CN109201099B - Composition capable of reducing CO and NOx emission, preparation method and application thereof, and fluidized catalytic cracking method - Google Patents

Composition capable of reducing CO and NOx emission, preparation method and application thereof, and fluidized catalytic cracking method Download PDF

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CN109201099B
CN109201099B CN201710543245.2A CN201710543245A CN109201099B CN 109201099 B CN109201099 B CN 109201099B CN 201710543245 A CN201710543245 A CN 201710543245A CN 109201099 B CN109201099 B CN 109201099B
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catalytic cracking
composition
fluid catalytic
cracking process
reducing
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CN109201099A (en
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田辉平
宋海涛
孙言
姜秋桥
王鹏
张杰潇
张万虹
李家兴
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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Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to EP18827377.5A priority patent/EP3693085A4/en
Priority to TW107123246A priority patent/TWI786147B/en
Priority to PCT/CN2018/094584 priority patent/WO2019007381A1/en
Priority to JP2020500124A priority patent/JP7114688B2/en
Priority to US16/626,742 priority patent/US11529612B2/en
Priority to AU2018298192A priority patent/AU2018298192B2/en
Priority to RU2020104054A priority patent/RU2772281C2/en
Publication of CN109201099A publication Critical patent/CN109201099A/en
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0063—Granulating
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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. The composition Fe and Co provided by the invention are used together as main metal elements to be matched, so that the composition has high hydrothermal stability, and the activity of reducing CO and NOx emission of regenerated flue gas is high.

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 N2While generating CO and NOx pollutantsAnd (5) dyeing the materials. 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 device3A method of venting by adding excess CO to the regenerator to assist combustionThe addition amount of the agent is 2-3 times of the minimum addition amount which can prevent the tail combustion of the dilute phase bed layer. 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
Aiming at NH in the regeneration process of the prior art3The invention provides a novel composition capable of reducing CO and NOx emission and a method for reducing CO and NOx emissionA method for preparing a composition capable of reducing CO and NOx emission, the composition capable of reducing CO and NOx emission prepared by the method, the application of the composition capable of reducing CO and NOx emission in flue gas treatment, and a fluidized catalytic cracking method. The composition capable of reducing the emission of CO and NOx provided by the invention has high catalytic conversion activity on reduced nitrides, is simple in preparation method, can be used in the fluidized catalytic cracking process, and can effectively reduce the emission of CO and NOx in catalytic cracking regeneration flue gas.
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 Fe and Co as active components in a matching way in the research process. The reason for this may presumably be due to: fe and Co are used as main metal elements together, and the composition which can reduce the emission of CO and NOx is composed of specific content and inorganic oxide, thereby being beneficial to reducing the generation of nitrogen-containing compounds in an oxidation state and promoting the decomposition of nitrogen-containing compounds in a reduction state.
Through further research, the solid obtained after spray drying is preferably treated at high temperature in a carbon-containing atmosphere after the spray drying, so that the emission of CO and NOx in the catalytic cracking regeneration flue gas can be more effectively reduced. In the preferred case, the structure of the composition capable of reducing CO and NOx emissions is further conditioned and stabilized so that the composition capable of reducing CO and NOx emissions is directed to NH3The catalytic conversion activity of the reduced nitrides is obviously improved, the hydrothermal stability is better, and the requirements of the regenerator hydrothermal environment on the composition capable of reducing the emission of CO and NOx are met.
Based on this, according to a first aspect of the present invention, there is provided a composition capable of reducing CO and NOx emissions, which composition consists of an inorganic oxide support and Fe and CO supported on the inorganic oxide support, the inorganic oxide support being contained in an amount of 60 to 95% by weight, based on the total amount of the composition, and the total content of Fe and CO being 5 to 40% by weight, calculated as oxides.
According to a second aspect of the present invention, there is provided a process for the preparation of a composition capable of reducing CO and NOx emissions, the process comprising:
mixing and pulping a precursor of an inorganic oxide carrier, a precursor of Fe, a precursor of Co and water to obtain slurry, carrying out spray drying on the slurry, and then roasting;
wherein the precursors of the inorganic oxide carrier, the Fe precursor and the Co precursor are used in such amounts that the content of the inorganic oxide carrier is 60 to 95 wt% based on the total amount of the composition and the total content of Fe and Co is 5 to 40 wt% in terms of oxides.
