CN109201079B - Can reduce CO and NOxDischarged composition, preparation method and application thereof and fluidized catalytic cracking method - Google Patents

Can reduce CO and NOxDischarged composition, preparation method and application thereof and fluidized catalytic cracking method Download PDF

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CN109201079B
CN109201079B CN201710542183.3A CN201710542183A CN109201079B CN 109201079 B CN109201079 B CN 109201079B CN 201710542183 A CN201710542183 A CN 201710542183A CN 109201079 B CN109201079 B CN 109201079B
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metal element
composition
precursor
content
reducing
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CN109201079A (en
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姜秋桥
宋海涛
田辉平
王鹏
陈妍
孙言
刘博�
朱玉霞
达志坚
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN201710542183.3A priority Critical patent/CN109201079B/en
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to US16/626,742 priority patent/US11529612B2/en
Priority to JP2020500124A priority patent/JP7114688B2/en
Priority to TW107123246A priority patent/TWI786147B/en
Priority to PCT/CN2018/094584 priority patent/WO2019007381A1/en
Priority to EP18827377.5A priority patent/EP3693085A4/en
Priority to AU2018298192A priority patent/AU2018298192B2/en
Priority to RU2020104054A priority patent/RU2772281C2/en
Publication of CN109201079A publication Critical patent/CN109201079A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
    • B01D53/8646—Simultaneous elimination of the components
    • B01D53/865—Simultaneous elimination of the components characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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, a third metal element and a fourth 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 and have higher activity of reducing CO and NOx emission of regenerated flue gas through further modification of at least one of group IA and/or IIA metal elements, at least one of group IB-VIIB non-noble metal elements and at least one of noble metal elements.

Description

Composition capable of reducing CO and NOx emission, preparation method and application thereof, and fluidized catalytic cracking method
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 gasxThe 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 be a noble metal dispersed on an inorganic oxide support.
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
Aim at the presentIn the process of technical regeneration, NH3The 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, and can effectively reduce the emission of CO and NOx in catalytic cracking regeneration flue gas when being used in the fluidized catalytic cracking process.
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, at least one of IB-VIIB group non-noble metal elements and at least one of noble metal elements as active components. The reason for this may presumably be due to: fe and Co are used as main metal elements together, and the further modification of at least one of the IA group metal elements and/or the IIA group metal elements, at least one of the IB group non-noble metal elements and at least one of the noble metal elements is beneficial to reducing the generation of nitrogen-containing compounds in an oxidation state and promoting the decomposition of the nitrogen-containing compounds in a reduction state.
Through further research, the solid matter obtained after spray drying is treated at high temperature in a carbon-containing atmosphere after spray drying and before precious metal element impregnation under the preferable condition, so that the emission of CO and NOx in catalytic cracking regeneration flue gas can be reduced more effectively; in a further preferable case, the solid product obtained after precious metal impregnation is subjected to alkali treatment, so that the emission of CO and NOx in the catalytic cracking regeneration flue gas can be reduced more effectively. 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 nitride in the reduced state is obviously improved, and the method has better performanceHydrothermal stability, meeting the requirements of the regenerator hydrothermal environment for compositions capable of reducing CO and NOx emissions.
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, a third metal element and a fourth 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, the third metal element is selected from at least one of group IB-VIIB non-noble metal elements, and the fourth 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 process for the preparation of a composition capable of reducing CO and NOx emissions, the process comprising:
(1) 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 carrying out first roasting to obtain a semi-finished product composition;
(2) taking a solution containing a precursor of a fourth metal element as an impregnation solution, impregnating the semi-finished product composition obtained in the step (1) to obtain a solid product, and then drying and/or carrying out second roasting on the solid product;
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; the fourth metal element is at least one selected from noble metal elements;
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, in the preparation method of the composition capable of reducing CO and NOx emission, the utilization rate of precious metals is high, and the production cost is low; in addition, the composition capable of reducing the emission of CO and NOx provided by the invention is used as an auxiliary agent for reducing the emission of CO and NOx in fluid catalytic cracking, so that the yield of coke and dry gas in FCC products is low. 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 an 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 a 100% steam atmosphere to perform catalytic cracking reaction-regeneration evaluation, and compared with the composition D-3 capable of reducing CO and NOx emissions prepared by the prior art using an active component saturated impregnation method, when the composition capable of reducing CO and NOx emissions provided in example 3 of the present invention is used, the NOx emission concentration in the completely regenerated flue gas is reduced from 264ppm to 34 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, a third metal element and a fourth 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, the third metal element is selected from at least one of group IB-VIIB non-noble metal elements, and the fourth metal element is selected from at least one of noble metal elements.
