CN111774079A

CN111774079A - Composition capable of reducing emission of CO and NOx, preparation method and application thereof

Info

Publication number: CN111774079A
Application number: CN202010524208.9A
Authority: CN
Inventors: 姜秋桥; 宋海涛; 王鹏; 陈妍; 孙言; 刘博�; 田辉平; 朱玉霞; 达志坚
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2017-07-05
Filing date: 2017-07-05
Publication date: 2020-10-16
Anticipated expiration: 2037-07-05
Also published as: CN111774079B; CN109201075B; CN109201075A

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, 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 the IA and/or IIA group metal elements and at least one of IB-VIIB group non-noble metal elements, and has higher activity of reducing CO and NOx emission of regenerated flue gas.

Description

Composition capable of reducing emission of CO and NOx, preparation method and application thereof

Technical Field

The invention relates to the field of catalytic cracking, in particular to a composition capable of reducing CO and NOx emission, a preparation method of the composition capable of reducing CO and NOx emission, a composition capable of reducing CO and NOx emission prepared by the method, application of the composition capable of reducing CO and NOx emission and a fluidized catalytic cracking method.

Background

The continuous rise of the price of the crude oil greatly increases the processing cost of a refinery, and the refinery reduces the cost by purchasing low-price inferior oil on one hand; on the other hand, the economic benefit is increased by deep processing of heavy oil. Catalytic cracking plays a major role in refineries as an important means for processing heavy oil in refineries, and is not only a main means for balancing heavy oil in refineries and producing clean fuel, but also an attention point for energy conservation and efficiency improvement of refineries. Catalytic cracking is a rapid catalytic reaction system with a catalyst rapidly deactivated, and the problem of catalyst regeneration is always the main line of catalytic cracking development.

In the process of Fluid Catalytic Cracking (FCC), raw oil and a regenerated catalyst are in rapid contact in a riser to carry out catalytic cracking reaction, coke generated by the reaction is deposited on the catalyst to cause the deactivation of the catalyst, the coke-formed deactivated catalyst enters a regenerator after being stripped and contacts with regenerated air or air rich in oxygen entering the bottom of the regenerator to carry out coke-burning regeneration. The regenerated catalyst is circulated back to the reactor to participate in the catalytic cracking reaction again. According to the content of the surplus oxygen in the flue gas in the regeneration process or the sufficient degree of CO oxidation, the catalytic cracking device can be divided into complete regeneration operation and incomplete regeneration operation.

In the complete regeneration process, the coke and the nitrogen-containing compounds in the coke generate CO under the action of regeneration air₂And N₂And also produces pollutants such as CO and NOx. The use of catalytic promoters is an important technical measure for controlling CO and NOx emission pollution.

An auxiliary agent for reducing CO emission of regeneration flue gas is generally called a CO combustion improver, for example, CN1022843C discloses a noble metal loaded carbon monoxide combustion improver, the active component of the noble metal loaded carbon monoxide combustion improver is 1-1000ppm platinum or 50-1000ppm palladium, the carrier comprises (1) microsphere particles of 99.5-50% of cracking catalyst or matrix thereof and (2) 0.5-50% of Al₂O₃、0-20％RE₂O₃And 0-15% ZrO₂Composition (2) is (1) the outer coating of the particles.

An aid for controlling flue gas NOx emissions, commonly referred to as a NOx emission reduction aid or NOx reduction aid, for example CN102371150A discloses a non-precious metal composition for reducing NOx emissions from catalytically cracked regenerated flue gas, said composition having a bulk ratio of not more than 0.65 g/ml and comprising, in terms of oxides based on the weight of the composition: (1)50-99 wt% of inorganic oxide carrier, (2)0.5-40 wt% of one or more non-noble metal elements selected from IIA, IIB, IVB and VIB, and (3)0.5-30 wt% of rare earth elements. The composition is used for fluidized catalytic cracking, and can remarkably reduce the emission of NOx in regeneration flue gas.

And the auxiliary agents capable of simultaneously reducing the emission of CO and NOx in the regenerated flue gas can give consideration to both CO combustion supporting and NOx emission reduction, and the application of the auxiliary agents is increasingly common along with the increasing strictness of environmental protection regulations. For example, CN1688508A discloses a composition for reducing NOx and CO emissions from fluid catalytic cracking flue gas and its use, said composition comprising copper and/or cobalt and a support selected from the group consisting of hydrotalcite-like compounds, spinels, alumina, zinc titanate, zinc aluminate, zinc titanate/zinc aluminate. CN102371165A discloses a low bulk ratio composition for reducing CO and NOx emissions from FCC regenerated flue gas, which contains rare earth elements and one or more non-noble metal elements, preferably non-noble metal supported on Y-type zeolite. US6165933 discloses a CO combustion supporting composition (CO agent) for reducing NOx emissions from a catalytic cracking process, said composition comprising: (i) an acidic metal oxide substantially free of zeolite; (ii) alkali metals, alkaline earth metals or mixtures thereof; (iii) (iii) an oxygen storage component and (iv) palladium, the inorganic oxide support preferably being a silica-alumina and the oxygen storage transition metal oxide preferably being a ceria. US7045056 discloses a composition for simultaneously reducing CO and NOx emissions from the flue gas of a catalytic cracking process, said composition comprising: (i) an inorganic oxide support; (ii) an oxide of cerium; (iii) a lanthanide oxide other than cerium, wherein the weight ratio of (ii) to (iii) is at least 1.66: 1; (iv) optionally one group IB and IIB transition metal oxide, and (v) at least one noble 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, calculated as oxides: (1)0.5 to 30% by weight of a rare earth element, (2)0.01 to 0.15% by weight of a noble metal element, and (3) the balance of an inorganic oxide support substantially free of alkali metals and alkaline earth metals; in the preparation method, the composition introduced with the noble metal is treated by alkaline solution before drying and/or roasting, and the disclosed composition is used for fluid catalytic cracking, can effectively avoid 'afterburning' caused by overhigh CO concentration of regenerated flue gas, can effectively control the emission concentration of CO and NOx in the regenerated flue gas, obviously reduces the emission of NOx in the flue gas, and basically does not cause adverse effect on the distribution of FCC products.

During incomplete regeneration, the flue gas from the regenerator has a very low NOx concentration and reduced nitrides such as NH due to low excess oxygen content and high CO concentration₃And higher concentration of HCN and the like. These reduced nitrides flow downstream with the flue gas, and if they are sufficiently oxidized in the CO boiler for energy recovery, NOx is formed; if not sufficiently oxidized, residual NH₃The ammonia nitrogen content of the wastewater of the downstream washing tower exceeds the standard or is easy to cause the SO in the flue gas_xThe ammonium salt generated by the reaction is separated out, so that salt deposition is caused in a waste boiler or other flue gas post-treatment equipment (such as SCR), and the long-period operation of the device is influenced. Thus, the incomplete regeneration process catalytically converts NH in the regenerator using a catalyst promoter₃And the NOx emission in the flue gas can be reduced, and the operation period of the device is prolonged.