According to a third aspect of the present invention, there is provided a composition capable of reducing CO and NOx emissions produced by the above-described production method.
According to a fourth aspect of the present invention there is provided the use of a composition as described above capable of reducing CO and NOx emissions in the treatment of flue gases.
According to a fifth aspect of the present invention, there is provided the use of a composition as described above capable of reducing CO and NOx emissions in catalytic cracking regeneration flue gas treatment.
According to a sixth aspect of the present invention there is provided a fluid catalytic cracking process comprising: the hydrocarbon oil is contacted with a catalyst for reaction, and then the catalyst after the contact reaction is regenerated, wherein the catalyst comprises a catalytic cracking catalyst and a composition capable of reducing CO and NOx emission, and the composition capable of reducing CO and NOx emission is the composition capable of reducing CO and NOx emission.
The composition capable of reducing the emission of CO and NOx provided by the invention is used as a catalytic cracking auxiliary agent, can keep higher hydrothermal stability in a regenerator hydrothermal environment, and has higher activity of reducing the emission of CO and NOx in regeneration flue gas. In addition, the preparation method of the composition capable of reducing CO and NOx emission provided by the invention is simple to operate and low in production cost. Compared with the FCC method using the prior CO and NOx emission reducing auxiliary agent, the FCC method using the composition capable of reducing the CO and NOx emission provided by the invention has the advantages of low consumption of the composition capable of reducing the CO and NOx emission and higher activity of reducing the CO and NOx emission.
For example, the composition capable of reducing CO and NOx emissions provided in example 3 of the present invention is uniformly mixed with FCC main catalyst (Cat-a) in an amount of 0.8 wt% based on the total weight of the catalyst, and then aged at 800 ℃ for 12 hours in an atmosphere of 100% steam for catalytic cracking reaction-regeneration evaluation, and compared with composition D-3 capable of reducing CO and NOx emissions prepared by a prior art saturated impregnation method with active components, when the composition capable of reducing CO and NOx emissions provided in the present invention is used, the NOx emission concentration in the incompletely regenerated flue gas under aerobic conditions is reduced from 109ppm to 57 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 invention provides a composition capable of reducing CO and NOx emission, which consists of an inorganic oxide carrier and Fe and Co loaded on the inorganic oxide carrier, wherein the content of the inorganic oxide carrier is 60-95 wt% based on the total amount of the composition, and the total content of the Fe and the Co is 5-40 wt% calculated by oxides.
The selection range of the content of Fe and Co in the composition is wide, and preferably, the content of the inorganic oxide carrier is 75-92 wt% based on the total amount of the composition, and the total content of Fe and Co is 8-25 wt% calculated by oxide; further preferably, the inorganic oxide support is present in an amount of 84 to 90 wt%, and the total amount of Fe and Co, calculated as oxides, is 10 to 16 wt%.
According to the invention, Fe and Co with specific total amount are used as metal elements in a matching way, the metal elements are less in dosage, and the emission activity of reducing CO and NOx is higher compared with the prior art.
In the present invention, the NH content of the composition can be increased by using Fe and Co as the metal elements3In 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: (0.1-10), more preferably 1: (0.3-3), more preferably 1: (0.4-2). The inventor of the invention finds that Fe and Co in a specific ratio can generate better synergistic effect, and are more beneficial to improving the performance of the composition.
In the present invention, unless otherwise specified, Fe in terms of oxide means Fe in terms of Fe2O3In terms of Co in oxide, Co means Co in Co2O3And (6) counting.
According to a preferred embodiment of the invention, the Fe in the composition is at least partially present in the form of iron carbide, preferably Fe3C and/or Fe7C3. The amount of iron carbide present is not particularly limited in the present invention, and the presence of some iron carbide is effective to improve the performance of the composition that reduces CO and NOx emissions.
