO (at 37°, 65° and 31° in 2θ) , the diffraction peaks outside the range of 41°-50° have nothing to do with the diffraction peaks of FeC and elemental Co, and the present invention does not further analyze the spectrum.

Example 2

(1) 2.56kg of pseudo-boehmite was added to 13.9kg of deionized water for slurrying and dispersion, then 232mL of hydrochloric acid was added for acidification for 15min to obtain bauxite colloid, and 140g of iron nitrate and 60g 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 160 g of MgO to 480 g of water, stir for 10 min, add to the first solution, stir for 20 min to obtain a slurry, and spray the slurry Dry, take 150g of the particles obtained by spray drying and transfer it to a tube furnace, introduce a _CO /N mixed gas with a CO concentration of 10% by volume at a flow rate of 100mL/min, and treat at 500 ° C for 3h 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. The XRD analysis results of composition S-2 were similar to those of Example 1. In the XRD spectrum of composition S-2 treated with carbon-containing atmosphere, not only the diffraction peaks of MgO at about 43.0°, but also the diffraction peaks of Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ are found at about 45.0° , and the diffraction peaks at about 43.0° and 45.0° are obviously stronger and shifted to the left, which is attributed to the composition S-2 treated with carbon-containing atmosphere, and the diffraction peaks appear at 2θ of 42.6° and 44.9° , 2θ is 42.6°, and the diffraction peak at 44.9° is the diffraction peak of FeC (Fe ₃ C and Fe ₇ C ₃ ). In addition, compared with composition S-5, composition S-2 has a diffraction peak at 44.2°, and the diffraction peak at 2θ of 44.2° is the diffraction peak of elemental cobalt.

Example 3

(1) 2.34kg of pseudo-boehmite was added to 12.7kg of deionized water for slurrying and dispersion, then 212mL of hydrochloric acid was added for acidification for 15min to obtain bauxite colloid, and 100g of iron nitrate and 200g of cobalt nitrate in terms of metal oxide were added to 4000mL of water Stir until fully dissolved, add bauxite colloid into it, stir for 15 min, to obtain the first solution; add 200 g of MgO to 600 g of water, stir for 10 min, add to the first solution, stir for 20 min to obtain a slurry, and spray the slurry Dry, take 150g of the particles obtained by spray drying and transfer it to a tube furnace, introduce a _CO /N mixed gas with a CO concentration of 10% by volume at a flow rate of 100mL/min, and treat at 650 ° C for 1h 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. The XRD analysis results of composition S-3 were similar to those of Example 1. In the XRD spectrum of the composition S-3 treated with carbon-containing atmosphere, not only the diffraction peaks of MgO at about 43.0°, but also the diffraction peaks of Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ are found at about 45.0° , and the diffraction peaks at about 43.0° and 45.0° are obviously stronger and shifted to the left, which is attributed to the composition S-3 treated with carbon-containing atmosphere, and the diffraction peaks appear at 2θ of 42.6° and 44.9° , 2θ is 42.6°, and the diffraction peak at 44.9° is the diffraction peak of FeC (Fe ₃ C and Fe ₇ C ₃ ). In addition, compared with composition S-3, composition S-1 has a diffraction peak at 44.2°, and the diffraction peak at 2θ of 44.2° is the diffraction peak of elemental cobalt.

Example 4

(1) 2.25kg of pseudo-boehmite was added to 12.2kg of deionized water for slurrying and dispersion, then 204mL of hydrochloric acid was added for acidification for 15min to obtain bauxite colloid, and 200g of iron nitrate and 120g 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 240 g of MgO into 720 g of water, stir for 10 min and add to the first solution, stir for 20 min to obtain a slurry, and carry out the Spray drying, transfer 150 g of the particles obtained by spray drying to a tube furnace, pass a CO/N ₂ mixed gas with a CO concentration of 10% by volume at a flow rate of 100 mL/min, and treat at 600 ° C for 1.5 h to obtain a semi-finished product combination thing;