US5021144 discloses a method for reducing NH in flue gas of incomplete regeneration FCC device₃The method of discharging is to add excess CO combustion improver into the regenerator in an amount 2-3 times the minimum addition to prevent lean bed afterburning. The method can reduce NH in flue gas of incomplete regeneration FCC device₃But the emission is large, the energy consumption is high, and the environmental protection is not facilitated.

US4755282 discloses a process for reducing NH in flue gas of a partially or incompletely regenerated FCC unit₃A method of venting. The method comprises adding ammonia decomposition catalyst with particle size of 10-40 μm into regenerator, maintaining the catalyst in dilute phase bed layer at a certain concentration, and adding NH₃Conversion to N₂And water. The active component of the ammonia decomposition catalyst may beNoble metals dispersed on inorganic oxide supports.

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

Currently, for controlling the flue gas NH of incomplete regenerators₃And NOx emission auxiliary agent technical research and application reports are relatively few, and because the difference between the smoke composition of an incomplete regeneration device and a complete regeneration device is obvious, the existing catalytic auxiliary agent suitable for the complete regeneration device has an undesirable application effect on the incomplete regeneration device. The auxiliary agent composition disclosed in the above technology can catalyze and convert NH in flue gas to a certain extent₃Nitride in reduced state, but for NH in flue gas₃The catalytic conversion activity of the nitride in reduced state is still to be improved to slow down NH₃And the influence of deposited salt on the operation of equipment is avoided, so that the development of a flue gas pollutant emission reduction auxiliary agent suitable for an incomplete regeneration device is needed, and the emission of flue gas NOx is further reduced.

Disclosure of Invention

Aiming at NH in the regeneration process of the prior art₃The invention provides a novel composition capable of reducing CO and NOx emission, a preparation method of the composition capable of reducing CO and NOx emission, the composition capable of reducing CO and NOx emission prepared by the method, application of the composition capable of reducing CO and NOx emission in flue gas treatment and a fluidized catalytic cracking method. The composition capable of reducing the emission of CO and NOx provided by the invention has high catalytic conversion activity on reduced nitrides, is simple in preparation method, can be used in the fluidized catalytic cracking process, and can effectively reduce the emission of CO and NOx in catalytic cracking regeneration flue gas.

In the research process, the inventor of the invention finds that the emission of CO and NOx in the catalytic cracking regeneration flue gas can be effectively reduced by using inorganic oxide as a carrier and combining a VIII group non-noble metal element containing Fe and Co with at least one of IA and/or IIA group metal elements and at least one of IB-VIIB group non-noble metal elements as active components. The reason for this may presumably be due to: fe and Co are jointly used as main metal elements, and the generation of nitrogen-containing compounds in an oxidation state can be reduced and the decomposition of nitrogen-containing compounds in a reduction state can be promoted by further modifying at least one of IA and/or IIA group metal elements and at least one of IB-VIIB group non-noble metal elements.

Through further research, the solid obtained after spray drying is preferably treated at high temperature in a carbon-containing atmosphere after the spray drying, so that the emission of CO and NOx in the catalytic cracking regeneration flue gas can be more effectively reduced. In the preferred case, the structure of the composition capable of reducing CO and NOx emissions is further conditioned and stabilized so that the composition capable of reducing CO and NOx emissions is directed to NH₃The catalytic conversion activity of the reduced nitrides is obviously improved, the hydrothermal stability is better, and the requirements of the regenerator hydrothermal environment on the composition capable of reducing the emission of CO and NOx are met.

In view of 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: the metal oxide carrier comprises an inorganic oxide carrier and a first metal element, a second metal element and a third metal element which are loaded on the inorganic oxide carrier, wherein the first metal element is selected from non-noble metal elements in a VIII group, the first metal element comprises Fe and Co, and 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 group IB-VIIB non-noble metal elements.

According to a second aspect of the present invention, there is provided a process for the preparation of a composition capable of reducing CO and NOx emissions, the process comprising: mixing and pulping a precursor of an inorganic oxide carrier, a first metal element precursor, a second metal element precursor, a third metal element precursor and water to obtain slurry, carrying out spray drying on the slurry, and then roasting;

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

in the first metal element precursor, the dosage of the precursor of Fe and the precursor of Co is such that the weight ratio of Fe to Co in the prepared composition 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 produced by the above-described production method.

According to a fourth aspect of the present invention there is provided the use of a composition as described above capable of reducing CO and NOx emissions in the treatment of flue gases.

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

According to a sixth aspect of the present invention there is provided a fluid catalytic cracking process comprising: the hydrocarbon oil is contacted with a catalyst for reaction, and then the catalyst after the contact reaction is regenerated, wherein the catalyst comprises a catalytic cracking catalyst and a composition capable of reducing CO and NOx emission, and the composition capable of reducing CO and NOx emission is the composition capable of reducing CO and NOx emission.

The composition capable of reducing the emission of CO and NOx provided by the invention is used as a catalytic cracking auxiliary agent, can keep higher hydrothermal stability in a regenerator hydrothermal environment, and has higher activity of reducing the emission of CO and NOx in regeneration flue gas. In addition, the preparation method of the composition capable of reducing CO and NOx emission provided by the invention is simple to operate and low in production cost. Compared with the FCC method using the prior CO and NOx emission reducing auxiliary agent, the FCC method using the composition capable of reducing the CO and NOx emission provided by the invention has the advantages of low consumption of the composition capable of reducing the CO and NOx emission and higher activity of reducing the CO and NOx emission.

For example, the composition capable of reducing CO and NOx emissions provided in example 3 of the present invention is uniformly mixed with FCC main catalyst (Cat-a) in an amount of 0.8 wt% based on the total weight of the catalyst, and then aged at 800 ℃ for 12 hours in an atmosphere of 100% steam for catalytic cracking reaction-regeneration evaluation, and compared with composition D-3 capable of reducing CO and NOx emissions prepared by a prior art saturated impregnation method with active components, when the composition capable of reducing CO and NOx emissions provided in the present invention is used, the NOx emission concentration in the incompletely regenerated flue gas under aerobic conditions is reduced from 109ppm to 45 ppm.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

figure 1 is an XRD pattern of the compositions capable of reducing CO and NOx emissions made in examples 1 and 5.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The present invention provides a composition capable of reducing CO and NOx emissions, the composition comprising: the metal oxide carrier comprises an inorganic oxide carrier and a first metal element, a second metal element and a third metal element which are loaded on the inorganic oxide carrier, wherein the first metal element is selected from non-noble metal elements in a VIII group, the first metal element comprises Fe and Co, and 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 group IB-VIIB non-noble metal elements.

The content of the first metal element, the second metal element and the third metal element in the composition is selected in a wide range, and preferably, the content of the inorganic oxide carrier is 10 to 90 weight percent based on the total amount of the composition, the content of the first metal element is 0.5 to 50 weight percent, the content of the second metal element is 0.5 to 20 weight percent and the content of the third metal element is 0.5 to 20 weight percent in terms of oxide; further preferably, the content of the inorganic oxide carrier is 50 to 90 wt%, and the content of the first metal element is 3 to 30 wt%, the content of the second metal element is 1 to 20 wt%, and the content of the third metal element is 1 to 10 wt% in terms of oxide; still more preferably, the content of the inorganic oxide support is 55 to 85 wt%, the content of the first metal element is 5 to 25 wt%, the content of the second metal element is 5 to 15 wt%, and the content of the third metal element is 2 to 8 wt% in terms of oxide; most preferably, the inorganic oxide support has a content of 66 to 85 wt%, the first metal element has a content of 6 to 16 wt%, the second metal element has a content of 5 to 12 wt%, and the third metal element has a content of 3 to 8 wt%, calculated as an oxide.