According to a preferred embodiment of the invention, the Co in the composition is at least partly present in the form of elemental cobalt. The present invention is not particularly limited as to the amount of elemental cobalt present, as long as some elemental cobalt is present, the performance of the composition that is effective in reducing CO and NOx emissions is enhanced.
In the existing compositions for reducing CO and NOx emissions, the metal elements in the compositions are mostly present in the form of oxidized state. In the preparation process of the composition, the composition is preferably roasted in a carbon-containing atmosphere, so that part of FeO is converted into iron carbide and part of CoO is converted into elemental cobalt.
The existence of the iron carbide and/or the simple substance cobalt can enable the composition to better promote the decomposition of the nitrogen-containing compounds in a reduction state, reduce the generation of nitrogen oxides and promote the reduction of the nitrogen oxides to a certain extent.
According to the composition provided by the invention, preferably, the XRD pattern of the composition has diffraction peaks at 42.6 degrees, 44.2 degrees and 44.9 degrees of 2 theta.
Specifically, diffraction peaks of iron carbide at 42.6 ° and 44.9 ° of 2 θ; the diffraction peak of the simple substance cobalt is at 44.2 degrees 2 theta.
According to a preferred embodiment of the present invention, the present invention provides a composition having an XRD pattern with a diffraction peak at 44.9 ° 2 θ stronger than a diffraction peak at 42.6 ° 2 θ.
According to the composition provided by the present invention, the inorganic oxide support may be various inorganic oxide supports conventionally used in the art, for example, at least one selected from the group consisting of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite, and perovskite. In the present invention, the spinel may be various commonly used spinels, and may be at least one of magnesium aluminate spinel, zinc aluminate spinel, and titanium aluminate spinel, for example.
According to a preferred embodiment of the present invention, the inorganic oxide support is selected from at least one of alumina, spinel and perovskite, and is further preferably alumina.
In the present invention, the alumina may be at least one selected from the group consisting of γ -alumina, δ -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.
According to a most preferred embodiment of the present invention, the combination of specific amounts of Fe and Co as metal elements can greatly improve the NH-to-NH ratio of the composition capable of reducing 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 one embodiment of the invention, the composition consists of alumina and Fe and Co supported on the alumina in a weight ratio of Fe to Co, calculated as oxides, of 1: (0.4-2), based on the total weight of the composition, the content of the alumina is 84-90 wt%, and the total content of the Fe and the Co is 10-16 wt% calculated by oxide.
In the invention, the contents of all components in the composition capable of reducing the emission of CO and NOx are measured by adopting an X-ray fluorescence spectrum analysis method (a petrochemical engineering analysis method (RIPP experimental method), compilation of Yangcui and the like, published by scientific publishing company in 1990).
The present invention also provides a method for preparing a composition capable of reducing CO and NOx emissions, the method comprising:
mixing and pulping a precursor of an inorganic oxide carrier, a precursor of Fe, a precursor of Co and water to obtain slurry, carrying out spray drying on the slurry, and then roasting;
wherein the precursors of the inorganic oxide carrier, the Fe precursor and the Co precursor are used in such amounts that the content of the inorganic oxide carrier is 60 to 95 wt% based on the total amount of the composition and the total content of Fe and Co is 5 to 40 wt% in terms of oxides.
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 selection of the inorganic oxide carrier is as described above, and is not described herein 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 mixing and beating, 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 Fe precursor and the Co precursor are respectively selected from water-soluble salts of Fe and Co, such as nitrate, chloride, chlorate, sulfate, and the like, and the present invention is not particularly limited thereto.
According to the preparation method, the selection range of the using amounts of the Fe precursor and the Co precursor is wide, and preferably, the using amounts of the Fe precursor and the Co precursor of the inorganic oxide carrier are such that the content of the inorganic oxide carrier is 75-92 wt% based on the total amount of the composition, and the total content of the Fe and the Co is 8-25 wt% calculated by oxide; further preferably, the inorganic oxide support is present in an amount of 84 to 90 wt%, and the total amount of Fe and Co, calculated as oxides, is 10 to 16 wt%.