The content of the first metal element, the second metal element, the third metal element and the fourth metal element in the composition is selected in a wide range, and preferably, the content of the inorganic oxide carrier is 10 to 90 wt% based on the total amount of the composition, the content of the first metal element is 0.5 to 50 wt% in terms of oxide, the content of the second metal element is 0.5 to 20 wt%, the content of the third metal element is 0.5 to 20 wt%, and the content of the fourth metal element is 0.001 to 0.15 wt% in terms of element; further preferably, the content of the inorganic oxide support is 50 to 90% by weight, the content of the first metal element is 3 to 30% by weight, the content of the second metal element is 1 to 20% by weight, the content of the third metal element is 1 to 10% by weight, and the content of the fourth metal element is 0.005 to 0.1% by weight, in terms of elements, based on the oxide; still more preferably, the inorganic oxide support has a content of 55 to 85 wt% in terms of oxide, the first metal element has a content of 5 to 25 wt%, the second metal element has a content of 5 to 15 wt%, the third metal element has a content of 2 to 8 wt%, and the fourth metal element has a content of 0.01 to 0.08 wt% in terms of element; 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%, the third metal element has a content of 3 to 8 wt%, and the fourth metal element has a content of 0.05 to 0.07 wt%, calculated as elements, in terms of 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.
In the present invention, the first metal element may contain Fe and Co as long as it can increase NH content of the composition3In order to further exhibit the synergistic effect of Fe and Co, the catalytic conversion activity of the reduced nitrides is preferably such that 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).
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 before being impregnated with the noble metal, 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; the noble metal element includes 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, 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 the composition provided by the present invention, preferably, the fourth metal element is at least one selected from Pt, Ir, Pd, Ru and Rh, and most preferably Ru.
According to a most preferred embodiment of the present invention, the combination of Fe, Co, Mg, Mn and Ru as active components substantially increases the NH contribution of the composition to reduce CO and NOx emissions3The 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, Mn and Ru 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%, the content of Mn is 3-8 wt%, and the content of Ru is 0.05-0.07 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:
(1) 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 carrying out first roasting to obtain a semi-finished product composition;
(2) taking a solution containing a precursor of a fourth metal element as an impregnation solution, impregnating the semi-finished product composition obtained in the step (1) to obtain a solid product, and then drying and/or carrying out second roasting on the solid product;
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; the fourth metal element is at least one selected from noble metal elements;
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).
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, the third metal element and the fourth metal element are selected as described above, and are not described again.
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, the third metal element precursor, and the fourth metal element precursor are respectively selected from water-soluble salts of the first metal element, the second metal element, the third metal element, and the fourth 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, the third metal element precursor and the fourth metal element precursor is wide, and preferably, the precursor of the inorganic oxide carrier, the precursor of the first metal element, the precursor of the second metal element, the precursor of the third metal element and the precursor of the fourth metal element are used in such amounts that, in the prepared composition, the content of the inorganic oxide carrier is 10-90 wt% based on the total weight of the composition, calculated by oxide, the content of the first metal element is 0.5-50 wt%, the content of the second metal element is 0.5-20 wt%, and the content of the third metal element is 0.5-20 wt%, the content of the fourth metal element is 0.001-0.15 wt% calculated by element; further preferably, the content of the inorganic oxide support is 50 to 90% by weight, the content of the first metal element is 3 to 30% by weight, the content of the second metal element is 1 to 20% by weight, the content of the third metal element is 1 to 10% by weight, and the content of the fourth metal element is 0.005 to 0.1% by weight, in terms of elements, based on the oxide; still more preferably, the inorganic oxide support has a content of 55 to 85 wt% in terms of oxide, the first metal element has a content of 5 to 25 wt%, the second metal element has a content of 5 to 15 wt%, the third metal element has a content of 2 to 8 wt%, and the fourth metal element has a content of 0.01 to 0.08 wt% in terms of element; 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%, the third metal element has a content of 3 to 8 wt%, and the fourth metal element has a content of 0.05 to 0.07 wt%, calculated as elements, in terms of 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, the third metal element precursor calculated by the IB-VIIB group non-noble metal element oxide and the fourth metal element precursor calculated by the noble metal element is 10-90: 0.5-50: 0.5-20: 0.5-20: 0.001-0.15; further, it may be 50 to 90: 3-30: 1-20: 1-10: 0.005-0.1; still further, it may be 55-85: 5-25: 5-15: 2-8: 0.01-0.08, and can also be 66-85: 6-16: 5-12: 3-8: 0.05-0.07.