The first metal element comprises Fe and Co, and the invention does not exclude that the first metal element also comprises elements other than Fe and Co in the VIII group 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 is only Fe and Co.

In the present invention, the first metal element may contain Fe and Co as long as it can increase NH content of the composition₃The catalytic conversion activity of the nitride in an equireduced state is excellent in order to further exert the synergistic effect of Fe and CoOptionally, the weight ratio of Fe to Co calculated as oxides is 1: (0.1 to 10), more preferably 1 (0.3 to 3), still more preferably 1: (0.5-2). The inventor of the invention finds that Fe and Co in a specific ratio can generate better synergistic effect, and are more beneficial to improving the performance of the composition.

In the present invention, unless otherwise specified, Fe in terms of oxide means Fe in terms of Fe₂O₃In terms of Co in oxide, Co means Co in Co₂O₃And (6) counting.

According to a preferred embodiment of the invention, the Fe in the composition is at least partially present in the form of iron carbide, preferably Fe₃C and/or Fe₇C₃. The amount of iron carbide present is not particularly limited in the present invention, and the presence of some iron carbide is effective to improve the performance of the composition that reduces CO and NOx emissions.

According to a preferred embodiment of the invention, the Co in the composition is at least partly present in the form of elemental cobalt. The present invention is not particularly limited as to the amount of elemental cobalt present, as long as some elemental cobalt is present, the performance of the composition that is effective in reducing CO and NOx emissions is enhanced.

In the existing compositions for reducing CO and NOx emissions, the metal elements in the compositions are mostly present in the form of oxidized state. In the preparation process of the composition, the composition is preferably roasted 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 existence of the iron carbide and/or the simple substance cobalt can enable the composition to better promote the decomposition of the nitrogen-containing compounds in a reduction state, reduce the generation of nitrogen oxides and promote the reduction of the nitrogen oxides to a certain extent.

According to the composition provided by the invention, preferably, the XRD pattern of the composition has diffraction peaks at 42.6 degrees, 44.2 degrees and 44.9 degrees of 2 theta.

Specifically, diffraction peaks of iron carbide at 42.6 ° and 44.9 ° of 2 θ; the diffraction peak of the simple substance cobalt is at 44.2 degrees 2 theta.

According to a preferred embodiment of the present invention, the present invention provides a composition having an XRD pattern with a diffraction peak at 44.9 ° 2 θ stronger than a diffraction peak at 42.6 ° 2 θ.

According to the composition provided by the present invention, the inorganic oxide support may be various inorganic oxide supports conventionally used in the art, for example, at least one selected from the group consisting of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite, and perovskite. In the present invention, the spinel may be various commonly used spinels, and may be at least one of magnesium aluminate spinel, zinc aluminate spinel, and titanium aluminate spinel, for example.

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 further preferably alumina.

In the present invention, the alumina may be at least one selected from the group consisting of γ -alumina, η -alumina, ρ -alumina, κ -alumina and χ -alumina, and the present invention is not particularly limited thereto.

The alumina may be derived from various sols or gels of aluminum, or aluminum hydroxide. The aluminum hydroxide may be selected from at least one of gibbsite, surge dam, nordstrandite, diaspore, boehmite, and pseudoboehmite. Preferably, the alumina source is selected from pseudoboehmite.

The inorganic oxide support may be commercially available or may be prepared by a conventional method.

In the present invention, the group IA metal elements include, but are not limited to, Na and/or K; the group IIA metal element includes, but is not limited to, at least one of Mg, Ca, Sr, and Ba. In the invention, the non-noble metal elements in groups IB-VIIB refer to non-noble metals from groups IB to VIIB in the periodic table of elements, including non-noble metals in groups IB, metals in groups IIB, metals in groups IIIB, metals in groups IVB, metals in groups VB, metals in groups VIB and metals in groups VIIB, specifically, the non-noble metal elements in groups IB-VIIB include but are not limited to at least one of Cu, Zn, Cd, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Re and rare earth elements; the rare earth elements include, but are not limited to, at least one of La, Ce, Pr, Nd, Pm, Sm, and Eu.

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, further preferably K and/or Mg, and most preferably Mg.

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

According to a most preferred embodiment of the present invention, the NH pair of the composition capable of reducing CO and NOx emissions is substantially improved by using Fe, Co, Mg and Mn in combination as metal elements₃The catalytic conversion activity of the reduced nitrides and enables the composition capable of reducing the emission of CO and NOx to have more excellent hydrothermal stability.

According to a particular embodiment of the invention, the composition comprises: alumina and Fe, Co, Mg and Mn loaded on the alumina, wherein the weight ratio of Fe to Co is 1: (0.5-2), based on the total weight of the composition, the content of alumina is 66-85 wt%, the total content of Fe and Co is 6-16 wt%, the content of Mg is 5-12 wt%, and the content of Mn is 3-8 wt%.

In the invention, the contents of all components in the composition capable of reducing the emission of CO and NOx are measured by adopting an X-ray fluorescence spectrum analysis method (a petrochemical engineering analysis method (RIPP experimental method), compilation of Yangcui and the like, published by scientific publishing company in 1990).

The present invention also provides a method for preparing a composition capable of reducing CO and NOx emissions, the method comprising: mixing and pulping a precursor of an inorganic oxide carrier, a first metal element precursor, a second metal element precursor, a third metal element precursor and water to obtain slurry, carrying out spray drying on the slurry, and then roasting;

In the present invention, the precursor of the inorganic oxide support includes various substances that can be obtained by a subsequent firing treatment, and the present invention is not particularly limited thereto.

According to the preparation method provided by the invention, the inorganic oxide carrier and the first metal element, the second metal element and the third metal element are selected as described above, and are not described again here.

In the present invention, the precursor of alumina may be selected from various sols or gels of aluminum, or aluminum hydroxide. The aluminum hydroxide may be selected from at least one of gibbsite, surge dam, nordstrandite, diaspore, boehmite, and pseudoboehmite. Most preferably, the precursor of the alumina is pseudoboehmite.

According to the preparation method provided by the invention, preferably, before pulping, the precursor of the alumina is subjected to acidification peptization treatment, wherein the acidification peptization treatment can be carried out according to the conventional technical means in the field, and further preferably, the acid used in the acidification peptization treatment is hydrochloric acid.

The selection range of the acidification peptization conditions is wide, and preferably, the acidification peptization conditions comprise: the acid-aluminum ratio is 0.12-0.22: 1, the time is 20-40 min.

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

The specific implementation mode of the acidification peptization treatment can be as follows: adding pseudo-boehmite into water, pulping, dispersing, adding hydrochloric acid, and acidifying for 30min at an aluminum-acid ratio of 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 nitrate, chloride, chlorate, sulfate, and the like, and the present invention is not particularly limited thereto.