The present invention provides a method for preparing a composition capable of reducing CO and NOx emissions, preferably,
the mass ratio of the Fe precursor and the Co precursor counted by metal elements to the inorganic oxide carrier precursor counted by oxide is 5-40: 60-95; further, it may be 8 to 25: 75-92, further, 10-16: 84-90.
According to a preferred embodiment of the invention, the Fe and Co precursors are used in amounts such that the resulting composition preferably has a weight ratio of Fe to Co, calculated as oxides, of 1: (0.1-10), more preferably 1: (0.3-3), more preferably 1: (0.4-2). The preferable proportion of Fe and Co in the invention enables Fe and Co to better play a synergistic effect, and is more beneficial to improving the catalytic conversion activity of the composition on the original nitride.
According to the invention, the slurry preferably has a solids content of 8 to 30% by weight.
According to the present invention, the method of mixing and beating the precursor of the inorganic oxide carrier, the precursor of Fe, the precursor of Co, and water is not particularly limited, and the method of mixing and beating the precursor of the inorganic oxide carrier, the precursor of Fe, the precursor of Co, and water is not particularly limited, as long as the three are mixed and then beaten to obtain a slurry.
In the present invention, the spray drying may be carried out according to a conventional technique in the art, and the present invention is not particularly limited thereto, and preferably the spray drying conditions are such that the average particle size of the spray-dried particles is 60 to 75 μm and the particle size distribution is mainly in the range of 20 to 100. mu.m, and more preferably the spray drying conditions are such that 50% or more of the particles having a particle size of 40 to 80 μm are contained in the spray-dried particles.
According to the invention, the calcination effectively increases the NH pair of the composition capable of reducing CO and NOx emissions by means of the conventional technical means in the field3Catalytic conversion activity of reduced nitrides, but to further increase NH of compositions capable of reducing CO and NOx emissions3The catalytic conversion activity and hydrothermal stability of the nitride in an isoreduced state, and preferably the calcination is carried out in a carbon-containing atmosphere. The inventors of the present invention have studiedIt has been unexpectedly found that subjecting the calcination to a carbonaceous atmosphere can result in a composition that reduces CO and NOx emissions versus NH3The catalytic conversion activity and the hydrothermal stability of the nitride in the reduced state are both obviously improved. 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 composition S-5 which had not been subjected to the carbon-containing atmosphere had Al at 45.5 °2O3And Co2AlO4And the XRD spectrum of the composition S-1 treated in the carbon-containing atmosphere has Al not only at about 45.5 DEG2O3And Co2AlO4And obvious diffraction peaks appear at about 42.6 degrees and at about 45.0 degrees, which is attributed to the fact that FeC (Fe) appears at 42.6 degrees and 44.9 degrees 2 theta of the composition S-1 treated by the carbon-containing atmosphere3C and Fe7C3) The diffraction peak of (1). In addition, composition S-1 exhibited a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ in terms of 2. theta. was a diffraction peak of elemental cobalt, as compared with composition S-5.
It should be noted that FIG. 1 shows only XRD patterns in the range of 41 to 50, primarily to illustrate the presence of Fe and Co in the composition. Outside the range of 41 ° to 50 °, other diffraction peaks are present, for example, diffraction peaks for FeO (at 37 °, 65 ° and 59 ° for 2 θ) and CoO (at 37 °, 65 ° and 31 ° for 2 θ), which are not further explained by the present invention.
According to a preferred embodiment of the present invention, the conditions of the calcination include: the reaction is carried out in a carbon-containing atmosphere at a temperature of 400-1000 ℃, preferably 450-650 ℃, more preferably 500-650 ℃, and for a time of 0.1-10h, preferably 1-3 h.
In the present invention, the pressure for the calcination is not particularly limited, and the calcination may be carried out under normal pressure. For example, it can be carried out at from 0.01 to 1MPa (absolute).
In the present invention, the carbon-containing atmosphere is provided by a gas containing a carbon-containing element, and the gas containing a carbon-containing element is preferably selected from gases containing a carbon-containing element having reducibility, further preferably containing at least one of CO, methane, and ethane, and most preferably CO.
According to the present invention, the gas containing carbon element may further contain a part of inert gas, and the inert gas may be various inert gases conventionally used in the art, and is preferably at least one selected from nitrogen, argon and helium, and is further preferably nitrogen.