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 weight ratio of Fe to Co, calculated as oxides, in the resulting composition is preferably 1: (0.1 to 10), more preferably 1 (0.3 to 3), still more preferably 1: (0.5-2).
According to the present invention, it is preferred that the slurry in step (1) has a solid 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 first calcination in step (1) is effective in increasing the NH content of the composition capable of reducing CO and NOx emissions, using means conventional in the art3Catalytic 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, preferably the first calcination is carried out in a carbon-containing atmosphere. The inventors of the present invention have surprisingly found during their research that the first calcination carried out in a carbonaceous atmosphere makes it possible to make NH compatible with a composition capable of reducing the emissions of CO and NOx3The catalytic conversion activity and the hydrothermal stability of the nitride in the reduced state are both obviously improved, and the semi-finished product composition obtained by the first roasting in the carbon-containing atmosphere is more beneficial to the subsequent loading of the noble metal elements. 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 fact that the high temperature treatment further promotes 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 first firing 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 first 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 first roasting may be performed in a roasting furnace, and the roasting furnace may be a rotary roasting furnace used in the production of the catalytic cracking catalyst and the auxiliary. The gas containing carbon element is in countercurrent contact with the solid material in the roasting furnace.
According to the production method of the present invention, the impregnation in the step (2) is not particularly limited, and may be carried out according to a conventional technique in the art, and may be a saturated impregnation or an excess impregnation, preferably an excess impregnation.
According to one embodiment of the present invention, the semi-finished composition may be added to water, and then the solution of the precursor of the fourth metal element may be added thereto and stirred.
The solid product can be obtained by filtering the mixture obtained after impregnation. The filtration can be carried out according to the conventional technical means in the field.
According to the production method of the present invention, it is preferable that the method further comprises: after the impregnation in step (2), the solid product is subjected to an alkali treatment before drying and/or second roasting. By adopting the preferred embodiment of the invention, the base treatment is carried out after the precious metal element is impregnated, so that the precious metal element (fourth metal element) and the first metal element, the second metal element and the third metal element can be more closely combined, the synergistic effect of the first metal element, the second metal element and the third metal element can be more favorably exerted, and the improvement of the NH emission of the composition capable of reducing CO and NOx emission on NH can be more favorably realized3Catalytic conversion activity and hydrothermal stability of the nitride in an isoreduced state.
According to an embodiment of the present invention, the alkali treatment method may include: and mixing the solid product with an alkaline solution for pulping, or leaching the solid product by using the alkaline solution.
The selection range of the alkaline solution is wide, the alkaline solution is preferably a non-metal element alkaline solution, and more preferably an ammonia solution and/or an alkaline ammonium salt solution. The alkaline ammonium salt solution may be at least one of an ammonium carbonate solution, an ammonium bicarbonate solution, and a diammonium phosphate solution. Most preferably according to the invention the alkaline solution is ammonia.
The concentration and the dosage of the alkaline solution are selected in a wide range, for example, the concentration of the alkaline solution can be 0.01-10mol/L, preferably 0.05-5mol/L, and more preferably 0.5-2 mol/L; the volume of the alkaline solution may be used in an amount of 1 to 10 times, preferably 1.5 to 5 times, the pore volume of the solid product.
The concentration and amount of the alkaline solution can be selected by those skilled in the art according to the pore volume of the solid product to be obtained, for example, according to an embodiment of the present invention, when the pore volume of the solid product to be obtained is about 0.4 to 0.5mL/g and the amount of the solid product to be treated is 100g, 60 to 250mL of 0.5 to 2mol/L aqueous ammonia solution can be selected.