(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. The XRD analysis results of composition S-4 were similar to those of Example 1. In the XRD spectrum of composition S-4 treated with carbon-containing atmosphere, not only the diffraction peaks of MgO at about 43.0°, but also the diffraction peaks of Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ are found at about 45.0° , and the diffraction peaks at about 43.0° and 45.0° are obviously stronger and shifted to the left, which is attributed to the composition S-4 treated with carbon-containing atmosphere, and the diffraction peaks appear at 2θ of 42.6° and 44.9° , 2θ is 42.6°, and the diffraction peak at 44.9° is the diffraction peak of FeC (Fe ₃ C and Fe ₇ C ₃ ). In addition, compared with composition S-5, composition S-4 has a diffraction peak at 44.2°, and the diffraction peak at 2θ of 44.2° is the diffraction peak of elemental cobalt.

Example 5

According to the method of Example 1, the difference is that the CO/N ₂ mixed gas with a CO concentration of 10% by volume is replaced with air to obtain the composition S-5.

The content determination results of each component in composition S-5 are listed in Table 1. XRD analysis of composition S-5 was carried out. It can be seen from the XRD spectrum (as shown in Figure 1) that there are no obvious diffraction peaks at 2θ of 42.6°, 44.2° and 44.9°, which proves that Fe in composition S-5 and Co exist in the form of oxides.

Example 6

According to the method of embodiment 1, the difference is that step (2) does not include the step of rinsing the solid product with 80 mL of aqueous ammonia solution with a concentration of 2 mol/L, and the solid product is directly dried and roasted to obtain composition S-6 .

Table 1 shows the measurement results of the content of each component in composition S-6. The XRD analysis results of composition S-6 were similar to those of Example 1. In the XRD spectrum of composition S-6 treated with carbon-containing atmosphere, not only the diffraction peaks of MgO at about 43.0°, but also the diffraction peaks of Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ are found at about 45.0° , and the diffraction peaks at about 43.0° and 45.0° are obviously stronger and shifted to the left, which is attributed to the composition S-6 treated with carbon-containing atmosphere, and the diffraction peaks appear at 2θ of 42.6° and 44.9° , 2θ is 42.6°, and the diffraction peak at 44.9° is the diffraction peak of FeC (Fe ₃ C and Fe ₇ C ₃ ). In addition, compared with composition S-5, composition S-6 has a diffraction peak at 44.2°, and the diffraction peak at 2θ of 44.2° is the diffraction peak of elemental cobalt.

Example 7

According to the method of Example 1, the difference is that, in terms of metal oxide, the same mass of CaO is used to replace MgO to obtain composition S-7.

Table 1 shows the results of content determination of each component in composition S-7. The XRD analysis results of composition S-7 were similar to Example 1. In the XRD spectrum of composition S-7 treated with carbon-containing atmosphere, not only the diffraction peaks of MgO at about 43.0°, but also the diffraction peaks of Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ are found at about 45.0° , and the diffraction peaks at about 43.0° and 45.0° are obviously stronger and shifted to the left, which is attributed to the composition S-7 treated with carbon-containing atmosphere, and the diffraction peaks appear at 2θ of 42.6° and 44.9° , 2θ is 42.6°, and the diffraction peak at 44.9° is the diffraction peak of FeC (Fe ₃ C and Fe ₇ C ₃ ). In addition, compared with composition S-5, composition S-7 has a diffraction peak at 44.2°, and the diffraction peak at 2θ of 44.2° is the diffraction peak of elemental cobalt.

Example 8

According to the method of Example 1, the difference is that the amount of ferric nitrate calculated as metal oxide is 50 g, and the amount of cobalt nitrate is 150 g to obtain composition S-8.

Table 1 shows the results of determination of the content of each component in composition S-8. The XRD analysis results of composition S-8 were similar to Example 1. In the XRD spectrum of composition S-8 treated with carbon-containing atmosphere, not only the diffraction peaks of MgO at about 43.0°, but also the diffraction peaks of Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ are found at about 45.0° , and the diffraction peaks at about 43.0° and 45.0° are obviously stronger and shifted to the left, which is attributed to the composition S-8 treated with carbon-containing atmosphere, and the diffraction peaks appear at 2θ of 42.6° and 44.9° , 2θ is 42.6°, and the diffraction peak at 44.9° is the diffraction peak of FeC (Fe ₃ C and Fe ₇ C ₃ ). In addition, compared with composition S-5, composition S-8 has a diffraction peak at 44.2°, and the diffraction peak at 2θ of 44.2° is the diffraction peak of elemental cobalt.