According to a preferred embodiment of the present invention, the carbon-containing atmosphere is provided by a mixed gas containing CO and nitrogen, and the volume concentration of CO in the carbon-containing atmosphere is preferably 1 to 20%, and more preferably 4 to 10%. By adopting the preferred embodiment of the invention, the treatment requirements can be better met, and the safety of operators can be ensured.
In the present invention, the calcination may be performed in a calciner, which may be a rotary calciner used in the production of catalytic cracking catalysts and promoters. The gas containing carbon element is in countercurrent contact with the solid material in the roasting furnace.
The invention also provides a composition prepared by the preparation method and capable of reducing CO and NOx emission.
The composition capable of reducing CO and NOx emission prepared by the preparation method contains Fe and Co which are used as metal elements in a matching way, so that the composition capable of reducing CO and NOx emission can be 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 completely regenerated smoke and incompletely regenerated smoke, and the composition capable of reducing the emission of CO and NOx provided by the invention is more suitable for reducing the emission of CO and NOx in incompletely regenerated smoke. Therefore, the invention provides the application of the composition capable of reducing CO and NOx emission in the treatment of catalytic cracking incomplete regeneration flue gas.
The present invention also provides a fluid catalytic cracking process comprising: the hydrocarbon oil is contacted with a catalyst for reaction, and then the catalyst after the contact reaction is regenerated, wherein the catalyst comprises a catalytic cracking catalyst and a composition capable of reducing CO and NOx emission, and the composition capable of reducing CO and NOx emission is the composition capable of reducing CO and NOx emission.
According to the fluid catalytic cracking method provided by the invention, the content of the composition capable of reducing CO and NOx emission is preferably 0.05-5 wt%, more preferably 0.1-3 wt%, and even more preferably 0.5-2.5 wt% based on the total amount of the catalyst.
According to the fluidized catalytic cracking method provided by the invention, preferably, hydrocarbon oil is in contact reaction with a catalyst, and then the catalyst after the contact reaction is subjected to incomplete regeneration, and further preferably, the concentration of oxygen in flue gas generated by the incomplete regeneration is not more than 0.5% by volume.
The hydrocarbon oil is not particularly limited in the present invention, and may be various hydrocarbon oils conventionally treated in the field of catalytic cracking, such as vacuum gas oil, atmospheric residue, vacuum residue, deasphalted oil, coker gas oil, or hydrotreated oil.
The catalytic cracking catalyst is not particularly limited in the invention, and can be one or more of the existing catalytic cracking catalysts, and can be commercially available or prepared according to the existing method.
The composition capable of reducing the emission of CO and NOx provided by the invention can be an independent particle or can be a part of the whole catalytic cracking catalyst particle. Preferably, the composition of the present invention capable of reducing CO and NOx emissions is provided as a separate particle for use with the catalytic cracking catalyst particles.
In the present invention, the ppm refers to a volume concentration unless otherwise specified.
In the fluid catalytic cracking process of the present invention, the method of catalyst regeneration has no special requirements compared to the existing regeneration methods, including partial regeneration, incomplete regeneration and complete regeneration modes of operation. The regeneration method can be seen in pages 1234-1343 of catalytic cracking process and engineering published by Chenjun Wu Shu, Chinese petrochemical Press 2005. The preferred regeneration temperature is 650 deg.C-730 deg.C.
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.
The contents of the components in the compositions capable of reducing CO and NOx emissions in the following examples were measured by X-ray fluorescence spectroscopy (XRF), see in particular the methods of petrochemical analysis (RIPP test methods), edited by yang cuisine et al, published by scientific publishers in 1990, the compositions capable of reducing CO and NOx emissions in the examples were obtained by XRD spectroscopy using an X-ray diffractometer (Siemens D5005), and subjected to structural determination, Cu target, K α 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, it is produced by chemical reagents of the national drug group; pseudo-boehmite is an industrial grade product, the content of alumina is 64 weight percent, and the pore volume is 0.31 ml/g, which is produced by Shandong aluminum company; hydrochloric acid with the concentration of 36.5 weight percent, and the product is analytically pure and produced by Beijing chemical plants; carbon monoxide with a concentration of 10 vol%, nitrogen as a balance gas, produced by Beijing helium Pubei gas industries, Ltd; catalytic cracking catalyst industrial product (Cat-A, catalyst brand CGP-1), Na2O content 0.24 wt%, RE2O3Content 3.2 wt.%, Al2O348.0 wt%, and an average particle diameter of 67 μm, manufactured by China petrochemical catalyst, Inc.