In the step (2) of the present invention, only the solid product may be dried, only the solid product may be subjected to the second calcination, and the solid product may be dried and then subjected to the second calcination. In the present invention, the conditions for the drying and the second firing are not particularly limited, and may be performed according to a method conventionally used in the art. For example, the conditions of drying may include: the temperature is 60-150 ℃ and the time is 2-10 h.
The conditions of the second firing are not particularly limited in the present invention, the second firing may be performed in air or an inert atmosphere (e.g., nitrogen), and the conditions of the second firing may include: the temperature is 300-550 ℃, and the time is 1-10 h.
The invention also provides a composition prepared by the preparation method and capable of reducing CO and NOx emission.
The composition capable of reducing CO and NOx emission prepared by the preparation method contains Fe and Co, at least one of IA and/or IIA group metal elements, at least one of IB-VIIB group non-noble metal elements and at least one of noble metal elements, and the metal elements are used in combination, so that the composition capable of reducing CO and NOx emission is used for treating 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 complete regeneration flue gas and 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.
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; ruthenium chloride (RuCl)3) For analytical purity, the content of Ru is more than or equal to 37 percent, which has been a public limitation of new hundred million gold materialsProduction; 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; ammonia water with concentration of 25-28%, analytically pure, produced in Beijing chemical plant, and diluted for use; 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
(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, carrying out spray drying on the slurry, taking 150g of particles obtained by spray drying (the average particle size is 65 mu m, the particles with the particle size of 40-80 mu m account for 60%, the same below), transferring into a tubular furnace, and introducing CO/N with the CO concentration of 10 volume% at the flow rate of 100mL/min2Treating the mixed gas at 600 ℃ for 1.5h to obtain a semi-finished product composition;
(2) 100g of the semi-finished product composition is weighed and added into 700mL of water, and RuCl with the mass content of 12.5g/L calculated by metal elements is added34.8mL of the solution was stirred for 20min, filtered to obtain a solid product, and the solid product was rinsed with 80mL of 2mol/L aqueous ammonia solution, dried (100 ℃ C., 4h), and calcined (400 ℃ C., 2h) to obtain the 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 the composition S-1, and the XRD spectrum is shown in FIG. 1, and it can be seen from FIG. 1 that the composition S-5 which had not been subjected to the carbon-containing atmosphere treatment had 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 150g 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/min2Mixing the gases inTreating at 500 deg.C for 3h to obtain semi-finished product composition;
(2) 100g of the semi-finished product composition is weighed and added into 700mL of water, and RuCl with the mass content of 12.5g/L calculated by metal elements is added34.4mL of the solution was stirred for 20min, filtered to obtain a solid product, and the solid product was rinsed with 100mL of 2mol/L aqueous ammonia solution, dried (100 ℃ C., 4h), and calcined (400 ℃ C., 2h) 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 150g 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/min2Treating the mixed gas at 650 ℃ for 1h to obtain a semi-finished product composition;
(2) 100g of the semi-finished product composition is weighed and added into 700mL of water, and then the metal element is addedRuCl with a mass content of 12.5g/L34mL of the solution is stirred for 20min, and then filtered to obtain a solid product, 80mL of ammonia water solution with the concentration of 2mol/L is used for leaching the solid product, and the solid product is dried (100 ℃, 4 hours) and roasted (400 ℃, 2 hours) to obtain the 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 the diffraction peaks at around 43.0 ° and around 45.0 ° are significantly stronger and shifted to the left, due to the composition S-3 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-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 150g 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/min2Treating the mixed gas at 600 ℃ for 1.5h to obtain a semi-finished product composition;
(2) 100g of the semi-finished product composition is weighed and added into 700mL of water, and RuCl with the mass content of 12.5g/L calculated by metal elements is added35.2mL of the solution, stirring for 20min, filtering to obtain a solid product, eluting the solid product with 80mL of 2mol/L ammonia water solution, and drying (1)00 ℃ for 4h) and roasting (400 ℃ for 2h) to obtain the 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
The procedure of example 1 was followed, except that 80mL of the aqueous ammonia solution having a concentration of 2mol/L was not used in the step (2), and the solid product was directly dried and calcined to obtain a composition S-6.