According to the preparation method of the present invention, the selection range of the amounts of the first metal element precursor, the second metal element precursor and the third metal element precursor is wide, and preferably, the amounts of the inorganic oxide carrier precursor, the first metal element precursor, the second metal element precursor and the third metal element precursor are such that, in the prepared composition, the content of the inorganic oxide carrier is 10 to 90 wt%, the content of the first metal element is 0.5 to 50 wt%, the content of the second metal element is 0.5 to 20 wt%, and the content of the third metal element is 0.5 to 20 wt%, based on the total amount of the composition; further preferably, the content of the inorganic oxide carrier is 50 to 90 wt%, and the content of the first metal element is 3 to 30 wt%, the content of the second metal element is 1 to 20 wt%, and the content of the third metal element is 1 to 10 wt% in terms of oxide; still more preferably, the content of the inorganic oxide support is 55 to 85 wt%, the content of the first metal element is 5 to 25 wt%, the content of the second metal element is 5 to 15 wt%, and the content of the third metal element is 2 to 8 wt% in terms of oxide; most preferably, the inorganic oxide support has a content of 66 to 85 wt%, the first metal element has a content of 6 to 16 wt%, the second metal element has a content of 5 to 12 wt%, and the third metal element has a content of 3 to 8 wt%, calculated as an oxide.

According to the preparation method of the composition capable of reducing CO and NOx emission, preferably, the using mass ratio of the precursor of the inorganic oxide carrier calculated by oxides, the first metal element precursor calculated by the VIII group non-noble metal element oxide, the second metal element precursor calculated by the IA and/or IIA group metal element oxide and the third metal element precursor calculated by the IB-VIIB group non-noble metal element oxide is 10-90: 0.5-50: 0.5-20: 0.5-20; further, it may be 50 to 90: 3-30: 1-20: 1-10; still further, it may be 55-85: 5-25: 5-15: 2-8, and can also be 66-85: 6-16: 5-12: 3-8.

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

According to a preferred embodiment of the present invention, the precursors of Fe and Co in the first metal element precursor are used in such amounts that the resulting composition has a weight ratio of Fe to Co, calculated as oxides, of 1: (0.1 to 10), more preferably 1 (0.3 to 3), still more preferably 1: (0.5-2).

According to the invention, the slurry preferably has a solids content of 8 to 30% by weight.

According to the present invention, the method of mixing and beating the precursor of the inorganic oxide support, the first metal element precursor, the second metal element precursor, the third metal element precursor and water is not particularly limited, and the order of adding the precursor of the inorganic oxide support, the first metal element precursor, the second metal element precursor and the third metal element precursor is also not limited, as long as the precursor of the inorganic oxide support, the first metal element precursor, the second metal element precursor and the third metal element precursor are contacted with water, preferably, the first metal element precursor and the third metal element precursor are dissolved in water first, then the precursor of the inorganic oxide support (preferably, the acidified precursor of the inorganic oxide support) is added to obtain the first solution, the second metal element precursor is mixed with water, obtaining a second solution, finally mixing the first solution and the second solution, and then pulping to obtain slurry.

In the present invention, the spray drying may be carried out according to a conventional technique in the art, and the present invention is not particularly limited thereto, and preferably the spray drying conditions are such that the average particle size of the spray-dried particles is 60 to 75 μm and the particle size distribution is mainly in the range of 20 to 100. mu.m, and more preferably the spray drying conditions are such that 50% or more of the particles having a particle size of 40 to 80 μm are contained in the spray-dried particles.

According to the invention, the calcination effectively increases the NH pair of the composition capable of reducing CO and NOx emissions by means of the conventional technical means in the field₃Catalytic conversion activity of reduced nitrides, but to further increase NH of compositions capable of reducing CO and NOx emissions₃The catalytic conversion activity and hydrothermal stability of the nitride in an isoreduced state, and preferably the calcination is carried out in a carbon-containing atmosphere. The inventors of the present invention have surprisingly found during their research that the calcination carried out in a carbonaceous atmosphere makes it possible to reduce the emission of CO and NOx by treating NH with a composition capable of reducing the emission of CO and NOx₃The catalytic conversion activity and the hydrothermal stability of the nitride in the reduced state are both obviously improved, and the roasting in the carbon-containing atmosphere is more favorable for adjusting the relationship between each active metal component and the carrier. The improvement of activity is related to the conversion of the active components from oxides to carbides and to the reduction state, while the improvement of hydrothermal stability may be related to the carbon-containing high-temperature treatment further promoting the bonding, fusion and crosslinking of the active components in the composition. It can be seen from the XRD contrast spectrum that the obvious iron carbide peak pattern and the peak pattern of the simple substance cobalt appear after the treatment. Specifically, as shown in FIG. 1, the XRD pattern of the composition S-5 which had not been subjected to the carbon-containing atmosphere treatment showed a diffraction peak of MgO at around 43.0 ℃ and Al at around 45.0 °₂O₃、Co₂AlO₄And MgAl₂O₄The XRD spectrum of the composition S-1 treated in the carbon-containing atmosphere has not only a diffraction peak of MgO at about 43.0 degrees but also Al at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄And the diffraction peaks at around 43.0 ° and around 45.0 ° are significantly stronger and shifted to the left, due to the fact that the composition S-1 treated with the carbon-containing atmosphere has diffraction peaks at 42.6 ° and 44.9 ° 2 θ, and the diffraction peaks at 42.6 ° and 44.9 ° 2 θ are FeC (Fe)₃C and Fe₇C₃) The diffraction peak of (1). In addition, composition S-1 exhibited a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ in terms of 2. theta. was a diffraction peak of elemental cobalt, as compared with composition S-5.

It should be noted that FIG. 1 shows only XRD patterns in the range of 41 to 50, primarily to illustrate the presence of Fe and Co in the composition. Outside the range of 41 ° to 50 °, other diffraction peaks are present, for example, diffraction peaks for FeO (at 37 °, 65 ° and 59 ° for 2 θ) and CoO (at 37 °, 65 ° and 31 ° for 2 θ), which are not further explained by the present invention.

According to a preferred embodiment of the present invention, the conditions of the calcination include: the reaction is carried out in a carbon-containing atmosphere at a temperature of 400-1000 ℃, preferably 450-650 ℃, more preferably 500-650 ℃, and for a time of 0.1-10h, preferably 1-3 h.

In the present invention, the pressure for the calcination is not particularly limited, and the calcination may be carried out under normal pressure. For example, it can be carried out at from 0.01 to 1MPa (absolute).

In the present invention, the carbon-containing atmosphere is provided by a gas containing a carbon-containing element, and the gas containing a carbon-containing element is preferably selected from gases containing a carbon-containing element having reducibility, further preferably containing at least one of CO, methane, and ethane, and most preferably CO.

According to the present invention, the gas containing carbon element may further contain a part of inert gas, and the inert gas may be various inert gases conventionally used in the art, and is preferably at least one selected from nitrogen, argon and helium, and is further 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 to 20%, and more preferably 4 to 10%. By adopting the preferred embodiment of the invention, the treatment requirements can be better met, and the safety of operators can be ensured.