Example 1
(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) 100g, cobalt nitrate (calculated as Co)2O3Calculated by the following steps) 100g of the alumina powder is added into 3500mL of water and stirred until the alumina powder is fully dissolved, the alumina powder colloid is added into the water and stirred for 20min to obtain slurry, the slurry is sprayed and dried, 100g of particles obtained by spraying and drying (the average particle size is 65 μm, the particles with the particle size of 40-80 μm account for 60 percent, the same is carried out below) are taken and transferred into a tubular furnace, and CO/N with the CO concentration of 10 volume percent is introduced at the flow rate of 100mL/min2The mixed gas was treated at 600 ℃ for 1.5 hours to obtain composition S-1.
The results of measuring the contents of the respective components in the composition S-1 are shown in Table 1.
XRD analysis was performed on the composition S-1, and the XRD spectrum is shown in FIG. 1, as can be seen from FIG. 1,
the XRD pattern of composition S-5 without carbon containing atmosphere treatment showed Al at 45.5 °2O3And Co2AlO4And the XRD spectrum of the composition S-1 treated in the carbon-containing atmosphere has Al not only at about 45.5 DEG2O3And Co2AlO4And obvious diffraction peaks appear at about 42.6 degrees and at about 45.0 degrees, which is attributed to the fact that FeC (Fe) appears at 42.6 degrees and 44.9 degrees 2 theta of the composition S-1 treated by the carbon-containing atmosphere3C 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 2.56kg of pseudo-boehmite into 13.9kg of deionized water, pulping and dispersing, then adding 232mL of hydrochloric acid, acidifying for 15min to obtain an aluminum-stone colloid, adding 140g of ferric nitrate and 60g of cobalt nitrate in terms of metal oxide into 3500mL of water, stirring until the ferric nitrate and the cobalt nitrate are fully dissolved, adding the aluminum-stone colloid into the water, stirring for 20min to obtain slurry, performing spray drying on the slurry, taking 100g of particles obtained by spray drying, transferring the particles into a tubular furnace, and introducing CO/N with the CO concentration of 10 vol% at the flow rate of 100mL/min2The mixed gas was treated at 500 ℃ for 3 hours to obtain composition S-2.
The results of measuring the contents of the respective components in the composition S-2 are shown in Table 1. The XRD analysis of composition S-2 was similar to that of example 1. In the XRD spectrogram of the composition S-2 treated by the carbon-containing atmosphere, Al is arranged at about 45.5 DEG2O3And Co2AlO4And obvious diffraction peaks appear at about 42.6 degrees and at about 45.0 degrees, which are attributed to the fact that the composition S-2 treated by the carbon-containing atmosphere has FeC (Fe) at 42.6 degrees and 44.9 degrees of 2 theta3C 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 2.34kg of pseudo-boehmite into 12.7kg of deionized water, pulping and dispersing, then adding 212mL of hydrochloric acid, acidifying for 15min to obtain an aluminum-stone colloid, adding 100g of ferric nitrate and 200g of cobalt nitrate in terms of metal oxide into 4000mL of water, stirring until the ferric nitrate and the cobalt nitrate are fully dissolved, adding the aluminum-stone colloid into the water, stirring for 20min to obtain slurry, performing spray drying on the slurry, transferring 100g of particles obtained by spray drying into a tubular furnace, introducing CO/N with the CO concentration of 10 vol% at the flow rate of 100mL/min, and stirring for 20min2The gas mixture was treated at 650 ℃ for 1 hour to obtain composition S-3.