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 about 43.0 DEG and at about 45.0 DEG are remarkably strong and directed towardLeft shift due to composition S-6 treated with a carbon-containing atmosphere, diffraction peaks at 42.6 ° and 44.9 ° 2 θ, FeC (Fe) at 42.6 ° and 44.9 ° 2 θ3C 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
Composition S-7 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-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, composition S-7 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 8
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-8.
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 diffraction peaks at around 43.0 DEG and at around 45.0 DEG become significantly stronger and shifted to the left, due to the composition S treated with a carbon-containing atmosphere-8, diffraction peaks at 42.6 ° and 44.9 ° 2 θ, and FeC (Fe) at 42.6 ° and 44.9 ° 2 θ3C 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 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-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 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 10
Composition S-10 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-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 diffraction peaks at around 43.0 DEG and at around 45.0 DEG are significantly stronger and shifted to the left, due to the composition S-10 treated with a carbon-containing atmosphere, appearing at 42.6 DEG and 44.9 DEG 2 thetaDiffraction peaks at 42.6 ° and 44.9 ° 2 θ are FeC (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.
Example 11
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 obtain composition S-11.
The results of measuring the contents of the respective components in the composition S-11 are shown in Table 1. The XRD analysis of composition S-11 was similar to that of example 1. The XRD spectrum of the composition S-11 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-11 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-11 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 gThe dried gamma-alumina microsphere carrier is prepared by 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 ℃ and roasting at 600 ℃ for 1 hour after impregnation, then impregnating with a solution prepared from 2.7g of copper nitrate and 18mL of water, and drying at 120 ℃ and roasting at 600 ℃ for 1 hour to obtain the 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
Figure BDA0001342092440000211
Note: the contents of the first metal element, the second metal element and the third metal element are calculated by oxide and the unit is weight percent, and the content of the fourth metal element is calculated by element and the unit is weight percent.
Test example 1
The experimental examples are intended to reduce the effects of CO and NOx emissions in the complete regeneration flue gas and the effect on FCC product distribution for the compositions provided in the above examples and comparative examples.
The composition capable of reducing the emission of CO and NOx is uniformly mixed with a catalytic cracking catalyst (Cat-A) (the composition capable of reducing the emission of CO and NOx accounts for 0.8 wt% of the total amount of the composition capable of reducing the emission of CO and NOx and the catalytic cracking catalyst), and after aging for 12 hours at 800 ℃ in a 100% steam atmosphere, catalytic cracking reaction-regeneration evaluation is carried out.
The catalytic cracking reaction-regeneration evaluation was carried out on a small fixed fluidized bed apparatus, the loading of the aged catalyst was 9g, the reaction temperature was 500 ℃, the catalyst-to-oil weight ratio was 6, and the properties of the feedstock oil are shown in table 2. The gas product is analyzed by on-line chromatography to obtain cracked gas composition; the liquid product is subjected to off-line chromatographic analysis to obtain the yields of gasoline, diesel oil and heavy oil. After the reaction, the reaction is carried out by N2Steam stripping for 10min, carrying out in-situ coke burning regeneration, wherein the flow rate of the regeneration air is 200mL/min, the regeneration time is 15min, and the initial regeneration temperature is the same as the reaction temperature. Collecting flue gas in the regeneration process according to CO after regeneration2The yield of coke was integrated by an infrared analyzer and the FCC product distribution was obtained after all product yields were normalized, see table 3, where in table 3 the conversion rate refers to the sum of the yields of dry gas, liquefied gas, gasoline and coke. The concentrations of NOx and CO in the flue gas were measured using a Testo350Pro flue gas analyzer and the results are shown in table 4.