In the present invention, the calcination may be performed in a calciner, which may be a rotary calciner used in the production of catalytic cracking catalysts and promoters. The gas containing carbon element is in countercurrent contact with the solid material in the roasting furnace.

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

The composition capable of reducing the emission of CO and NOx prepared by the preparation method contains at least one of Fe, Co, IA and/or IIA metal elements and at least one of IB-VIIB non-noble metal elements, and the metal elements are used in combination, so that the composition capable of reducing the emission of CO and NOx can reduce NH₃The catalytic conversion activity of the iso-reduced nitrides is obviously improved, and the composition capable of reducing the emission of CO and NOx has better hydrothermal stability.

The invention also provides the application of the composition capable of reducing the emission of CO and NOx in the treatment of flue gas. The composition provided by the invention can be used for treating any flue gas with the requirement of reducing CO and NOx emission.

The invention also provides application of the composition capable of reducing CO and NOx emission in catalytic cracking regeneration flue gas treatment. The composition capable of reducing the emission of CO and NOx is particularly suitable for reducing the emission of CO and NOx in completely regenerated smoke and incompletely regenerated smoke, and the composition capable of reducing the emission of CO and NOx provided by the invention is more suitable for reducing the emission of CO and NOx in incompletely regenerated smoke. Therefore, the invention provides the application of the composition capable of reducing CO and NOx emission in the treatment of catalytic cracking incomplete regeneration flue gas.

The present invention also provides a fluid catalytic cracking process comprising: the hydrocarbon oil is contacted with a catalyst for reaction, and then the catalyst after the contact reaction is regenerated, wherein the catalyst comprises a catalytic cracking catalyst and a composition capable of reducing CO and NOx emission, and the composition capable of reducing CO and NOx emission is the composition capable of reducing CO and NOx emission.

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

According to the fluidized catalytic cracking method provided by the invention, preferably, hydrocarbon oil is in contact reaction with a catalyst, and then the catalyst after the contact reaction is subjected to incomplete regeneration, and further preferably, the concentration of oxygen in flue gas generated by the incomplete regeneration is not more than 0.5% by volume.

The hydrocarbon oil is not particularly limited in the present invention, and may be various hydrocarbon oils conventionally treated in the field of catalytic cracking, such as vacuum gas oil, atmospheric residue, vacuum residue, deasphalted oil, coker gas oil, or hydrotreated oil.

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

The composition capable of reducing the emission of CO and NOx provided by the invention can be an independent particle or can be a part of the whole catalytic cracking catalyst particle. Preferably, the composition of the present invention capable of reducing CO and NOx emissions is provided as a separate particle for use with the catalytic cracking catalyst particles.

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

In the fluid catalytic cracking process of the present invention, the method of catalyst regeneration has no special requirements compared to the existing regeneration methods, including partial regeneration, incomplete regeneration and complete regeneration modes of operation. The regeneration method can be seen in pages 1234-1343 of catalytic cracking process and engineering published by Chenjun Wu Shu, Chinese petrochemical Press 2005. The preferred regeneration temperature is 650 deg.C-730 deg.C.

The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.

The contents of the components in the compositions capable of reducing CO and NOx emissions in the following examples were measured by X-ray fluorescence spectroscopy (XRF), which is described in detail in the methods of petrochemical analysis (RIPP test), edited by yangchini et al, published by the scientific press in 1990. In the examples, the composition capable of reducing CO and NOx emissions was subjected to structural determination using an XRD spectrum obtained by an X-ray diffractometer (Siemens CO., model D5005), Cu target, ka radiation, solid detector, tube voltage 40kV, and tube current 40 mA.

The raw materials used in the examples and comparative examples: cobalt nitrate [ Co (NO)₃)₂·6H₂O]For analytical purposes, ferric nitrate [ Fe (NO)₃)₃·9H₂O]For analytical purification, potassium permanganate [ KMnO ]₄]For analytical purity, magnesium oxide [ MgO]For analytical purification, it is produced by chemical reagents of the national drug group; pseudo-boehmite is an industrial grade product, the content of alumina is 64 weight percent, and the pore volume is 0.31 ml/g, which is produced by Shandong aluminum company; hydrochloric acid with the concentration of 36.5 weight percent, and the product is analytically pure and produced by Beijing chemical plants; carbon monoxide with a concentration of 10 vol%, nitrogen as a balance gas, produced by Beijing helium Pubei gas industries, Ltd; catalytic cracking catalyst industrial product (Cat-A, catalyst brand CGP-1), Na₂O content 0.24 wt%, RE₂O₃Content 3.2 wt.%, Al₂O₃48.0 wt%, and an average particle diameter of 67 μm, manufactured by China petrochemical catalyst, Inc.

Example 1

Adding 2.62kg of pseudo-boehmite into 14.2kg of deionized water, pulping and dispersing, then adding 238mL of hydrochloric acid, acidifying for 15min to obtain aluminum-aluminum colloid, and adding ferric nitrate (calculated as Fe) calculated by metal oxide₂O₃Calculated as Co) 60g, cobalt nitrate (calculated as Co)₂O₃In the following, the same applies) 60g, KMnO₄Adding 100g (calculated as MnO, the same below) into 3500mL of water, stirring until the solution is fully dissolved, adding the aluminum colloid into the solution, and stirring for 15min to obtain a first solution; adding 100g of MgO into 300g of water, stirring for 10min, adding into the first solution, stirring for 20min to obtain slurry, spray-drying the slurry, taking 100g of particles obtained by spray-drying (average particle size is 65 μm, particles with particle size of 40-80 μm account for 60%, the same applies below) and transferring into a tubular furnace, and introducing CO/N with CO concentration of 10 vol% at a flow rate of 100mL/min₂The mixed gas was treated at 600 ℃ for 1.5 hours to obtain composition S-1.

The results of measuring the contents of the respective components in the composition S-1 are shown in Table 1.

XRD analysis was performed on composition S-1, with the XRD pattern shown in FIG. 1, and it can be seen from FIG. 1 thatThe XRD spectrum of the composition S-5 treated by the carbon-containing atmosphere has a diffraction peak of MgO at about 43.0 degrees and Al at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄The XRD spectrum of the composition S-1 treated in the carbon-containing atmosphere has not only a diffraction peak of MgO at about 43.0 degrees but also Al at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄And the diffraction peaks at around 43.0 ° and around 45.0 ° are significantly stronger and shifted to the left, due to the fact that the composition S-1 treated with the carbon-containing atmosphere has diffraction peaks at 42.6 ° and 44.9 ° 2 θ, and the diffraction peaks at 42.6 ° and 44.9 ° 2 θ are FeC (Fe)₃C and Fe₇C₃) The diffraction peak of (1). In addition, composition S-1 exhibited a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ in terms of 2. theta. was a diffraction peak of elemental cobalt, as compared with composition S-5.