Example 9

According to the method of Example 1, the difference is that the amount of ferric nitrate calculated as metal oxide is 150 g, and the amount of cobalt nitrate is 50 g to obtain composition S-9.

The content determination results of each component in composition S-9 are listed in Table 1. The XRD analysis results of composition S-9 were similar to those of Example 1. In the XRD spectrum of composition S-9 treated with carbon-containing atmosphere, not only the diffraction peaks of MgO at about 43.0°, but also the diffraction peaks of Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ are found at about 45.0° , and the diffraction peaks at about 43.0° and 45.0° are obviously stronger and shifted to the left, which is attributed to the composition S-9 treated with carbon-containing atmosphere, and the diffraction peaks appear at 2θ of 42.6° and 44.9° , 2θ is 42.6°, and the diffraction peak at 44.9° is the diffraction peak of FeC (Fe ₃ C and Fe ₇ C ₃ ). In addition, compared with composition S-5, composition S-9 has a diffraction peak at 44.2°, and the diffraction peak at 2θ of 44.2° is the diffraction peak of elemental cobalt.

Example 10

According to the method of Example 1, the difference is that the mixed gas of CO/N ₂ with a concentration of 10 vol % is replaced with a mixed gas of ethane/nitrogen with a concentration of 10 vol % of ethane to obtain the composition S-10.

The content determination results of each component in composition S-10 are listed in Table 1. The XRD analysis results of composition S-10 were similar to Example 1. In the XRD spectrum of the composition S-10 treated with carbon-containing atmosphere, not only the diffraction peaks of MgO at about 43.0°, but also the diffraction peaks of Al ₂ O ₃ , Co ₂ AlO ₄ and MgAl ₂ O ₄ are found at about 45.0° , and the diffraction peaks at about 43.0° and 45.0° are obviously stronger and shifted to the left, which is attributed to the composition S-10 treated with carbon-containing atmosphere, and the diffraction peaks appear at 2θ of 42.6° and 44.9° , 2θ is 42.6°, and the diffraction peak at 44.9° is the diffraction peak of FeC (Fe ₃ C and Fe ₇ C ₃ ). In addition, compared with composition S-5, composition S-10 has a diffraction peak at 44.2°, and the diffraction peak at 2θ of 44.2° is the diffraction peak of elemental cobalt.

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 in terms of metal oxide, the same mass of cobalt nitrate is used to replace the iron nitrate 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 and the second metal element are calculated as oxides, and the unit is wt%, and the content of the third metal element is calculated as the element, and the unit is wt%.

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 gasoline, diesel and heavy oil yields.

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

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

Numbering NOx concentration, ppm CO concentration, vol% Example 1 S-1 85 0.36 Comparative Example 1 D-1 194 0.35 Comparative Example 2 D-2 180 0.37 Comparative Example 3 D-3 264 0.48 Example 2 S-2 91 0.36 Example 3 S-3 51 0.34 Example 4 S-4 36 0.33 Example 5 S-5 89 0.36 Example 6 S-6 103 0.37 Example 7 S-7 92 0.36 Example 8 S-8 85 0.37 Example 9 S-9 90 0.35 Example 10 S-10 85 0.36

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 h, 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 52 72 2.79 Comparative Example 1 D-1 120 160 2.74 Comparative Example 2 D-2 107 156 2.82 Comparative Example 3 D-3 109 321 3.15 Example 2 S-2 57 74 2.77 Example 3 S-3 32 42 2.71 Example 4 S-4 twenty one 33 2.7 Example 5 S-5 54 75 2.77 Example 6 S-6 68 76 2.80 Example 7 S-7 56 78 2.78 Example 8 S-8 51 73 2.8 Example 9 S-9 55 75 2.76 Example 10 S-10 51 73 2.78