TABLE 2
Figure BDA0001342092440000221
Figure BDA0001342092440000231
TABLE 3
Product distribution Example 1 Example 2 Example 3 Example 4 Comparative example 3
Dry gas, wt% 1.72 1.70 1.72 1.71 1.73
Liquefied gas, wt% 19.27 19.39 19.57 19.50 19.20
Coke, wt.% 7.16 7.15 7.22 7.22 7.29
Gasoline, wt.% 49.66 49.62 49.48 49.26 49.44
Diesel oil, wt% 15.16 15.10 14.87 15.26 15.27
Heavy oil,% by weight 7.03 7.04 7.13 7.06 7.06
Conversion rate% 77.81 77.86 77.99 77.69 77.66
As can be seen from Table 3, the compositions of the present invention that reduce CO and NOx emissions when used in conjunction with a catalytic cracking catalyst result in lower yields of coke and dry gas in the FCC product.
TABLE 4
Figure BDA0001342092440000232
Figure BDA0001342092440000241
As can be seen from the data in Table 4, when the composition capable of reducing CO and NOx emissions provided by the invention is used in a catalytic cracking process, the composition capable of reducing CO and NOx emissions has better CO and NOx emissions reduction performance than the composition capable of reducing CO and NOx emissions provided by a comparative example, and the composition capable of reducing CO and NOx emissions after aging is used in the evaluation process, the composition capable of reducing CO and NOx emissions after aging still can effectively reduce CO and NOx emissions, so that the composition capable of reducing CO and NOx emissions provided by the invention has better hydrothermal stability.
Test example 2
The test example is used for reducing the emission of CO and NOx in incomplete regeneration flue gas for the composition capable of reducing the emission of CO and NOx 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 5.
TABLE 5
Numbering NOx concentration, ppm NH3Concentration, ppm CO concentration, vol%
Example 1 S-1 58 59 2.89
Comparative example 1 D-1 115 151 2.87
Comparative example 2 D-2 107 147 2.92
Comparative example 3 D-3 109 321 3.15
Example 2 S-2 52 58 2.81
Example 3 S-3 35 1 2.7
Example 4 S-4 27 3 2.7
Example 5 S-5 62 63 2.87
Example 6 S-6 75 62 2.91
Example 7 S-7 69 76 2.88
Example 8 S-8 65 72 2.9
Example 9 S-9 58 62 2.91
Example 10 S-10 61 63 2.88
Example 11 S-11 57 60 2.88
As can be seen from the data in Table 5, the use of the invention provides for the reduction of CO and NOx emissionsThe composition is used for the incomplete regeneration process of the catalytic cracking process, and has better CO and NH reduction compared with the composition capable of reducing CO and NOx emission provided by a 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.
As can be seen from the data in tables 4 and 5, the composition capable of reducing the emission of CO and NOx provided by the invention is suitable for complete regeneration and incomplete regeneration at the same time, 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 first firing preferred with the present invention under a carbonaceous atmosphere; as can be seen from a comparison of example 1 with example 6, the use of the preferred mode of the invention of alkali treatment after impregnation of the noble metal leads to a further improvement in the properties of the composition capable of reducing CO and NOx emissions; as can be seen from comparison of example 1 with examples 7 and 8, 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 9 and 10, the preferred Fe to Co mass ratio of the present invention further improves the performance of the composition which reduces CO and NOx emissions; as can be seen from the comparison of example 1 with example 11, the treatment with the preferred carbonaceous atmosphere according to the invention leads to a further improvement in the properties of the composition which enables the reduction of CO and NOx emissions; as can be seen from the comparison of example 1 with comparative examples 1 to3, 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 (40)

1. A composition capable of reducing CO and NOx emissions, characterized in that the composition consists of an inorganic oxide support and, supported on the inorganic oxide support, a first metal element selected from non-noble group VIII metal elements, a second metal element, a third metal element and a fourth metal element, the first metal element comprising Fe and CO in a weight ratio of Fe to CO, calculated as oxides, of 1: (0.05-20), the second metal element is selected from at least one of group IA and/or IIA metal elements, the third metal element is selected from at least one of Zr, V, W and Mn, the fourth metal element is selected from at least one of noble metal elements;
based on the total amount of the composition, the content of the inorganic oxide carrier is 10-90 wt%, and calculated by oxide, the content of the first metal element is 0.5-50 wt%, the content of the second metal element is 0.5-20 wt%, the content of the third metal element is 0.5-20 wt%, calculated by element, the content of the fourth metal element is 0.001-0.15 wt%.