It should be noted that FIG. 1 shows only XRD patterns in the range of 41 to 50, primarily to illustrate the presence of Fe and Co in the composition. Outside the range of 41-50 degrees, other diffraction peaks exist, for example, diffraction peaks of FeO (2 theta is at 37 degrees, 65 degrees and 59 degrees) and CoO (2 theta is at 37 degrees, 65 degrees and 31 degrees), and diffraction peaks outside the range of 41-50 degrees are not related to diffraction peaks of FeC and simple substance Co, and the invention does not carry out further spectrum analysis.

Example 2

(1) Adding 2.53kg of pseudo-boehmite into 13.7kg of deionized water, pulping and dispersing, adding 229mL of hydrochloric acid, acidifying for 15min to obtain an aluminum-aluminum colloid, and adding 100g of ferric nitrate, 60g of cobalt nitrate and KMnO in terms of metal oxide₄Adding 60g (calculated by MnO) into 3500mL of water, stirring until the mixture is fully dissolved, adding the aluminum colloid into the mixture, and stirring for 15min to obtain a first solution; adding 160g of MgO into 480g of water, stirring for 10min, adding into the first solution, stirring for 20min to obtain slurry, carrying out spray drying on the slurry, transferring 100g of particles obtained by spray drying into a tubular furnace, and introducing CO/N with the CO concentration of 10 volume percent at the flow rate of 100mL/min₂The mixed gas was treated at 500 ℃ for 3 hours to obtain composition S-2.

The results of measuring the contents of the respective components in the composition S-2 are shown in Table 1. The XRD analysis of composition S-2 was similar to that of example 1. In the XRD spectrum of the composition S-2 treated in the carbon-containing atmosphere, not only the diffraction peak of MgO is present at about 43.0 degrees, but also Al is present at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄And the diffraction peaks at around 43.0 ° and around 45.0 ° are significantly stronger and shifted to the left, due to the composition S-2 treated with the carbon-containing atmosphere, the diffraction peaks appear at 42.6 ° and 44.9 ° 2 θ, and the diffraction peaks at 42.6 ° and 44.9 ° 2 θ are fecs (Fe)₃C and Fe₇C₃) The diffraction peak of (1). In addition, composition S-2 exhibited a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ in terms of 2. theta. was a diffraction peak of elemental cobalt, as compared with composition S-5.

Example 3

(1) Adding 2.09kg of pseudo-boehmite into 11.3kg of deionized water, pulping and dispersing, then adding 190mL of hydrochloric acid, acidifying for 15min to obtain an aluminum-aluminum colloid, and adding 100g of ferric nitrate, 200g of cobalt nitrate and KMnO calculated by metal oxides₄160g (calculated by MnO) of the aluminum-based composite material is added into 4000mL of water and stirred until the aluminum-based composite material is fully dissolved, and the aluminum-based composite material is added into the water and stirred for 15min to obtain a first solution; adding 200g of MgO into 600g of water, stirring for 10min, adding into the first solution, stirring for 20min to obtain slurry, carrying out spray drying on the slurry, transferring 100g of particles obtained by spray drying into a tubular furnace, and introducing CO/N with the CO concentration of 10 vol% at the flow rate of 100mL/min₂The gas mixture was treated at 650 ℃ for 1 hour to obtain composition S-3.

The results of measuring the contents of the respective components in the composition S-3 are shown in Table 1. The XRD analysis of composition S-3 was similar to that of example 1. The XRD spectrum of the composition S-3 treated in the carbon-containing atmosphere has a diffraction peak of MgO at about 43.0 degrees and Al at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄And diffraction peaks at around 43.0 DEG and at around 45.0 DEG are significantly stronger and shifted to the left, due to the fact that the composition S-3 treated with a carbon-containing atmosphere shows diffraction peaks at 42.6 DEG and 44.9 DEG 2 theta and at 42.6 DEG and 44.9 DEG 2 thetaDiffraction peak FeC (Fe)₃C and Fe₇C₃) The diffraction peak of (1). In addition, composition S-3 exhibited a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ in terms of 2. theta. was a diffraction peak of elemental cobalt, as compared with composition S-5.

Example 4

(1) Adding 2.09kg of pseudo-boehmite into 11.3kg of deionized water, pulping and dispersing, then adding 190mL of hydrochloric acid, acidifying for 15min to obtain an aluminum-aluminum colloid, and adding 200g of ferric nitrate, 120g of cobalt nitrate and KMnO in terms of metal oxide₄Adding 100g (calculated by MnO) into 3500mL of water, stirring until the mixture is fully dissolved, adding the aluminum colloid into the mixture, and stirring for 15min to obtain a first solution; adding 240g of MgO into 720g of water, stirring for 10min, adding into the first solution, stirring for 20min to obtain slurry, carrying out spray drying on the slurry, transferring 100g of particles obtained by spray drying into a tubular furnace, and introducing CO/N with the CO concentration of 10 vol% at the flow rate of 100mL/min₂The mixed gas was treated at 600 ℃ for 1.5 hours to obtain composition S-4.

The results of measuring the contents of the respective components in the composition S-4 are shown in Table 1. The XRD analysis of composition S-4 was similar to that of example 1. The XRD spectrum of the composition S-4 treated in the carbon-containing atmosphere has a diffraction peak of MgO at about 43.0 degrees and Al at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄And the diffraction peaks at around 43.0 ° and around 45.0 ° are significantly stronger and shifted to the left, due to the composition S-4 treated with the carbon-containing atmosphere, the diffraction peaks appear at 42.6 ° and 44.9 ° 2 θ, and the diffraction peaks at 42.6 ° and 44.9 ° 2 θ are fecs (Fe)₃C and Fe₇C₃) The diffraction peak of (1). In addition, composition S-4 exhibited a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ in terms of 2. theta. was a diffraction peak of elemental cobalt, as compared with composition S-5.

Example 5

The procedure is as in example 1, except that the CO concentration is 10% by volume CO/N₂The mixed gas was replaced with air to obtain composition S-5.

The results of measuring the contents of the respective components in the composition S-5 are shown in Table 1. XRD analysis of the composition S-5 showed that there were no distinct diffraction peaks at 42.6, 44.2 and 44.9 degrees 2 theta as seen in XRD pattern (as shown in FIG. 1), demonstrating that both Fe and Co were present as oxides in the composition S-5.

Example 6

Composition S-6 was obtained by following the procedure of example 1, except that MgO was replaced with the same mass of CaO in terms of metal oxides.

The results of measuring the contents of the respective components in the composition S-6 are shown in Table 1. The XRD analysis of composition S-6 was similar to that of example 1. The XRD spectrum of the composition S-6 treated in the carbon-containing atmosphere has a diffraction peak of MgO at about 43.0 degrees and Al at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄And the diffraction peaks at around 43.0 ° and around 45.0 ° are significantly stronger and shifted to the left, due to the composition S-6 treated with the carbon-containing atmosphere, the diffraction peaks appear at 42.6 ° and 44.9 ° 2 θ, and the diffraction peaks at 42.6 ° and 44.9 ° 2 θ are fecs (Fe)₃C and Fe₇C₃) The diffraction peak of (1). In addition, composition S-6 exhibited a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ in terms of 2. theta. was a diffraction peak of elemental cobalt, as compared with composition S-5.