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. In particular, it can be seen from the comparison between Example 1 and Example 5 that the preferred first calcination of the present invention is carried out in a carbon-containing atmosphere, so that the performance of the composition capable of reducing CO and NOx emissions is further improved; It can be seen from the comparison of Example 6 that the preferred method of the present invention is to perform alkali treatment after impregnating precious metals, so that the performance of the composition capable of reducing CO and NOx emissions is further improved; from the comparison between Example 1 and Example 7, it can be seen that, The use of the preferred metal elements 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 of Example 1 with Example 8 and Example 9 that using the preferred Fe to Co mass ratio of the present invention, The performance of the composition capable of reducing CO and NOx emissions is further improved; from the comparison between Example 1 and Example 10, it can be seen that the preferred carbon-containing atmosphere of the present invention is used for treatment, so that the performance of the composition capable of reducing CO and NOx emissions is further improved ; It can be seen from the comparison between Example 1 and Comparative Examples 1-3 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.

Claims (45)

1. A composition capable of reducing CO and NOx emissions, characterized in that the composition consists of an inorganic oxide carrier and the first metal element, the second metal element and the third metal element supported on the inorganic oxide carrier , the first metal element is selected from the group VIII non-noble metal elements, and the first metal element includes Fe and Co, in terms of oxides, the weight ratio of Fe to Co is 1: (0.05-20), the The second metal element is selected from at least one of Na, K, Mg and Ca, and the third metal element is Ru; Based on the total amount of the composition, the content of the inorganic oxide carrier is 50-90% by weight, in terms of oxides, the content of the first metal element is 3-30% by weight, and the second metal element is The content of the third metal element is 1-20% by weight, and the content of the third metal element is 0.005-0.1% by weight in terms of elements. 2. The composition according to claim 1, wherein, based on the total amount of the composition, the content of the inorganic oxide carrier is 60-85% by weight, calculated as oxide, the content of the first metal element is 60-85% by weight. The content is 5-25% by weight, the content of the second metal element is 2-15% by weight, and the content of the third metal element is 0.01-0.08% by weight in terms of elements. 3. The composition of claim 1, wherein the weight ratio of Fe to Co is 1:(0.1-10) in terms of oxides. 4. The composition of claim 3, wherein the weight ratio of Fe to Co is 1:(0.3-3) in terms of oxide. 5. The composition of claim 4, wherein the weight ratio of Fe to Co in terms of oxide is 1:(0.4-2). 6. The composition of any one of claims 1-5, wherein, The Fe in the composition is at least partially in the form of iron carbide; The Co in the composition is present at least in part in the form of elemental cobalt. 7 . The composition according to claim 6 , wherein in the XRD pattern of the composition, there are diffraction peaks at 2θ of 42.6°, 44.2° and 44.9°. 8 . 8. The composition of any one of claims 1-5, wherein the inorganic oxide support is selected from the group consisting of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, pearls At least one of rock and perovskite. 9. The composition of claim 8, wherein the inorganic oxide support is selected from at least one of alumina, spinel, and perovskite. 10. The composition of claim 9, wherein the inorganic oxide support is alumina. 11. The composition of claim 1, wherein the second metal element is K and/or Mg. 12. The composition of claim 11, wherein the second metal element is Mg. 13. A method for preparing a composition capable of reducing CO and NOx emissions, characterized in that the method comprises: (1) mixing and beating the precursor of the inorganic oxide carrier, the first metal element precursor and the second 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 combination thing; (2) using the solution containing the third metal element precursor as the dipping solution, impregnating the semi-finished product composition obtained in step (1) to obtain a solid product, and then drying and/or second roasting the solid product; Wherein, the first metal element is selected from group VIII non-noble metal elements, and the first metal element includes Fe and Co; the second metal element is selected from at least one of Na, K, Mg and Ca; the third metal element for Ru; 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 amount of the precursor of the inorganic oxide carrier, the precursor of the first metal element, the precursor of the second metal element and the precursor of the third 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 50-90% by weight, 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 in terms of oxide, In element terms, the content of the third metal element is 0.005-0.1 wt %. 