2. The composition according to claim 1, wherein the inorganic oxide support is contained in an amount of 50 to 90% by weight, in terms of oxide, the first metal element is contained in an amount of 3 to 30% by weight, the second metal element is contained in an amount of 1 to 20% by weight, the third metal element is contained in an amount of 1 to 10% by weight, and the fourth metal element is contained in an amount of 0.005 to 0.1% by weight, in terms of element, based on the total amount of the composition.
3. The composition according to claim 1, wherein the inorganic oxide support is present in an amount of 55 to 85 wt% in terms of oxide, the first metal element is present in an amount of 5 to 25 wt%, the second metal element is present in an amount of 5 to 15 wt%, the third metal element is present in an amount of 2 to 8 wt%, and the fourth metal element is present in an amount of 0.01 to 0.08 wt%, based on the total amount of the composition.
4. A composition according to any one of claims 1 to3, wherein the weight ratio of Fe to Co, calculated as oxides, is from 1: (0.1-10).
5. The composition according to any one of claims 1 to3, wherein the weight ratio of Fe to Co, calculated as oxides, is 1 (0.3-3).
6. A composition according to any one of claims 1 to3, wherein the weight ratio of Fe to Co, calculated as oxides, is from 1: (0.5-2).
7. The composition according to any one of claims 1 to3,
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.
8. The composition of claim 7, wherein the composition has an XRD pattern with diffraction peaks at 42.6 °, 44.2 ° and 44.9 ° 2 θ.
9. The composition of any one of claims 1-3, wherein the inorganic oxide support is selected from at least one of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite, and perovskite.
10. The composition of any of claims 1-3, wherein the inorganic oxide support is selected from at least one of alumina, spinel, and perovskite.
11. The composition of any of claims 1-3, wherein the inorganic oxide support is alumina.
12. The composition according to any one of claims 1 to3,
the second metal element is at least one selected from Na, K, Mg and Ca;
the fourth metal element is at least one selected from the group consisting of Pt, Ir, Pd, Ru and Rh.
13. The composition of any one of claims 1-3, wherein the second metallic element is K and/or Mg;
the third metal element is Mn;
the fourth metal element is Ru.
14. The composition of claim 13, wherein the second metallic element is Mg.
15. A method for preparing a composition capable of reducing CO and NOx emissions, the method comprising:
(1) 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 carrying out first roasting to obtain a semi-finished product composition;
(2) taking a solution containing a precursor of a fourth metal element as an impregnation solution, impregnating the semi-finished product composition obtained in the step (1) to obtain a solid product, and then drying and/or carrying out second roasting on the solid product;
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 Zr, V, W and Mn; the fourth metal element is at least one selected from noble metal elements;
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);
the precursor of the inorganic oxide carrier, the precursor of the first metal element, the precursor of the second metal element, the precursor of the third metal element and the precursor of the fourth metal element are used in such amounts that, in the prepared composition, the content of the inorganic oxide carrier is 10 to 90 wt% based on the total amount of the composition, 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%, the content of the third metal element is 0.5 to 20 wt% based on the oxide, and the content of the fourth metal element is 0.001 to 0.15 wt% based on the elements.
16. The production method according to claim 15, wherein the conditions of the first firing include: under the atmosphere containing carbon, the temperature is 400-1000 ℃, and the time is 0.1-10 h.
17. The production method according to claim 16, wherein the conditions of the first firing include: the reaction is carried out in a carbon-containing atmosphere at the temperature of 450-650 ℃ for 1-3 h.
18. The production method according to claim 16, wherein the carbon-containing atmosphere is provided by a gas containing a carbon-containing element selected from at least one of CO, methane, and ethane.
19. The production method according to claim 18, wherein the elemental carbon-containing gas is CO.
20. The method of claim 19, wherein the carbon-containing atmosphere has a concentration of CO of 1-20% by volume.
21. The method of claim 20, wherein the carbon-containing atmosphere has a volume concentration of CO of 4-10%.
22. The production method according to any one of claims 15 to 21, wherein the inorganic oxide support has a content of 50 to 90% by weight in terms of oxide, the first metal element has a content of 3 to 30% by weight, the second metal element has a content of 1 to 20% by weight, the third metal element has a content of 1 to 10% by weight, and the fourth metal element has a content of 0.005 to 0.1% by weight in terms of element.