Example 7

The procedure is as in example 1, except that, calculated as metal oxide, the same mass of CeCl is used₂Replacement of KMnO₄To obtain composition S-7.

The results of measuring the contents of the respective components in the composition S-7 are shown in Table 1. The XRD analysis of composition S-7 was similar to that of example 1. The XRD spectrum of the composition S-7 treated in the carbon-containing atmosphere has a diffraction peak of MgO at about 43.0 degrees and Al at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄And the diffraction peaks at around 43.0 ° and around 45.0 ° are significantly stronger and shifted to the left, due to the composition S-7 treated with the carbon-containing atmosphere, the diffraction peaks appear at 42.6 ° and 44.9 ° 2 θ, and the diffraction peaks at 42.6 ° and 44.9 ° 2 θ are fecs (Fe)₃C and Fe₇C₃) The diffraction peak of (1). In addition, and groupCompared with the compound S-5, the compound S-7 has a diffraction peak at 44.2 degrees, and the diffraction peak at 44.2 degrees of 2 theta is the diffraction peak of simple substance cobalt.

Example 8

Composition S-8 was obtained in the same manner as in example 1 except that 30g of iron nitrate and 90g of cobalt nitrate, in terms of metal oxide, were used.

The results of measuring the contents of the respective components in the composition S-8 are shown in Table 1. The XRD analysis of composition S-8 was similar to that of example 1. In the XRD spectrum of the composition S-8 treated in the carbon-containing atmosphere, not only the diffraction peak of MgO is present at about 43.0 degrees, but also Al is present at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄And the diffraction peaks at around 43.0 ° and around 45.0 ° are significantly stronger and shifted to the left, due to the composition S-8 treated with the carbon-containing atmosphere, the diffraction peaks appear at 42.6 ° and 44.9 ° 2 θ, and the diffraction peaks at 42.6 ° and 44.9 ° 2 θ are fecs (Fe)₃C and Fe₇C₃) The diffraction peak of (1). In addition, composition S-8 exhibited a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ in terms of 2. theta. was a diffraction peak of elemental cobalt, as compared with composition S-5.

Example 9

Composition S-9 was obtained in the same manner as in example 1 except that the amount of iron nitrate was 90g and the amount of cobalt nitrate was 30g, in terms of metal oxide.

The results of measuring the contents of the respective components in the composition S-9 are shown in Table 1. The XRD analysis of composition S-9 was similar to that of example 1. The XRD spectrum of the composition S-9 treated in the carbon-containing atmosphere has a diffraction peak of MgO at about 43.0 degrees and Al at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄And the diffraction peaks at around 43.0 ° and around 45.0 ° are significantly stronger and shifted to the left, due to the fact that the composition S-9 treated with the carbon-containing atmosphere has diffraction peaks at 42.6 ° and 44.9 ° 2 θ, and the diffraction peaks at 42.6 ° and 44.9 ° 2 θ are FeC (Fe)₃C and Fe₇C₃) The diffraction peak of (1). In addition, composition S-9 was at 44.2 ℃ compared to composition S-5A diffraction peak appears, and a diffraction peak at 44.2 degrees 2 theta is a diffraction peak of simple substance cobalt.

Example 10

The procedure of example 1 was followed except that the CO/N concentration of 10 vol% was replaced with an ethane/nitrogen mixed gas having an ethane concentration of 10 vol%₂The gases were mixed to give composition S-10.

The results of measuring the contents of the respective components in the composition S-10 are shown in Table 1. The XRD analysis of composition S-10 was similar to that of example 1. In the XRD spectrum of the composition S-10 treated in the carbon-containing atmosphere, not only the diffraction peak of MgO is present at about 43.0 degrees, but also Al is present at about 45.0 degrees₂O₃、Co₂AlO₄And MgAl₂O₄And the diffraction peaks at around 43.0 ° and around 45.0 ° are significantly stronger and shifted to the left, due to the composition S-10 treated with the carbon-containing atmosphere, the diffraction peaks appear at 42.6 ° and 44.9 ° 2 θ, and the diffraction peaks at 42.6 ° and 44.9 ° 2 θ are fecs (Fe)₃C and Fe₇C₃) The diffraction peak of (1). In addition, composition S-10 exhibited a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ in terms of 2. theta. was a diffraction peak of elemental cobalt, as compared with composition S-5.

Comparative example 1

Composition D-1 was obtained by following the procedure of example 1 except that the cobalt nitrate was replaced with the same mass of iron nitrate based on the metal oxide.

The results of measuring the contents of the respective components in the composition D-1 are shown in Table 1.

Comparative example 2

Composition D-2 was obtained by following the procedure of example 1 except that the iron nitrate was replaced with the same mass of cobalt nitrate based on the metal oxide.

The results of measuring the contents of the respective components in the composition D-2 are shown in Table 1.

Comparative example 3

Reference is made to the method described in US6800586 for the preparation of a comparative composition. Taking 34.4 g of dried gamma-alumina microsphere carrier, impregnating alumina microspheres with a solution prepared from 10.09g of cerium nitrate, 2.13g of lanthanum nitrate and 18mL of water, drying at 120 ℃ after impregnation, roasting at 600 ℃ for 1 hour,then dipped in a solution prepared by 2.7g of copper nitrate and 18mL of water, dried at 120 ℃ and roasted at 600 ℃ for 1 hour to obtain a composition D-3. In the composition D-3, RE is calculated as oxide based on the total amount of the composition D-3₂O₃Is 12 wt% and CuO is 2.3 wt% (RE represents a lanthanide metal element).

TABLE 1

Note: the content of each component is calculated by oxide, and the unit is weight percent.

Test example 1

The test example is used for reducing the effect of CO and NOx emission in incomplete regeneration flue gas under aerobic condition on the compositions capable of reducing CO and NOx emission provided by the above examples and comparative examples.

The composition capable of reducing CO and NOx emissions was uniformly blended with the above catalytic cracking catalyst (Cat-A) (the composition capable of reducing CO and NOx emissions accounted for 2.2% by weight of the total amount of the composition capable of reducing CO and NOx emissions and the catalytic cracking catalyst), and subjected to catalytic cracking reaction-regeneration evaluation after aging at 800 ℃ for 12 hours in an atmosphere of 100% steam.

The catalytic cracking reaction-regeneration evaluation is carried out on a small fixed bed simulated flue gas NOx reduction device, the loading amount of an aged catalyst is 10g, the reaction temperature is 650 ℃, and the volume flow of raw material gas is 1500 mL/min. The feed gas contained 3.7 vol.% CO, 0.5 vol.% oxygen, 800ppm NH₃The balance being N₂. Analyzing the gas product by an on-line infrared analyzer to obtain reacted NH₃NOx and CO concentrations, and the results are shown in table 2.

TABLE 2

As can be seen from the data in Table 2, the composition capable of reducing CO and NOx emission provided by the invention is used for the incomplete regeneration process (aerobic condition) of the catalytic cracking process, and has better CO and NH reduction than the composition capable of reducing CO and NOx emission provided by the comparative example₃And NOx emission performance, and the composition which can reduce CO and NOx emission after aging is used in the evaluation process, and the composition which can reduce CO and NOx emission after aging removes CO and NH₃And the NOx activity is still higher, therefore, the composition capable of reducing the emission of CO and NOx provided by the invention has better hydrothermal stability.