14 . The preparation method according to claim 13 , wherein the conditions for the first calcination include: performing in a carbon-containing atmosphere, at a temperature of 400-1000° C., and a time of 0.1-10 h. 15 . 15 . The preparation method according to claim 14 , wherein the conditions for the first roasting comprise: a temperature of 450-650° C. and a time of 1-3 hours. 16 . 16. The preparation method according to claim 14, wherein the carbon-containing atmosphere is provided by a gas containing carbon elements selected from at least one of CO, methane and ethane. 17. The preparation method according to claim 16, wherein the carbon element-containing gas is CO. 18. The preparation method according to claim 17, wherein the volume concentration of CO in the carbon-containing atmosphere is 1-20%. 19. The preparation method according to claim 18, wherein the volume concentration of CO in the carbon-containing atmosphere is 4-10%. 20. The preparation method according to claim 13, wherein the method further comprises: after the impregnation in step (2), before drying and/or second roasting, performing an alkali treatment on the solid product. 21. The preparation method according to claim 20, wherein the alkali treatment method comprises: mixing and beating the solid product with an alkaline solution, or rinsing the solid product with an alkaline solution. 22. The preparation method according to claim 21, wherein the alkaline solution is a non-metallic element alkaline solution. 23. The preparation method according to claim 22, wherein the alkaline solution is ammonia water and/or alkaline ammonium salt solution. 24. The preparation method according to claim 21, wherein the concentration of the alkaline solution is 0.01-10 mol/L. 25. The preparation method according to claim 24, wherein the concentration of the alkaline solution is 0.05-5 mol/L. 26. The preparation method according to claim 21, wherein the volume dosage of the alkaline solution is 1-10 times the pore volume of the solid product. 27. The preparation method according to claim 26, wherein the volume dosage of the alkaline solution is 1.5-5 times the pore volume of the solid product. 28. The preparation method according to claim 13, wherein the content of the inorganic oxide carrier is 60-85% 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 2-15% by weight, and the content of the third metal element is 0.01-0.08% by weight in terms of elements. 29. The preparation method according to any one of claims 13-28, 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 is The ratio is 1:(0.1-10). 30. The preparation method according to claim 29, wherein the amount 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). 31. The preparation method according to claim 30, 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). 32. The preparation method according to any one of claims 13-28, wherein the inorganic oxide carrier is selected from the group consisting of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, pearl At least one of rock and perovskite. 33. The preparation method according to claim 32, wherein the inorganic oxide support is selected from at least one of alumina, spinel and perovskite. 34. The preparation method according to claim 33, wherein the inorganic oxide support is alumina. 35. The preparation method according to claim 34, wherein, before beating, acidizing and peptizing the alumina precursor is performed. 36. The preparation method according to claim 35, wherein the acid used in the acidified peptization treatment is hydrochloric acid, and the conditions of the acidified peptization treatment include: the ratio of acid to aluminum is 0.12-0.22:1, and the time is 20-40min . 37. The preparation method according to claim 13, wherein the second metal element is K and/or Mg. 38. The preparation method according to claim 37, wherein the second metal element is Mg. 39. The preparation method according to any one of claims 13-28, wherein the first metal element precursor, the second metal element precursor and the third metal element precursor are selected from the group consisting of the first metal element, Water-soluble salts of the second metal element and the third metal element. 40. A composition capable of reducing CO and NOx emissions prepared by the preparation method of any one of claims 13-39. 41. Use of a composition capable of reducing CO and NOx emissions according to any one of claims 1-12 and 40 in flue gas treatment. 42. Use of a composition capable of reducing CO and NOx emissions according to any one of claims 1-12 and 40 in catalytic cracking regeneration flue gas treatment. 43. A fluidized catalytic cracking method, the 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 any one of claims 1-12 and 40. 44. The fluid catalytic cracking method of claim 43, wherein the content of the composition capable of reducing CO and NOx emissions is 0.05-5 wt% based on the total amount of catalyst. 45. The fluid catalytic cracking method according to claim 44, wherein the content of the composition capable of reducing CO and NOx emissions is 0.1-3 wt% based on the total amount of catalyst.

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