The results of measuring the contents of the respective components in the composition S-3 are shown in Table 1. The XRD analysis of composition S-3 was similar to that of example 1. The XRD spectrum of the composition S-3 treated by the carbon-containing atmosphere is not only about 45.5 DEGWith Al2O3And Co2AlO4And obvious diffraction peaks appear at about 42.6 degrees and at about 45.0 degrees, which are attributed to the fact that the composition S-3 treated by the carbon-containing atmosphere has FeC (Fe) at 42.6 degrees and 44.9 degrees of 2 theta3C 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 2.25kg of pseudo-boehmite into 12.2kg of deionized water, pulping and dispersing, then adding 204mL of hydrochloric acid, acidifying for 15min to obtain an aluminum-stone colloid, adding 200g of ferric nitrate and 120g of cobalt nitrate in terms of metal oxide into 3500mL of water, stirring until the ferric nitrate and the cobalt nitrate are fully dissolved, adding the aluminum-stone colloid into the water, stirring for 20min to obtain slurry, carrying out spray drying on the slurry, transferring 100g of particles obtained by spray drying into a tubular furnace, introducing CO/N with the CO concentration of 10% at the flow rate of 100mL/min, and then adding2The mixed gas was treated at 600 ℃ for 1.5 hours to obtain composition S-4.
The results of measuring the contents of the respective components in the composition S-4 are shown in Table 1. The XRD analysis of composition S-4 was similar to that of example 1. In the XRD spectrogram of the composition S-4 treated by the carbon-containing atmosphere, Al is arranged at about 45.5 DEG2O3And Co2AlO4And obvious diffraction peaks appear at about 42.6 degrees and at about 45.0 degrees, which is attributed to the fact that FeC (Fe) appears at 42.6 degrees and 44.9 degrees 2 theta in the composition S-4 treated by the carbon-containing atmosphere3C and Fe7C3) The diffraction peak of (1). In addition, composition S-4 exhibited a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ in terms of 2. theta. was a diffraction peak of elemental cobalt, as compared with composition S-5.
Example 5
The procedure is as in example 1, except that the CO concentration is 10% by volume CO/N2The mixed gas was replaced with air to obtain composition S-5.
The results of measuring the contents of the respective components in the composition S-5 are shown in Table 1. XRD analysis of the composition S-5 showed that there were no distinct diffraction peaks at 42.6, 44.2 and 44.9 degrees 2 theta as seen in XRD pattern (as shown in FIG. 1), demonstrating that both Fe and Co were present as oxides in the composition S-5.
Example 6
Composition S-6 was obtained in the same manner as in example 1 except that 50g of iron nitrate and 150g of cobalt nitrate, in terms of metal oxide, were used.
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. In the XRD spectrogram of the composition S-6 treated by the carbon-containing atmosphere, Al is arranged at about 45.5 DEG2O3And Co2AlO4And obvious diffraction peaks appear at about 42.6 degrees and at about 45.0 degrees, which is attributed to the fact that the composition S-6 treated by the carbon-containing atmosphere has FeC (Fe) at 42.6 degrees and 44.9 degrees of 2 theta3C 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 in the same manner as in example 1 except that the amount of iron nitrate was 150g and the amount of cobalt nitrate was 50g, in terms of metal oxide.
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. In the XRD spectrum of the composition S-7 treated by the carbon-containing atmosphere, Al is arranged at about 45.5 DEG2O3And Co2AlO4And obvious diffraction peaks appear at about 42.6 degrees and at about 45.0 degrees, which is attributed to the fact that the composition S-7 treated by the carbon-containing atmosphere has FeC (Fe) at 42.6 degrees and 44.9 degrees of 2 theta3C 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 of example 1 was followed except that the CO/N concentration of 10% was replaced with an ethane/nitrogen mixed gas having an ethane concentration of 10%2The gases were mixed to give 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 spectrogram of the composition S-8 treated by the carbon-containing atmosphere, Al is arranged at about 45.5 DEG2O3And Co2AlO4And obvious diffraction peaks appear at about 42.6 degrees and at about 45.0 degrees, which is attributed to the fact that the composition S-8 treated by the carbon-containing atmosphere has FeC (Fe) at 42.6 degrees and 44.9 degrees of 2 theta3C 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.