Test example 2

The test example is used for reducing the effect of CO and NOx emission in the incompletely regenerated flue gas under the anaerobic condition on the compositions capable of reducing CO and NOx emission provided by the above examples and comparative examples.

The process of test example 1 was followed except that the feed gas contained 3.7 vol.% CO and 800ppm NH₃The balance being N₂. To obtain reacted NH₃NOx and CO concentrations, and the results are shown in table 3.

TABLE 3

As can be seen from Table 3, even though the incompletely regenerated flue gas is treated under oxygen-free conditions, the composition capable of reducing CO and NOx emissions provided by the invention has better CO and NH reduction than the composition capable of reducing CO and NOx emissions provided by the comparative example₃Emission performance, and the compositions used in the evaluation process are compositions capable of reducing CO and NOx emissions after aging, and compositions capable of reducing CO and NOx emissions after aging remove CO and NH₃The activity is still higher becauseTherefore, the composition capable of reducing the emission of CO and NOx provided by the invention has better hydrothermal stability.

As can be seen from the data in tables 2 and 3, the composition capable of reducing the emission of CO and NOx provided by the invention is suitable for incomplete regeneration under aerobic and anaerobic conditions, and has better regeneration flue gas treatment capacity. In particular, as can be seen from the comparison of example 1 with example 5, the performance of the composition capable of reducing the emission of CO and NOx is further improved by carrying out the calcination in a carbonaceous atmosphere, which is preferred according to the invention; as can be seen from comparison of example 1 with examples 6 and 7, the performance of the composition capable of reducing the emission of CO and NOx is further improved by using the preferred metal elements of the present invention; as can be seen from the comparison of example 1 with examples 8 and 9, the preferred Fe to Co mass ratio according to the invention allows a further improvement in the performance of the composition capable of reducing CO and NOx emissions; as can be seen from the comparison of example 1 with example 10, the treatment with the preferred carbonaceous atmosphere of the invention results in a further improvement in the performance of the composition which reduces CO and NOx emissions; as can be seen from the comparison of example 1 with comparative examples 1 to 3, the present invention enables the composition performance capable of reducing CO and NOx emissions to be greatly improved by using Fe and Co in combination.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

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

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A composition capable of reducing CO and NOx emissions, the composition comprising: the metal oxide carrier comprises an inorganic oxide carrier and a first metal element, a second metal element and a third metal element which are loaded on the inorganic oxide carrier, wherein the first metal element is selected from non-noble metal elements in a VIII group, the first metal element comprises Fe and Co, and 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 group IB-VIIB non-noble metal elements.

2. The composition of claim 1, wherein the inorganic oxide support is present in an amount of 10 to 90 wt%, based on the total amount of the composition, and the first metal element is present in an amount of 0.5 to 50 wt%, the second metal element is present in an amount of 0.5 to 20 wt%, and the third metal element is present in an amount of 0.5 to 20 wt%, calculated as an oxide;

preferably, the content of the inorganic oxide carrier is 50 to 90 wt%, and the content of the first metal element is 3 to 30 wt%, the content of the second metal element is 1 to 20 wt%, and the content of the third metal element is 1 to 10 wt% in terms of oxide;

further preferably, the content of the inorganic oxide support is 55 to 85 wt%, and the content of the first metal element is 5 to 25 wt%, the content of the second metal element is 5 to 15 wt%, and the content of the third metal element is 2 to 8 wt% in terms of oxide.

3. The composition of claim 1 or 2, wherein the weight ratio of Fe to Co, calculated as oxides, is 1: (0.1 to 10), preferably 1 (0.3 to 3), more preferably 1: (0.5-2).

4. The composition according to any one of claims 1 to 3,

the Fe in the composition is at least partially present in the form of iron carbide;

the Co in the composition is at least partially present in the form of elemental cobalt;

preferably, the composition has an XRD pattern with diffraction peaks at 42.6 °, 44.2 ° and 44.9 ° 2 θ.

5. The composition of any one of claims 1-4, wherein the inorganic oxide support is selected from at least one of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite, and perovskite;

preferably, the inorganic oxide support is selected from at least one of alumina, spinel and perovskite, and further preferably alumina.

6. The composition according to any one of claims 1 to 5,

the second metal element is at least one selected from Na, K, Mg and Ca, preferably K and/or Mg, and most preferably Mg;

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

7. A method for preparing a composition capable of reducing CO and NOx emissions, the method comprising: mixing and pulping a precursor of an inorganic oxide carrier, a first metal element precursor, a second metal element precursor, a third metal element precursor and water to obtain slurry, carrying out spray drying on the slurry, and then roasting;

8. The method of claim 7, wherein the firing conditions include: the reaction is carried out in a carbon-containing atmosphere at the temperature of 400-1000 ℃, preferably 450-650 ℃ and the time of 0.1-10h, preferably 1-3 h;

preferably, the carbon-containing atmosphere is provided by a gas containing carbon-containing elements selected from at least one of CO, methane and ethane, preferably CO;

preferably, the volume concentration of CO in the carbon-containing atmosphere is between 1 and 20%, preferably between 4 and 10%.

9. The production method according to claim 7 or 8, wherein the precursor of the inorganic oxide support, the precursor of the first metal element, the precursor of the second metal element and the precursor of the third metal element are used in amounts such that the obtained composition contains the inorganic oxide support in an amount of 10 to 90% by weight, the first metal element in an amount of 0.5 to 50% by weight, the second metal element in an amount of 0.5 to 20% by weight and the third metal element in an amount of 0.5 to 20% by weight, in terms of oxide, based on the total amount of the composition;

10. The production method according to any one of claims 7 to 9, wherein the Fe precursor and the Co precursor are used in amounts such that the weight ratio of Fe to Co, calculated as oxides, in the resultant composition is 1: (0.1 to 10), preferably 1 (0.3 to 3), more preferably 1: (0.5-2).

11. The production method according to any one of claims 7 to 10, wherein the inorganic oxide support is selected from at least one of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite, and perovskite; preferably, the inorganic oxide support is selected from at least one of alumina, spinel and perovskite, further preferably alumina;

preferably, before pulping, the precursor of the alumina is subjected to acidification peptization treatment, further preferably, the acid used in the acidification peptization treatment is hydrochloric acid, and the conditions of the acidification peptization treatment comprise: acid-aluminum ratio of 0.12-0.22: 1, the time is 20-40 min.

12. The production method according to any one of claims 7 to 11, wherein the second metal element is at least one selected from the group consisting of Na, K, Mg and Ca, preferably K and/or Mg, most preferably Mg;

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

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.

13. A composition capable of reducing CO and NOx emissions produced by the method of any one of claims 7 to 12.

14. Use of a composition according to any one of claims 1 to 6 and 13 for reducing CO and NOx emissions in the treatment of flue gases.

15. Use of a composition according to any one of claims 1 to 6 and 13 capable of reducing CO and NOx emissions in catalytic cracking regeneration flue gas treatment.