23. The production method according to any one of claims 15 to 21, wherein the inorganic oxide support has a content of 55 to 85 wt% in terms of oxide, the first metal element has a content of 5 to 25 wt%, the second metal element has a content of 5 to 15 wt%, the third metal element has a content of 2 to 8 wt%, and the fourth metal element has a content of 0.01 to 0.08 wt% in terms of element.
24. The production method according to any one of claims 15 to 21, 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: (0.1-10).
25. The method according to claim 24, 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 resulting composition is 1 (0.3-3).
26. The method of claim 25, wherein the Fe and Co precursors are used in amounts such that the resulting composition has a weight ratio of Fe to Co, calculated as oxides, of 1: (0.5-2).
27. The production method according to any one of claims 15 to 21, wherein the inorganic oxide support is selected from at least one of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite, and perovskite.
28. The production method according to claim 27, wherein the inorganic oxide support is selected from at least one of alumina, spinel, and perovskite.
29. The method of claim 28, wherein the inorganic oxide support is alumina.
30. The method of claim 29, wherein the precursor of alumina is subjected to an acid peptization treatment prior to pulping.
31. The preparation method of claim 30, wherein 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.
32. The production method according to any one of claims 15 to 21, wherein the second metal element is at least one selected from the group consisting of Na, K, Mg, and Ca;
the fourth metal element is at least one selected from Pt, Ir, Pd, Ru and Rh;
the first metal element precursor, the second metal element precursor, the third metal element precursor and the fourth metal element precursor are respectively selected from water-soluble salts of a first metal element, a second metal element, a third metal element and a fourth metal element.
33. The production method according to claim 32,
the second metal element is K and/or Mg;
the third metal element is Mn;
the fourth metal element is Ru.
34. The production method according to claim 33, wherein the second metal element is Mg.
35. A composition capable of reducing CO and NOx emissions produced by the method of any one of claims 15-34.
36. Use of a composition according to any one of claims 1 to 14 and 35 for reducing CO and NOx emissions in the treatment of flue gases.
37. Use of a composition according to any one of claims 1 to 14 and 35 capable of reducing CO and NOx emissions in catalytic cracking regeneration flue gas treatment.
38. A fluid catalytic cracking process, the 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 any one of claims 1 to 14 and 35.
39. The fluid catalytic cracking process of claim 38, wherein the composition capable of reducing CO and NOx emissions is present in an amount of 0.05 to 5 wt.%, based on the total amount of catalyst.
40. The fluid catalytic cracking process of claim 39, wherein the composition capable of reducing CO and NOx emissions is present in an amount of 0.1 to3 wt.%, based on the total amount of catalyst.
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CN111939889B (en) * 2019-05-17 2023-02-21 中国石油化工股份有限公司 Renewable NO oxidation catalyst, preparation method and application thereof
CN111939890B (en) * 2019-05-17 2023-02-21 中国石油化工股份有限公司 Low-temperature NO oxidation catalyst, preparation method thereof and application thereof in low-temperature flue gas treatment
CN115140736B (en) * 2022-05-16 2023-09-19 中南大学 Multicomponent composite ferrite modified activated carbon, preparation method thereof and application thereof in desulfurization and denitrification
CN115414944B (en) * 2022-08-29 2023-11-07 武汉科林化工集团有限公司 Preparation method of catalyst for producing isopropanol by acetone hydrogenation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102371150A (en) * 2010-08-26 2012-03-14 中国石油化工股份有限公司 Composition for reducing discharge of NOx in regeneration flue gas of fluid catalytic cracking (FCC)
CN104302392A (en) * 2012-08-27 2015-01-21 三井金属矿业株式会社 Exhaust gas purifying catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006015710A1 (en) * 2005-10-14 2007-04-26 Degussa Gmbh Mixed oxidation catalysts for the catalytic gas phase oxidation of olefins and process for their preparation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102371150A (en) * 2010-08-26 2012-03-14 中国石油化工股份有限公司 Composition for reducing discharge of NOx in regeneration flue gas of fluid catalytic cracking (FCC)
CN104302392A (en) * 2012-08-27 2015-01-21 三井金属矿业株式会社 Exhaust gas purifying catalyst

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