Comparative example 1
Composition D-1 was obtained by following the procedure of example 1 except that the cobalt nitrate was replaced with the same mass of iron nitrate based on the metal oxide.
The results of measuring the contents of the respective components in the composition D-1 are shown in Table 1.
Comparative example 2
Composition D-2 was obtained by following the procedure of example 1 except that the iron nitrate was replaced with the same mass of cobalt nitrate based on the metal oxide.
The results of measuring the contents of the respective components in the composition D-2 are shown in Table 1.
Comparative example 3
Reference is made to the method described in US6800586 for the preparation of a comparative composition. Taking 34.4 g of dried gamma-alumina microsphere carrier, impregnating alumina microspheres with a solution prepared from 10.09g of cerium nitrate, 2.13g of lanthanum nitrate and 18mL of water, drying at 120 ℃ after impregnation, roasting at 600 ℃ for 1 hour, impregnating with a solution prepared from 2.7g of copper nitrate and 18mL of water, drying at 120 ℃ and roasting at 600 ℃ for 1 hour to obtain a composition D-3. In the composition D-3, RE is calculated as oxide based on the total amount of the composition D-32O3Is 12 wt% and CuO is 2.3 wt% (RE represents a lanthanide metal element).
TABLE 1
Figure BDA0001342380220000201
Figure BDA0001342380220000211
Note: the content of each component is calculated by oxide, and the unit is weight percent.
Test example 1
The test example is used for reducing the effect of CO and NOx emission in incomplete regeneration flue gas under aerobic condition on the compositions capable of reducing CO and NOx emission provided by the above examples and comparative examples.
The composition capable of reducing CO and NOx emissions was uniformly blended with the above catalytic cracking catalyst (Cat-A) (the composition capable of reducing CO and NOx emissions accounted for 2.2% by weight of the total amount of the composition capable of reducing CO and NOx emissions and the catalytic cracking catalyst), and subjected to catalytic cracking reaction-regeneration evaluation after aging at 800 ℃ for 12 hours in an atmosphere of 100% steam.
The catalytic cracking reaction-regeneration evaluation is carried out on a small fixed bed simulated flue gas NOx reduction device, the loading amount of an aged catalyst is 10g, the reaction temperature is 650 ℃, and the volume flow of raw material gas is 1500 mL/min. The feed gas contained 3.7 vol.% CO, 0.5 vol.% oxygen, 800ppm NH3The balance being N2. Analyzing the gas product by an on-line infrared analyzer to obtain reacted NH3NOx and CO concentrations, and the results are shown in table 2.
TABLE 2
Figure BDA0001342380220000212
Figure BDA0001342380220000221
As can be seen from the data in Table 2, the composition capable of reducing CO and NOx emission provided by the invention is used for the incomplete regeneration process (aerobic condition) of the catalytic cracking process, and has better CO and NH reduction than the composition capable of reducing CO and NOx emission provided by the comparative example3And NOx emission performanceAnd the composition which can reduce the emission of CO and NOx after aging is used in the evaluation process, and the composition which can reduce the emission of CO and NOx after aging removes CO and NH3And the NOx activity is still higher, therefore, the composition capable of reducing the emission of CO and NOx provided by the invention has better hydrothermal stability.
Test example 2
The test example is used for reducing the effect of CO and NOx emission in the incompletely regenerated flue gas under the anaerobic condition on the compositions capable of reducing CO and NOx emission provided by the above examples and comparative examples.
The process of test example 1 was followed except that the feed gas contained 3.7 vol.% CO and 800ppm NH3The balance being N2. To obtain reacted NH3NOx and CO concentrations, and the results are shown in table 3.
TABLE 3
Figure BDA0001342380220000222
Figure BDA0001342380220000231
As can be seen from Table 3, even though the incompletely regenerated flue gas is treated under oxygen-free conditions, the composition capable of reducing CO and NOx emissions provided by the invention has better CO and NH reduction than the composition capable of reducing CO and NOx emissions provided by the comparative example3Emission performance, and the compositions used in the evaluation process are compositions capable of reducing CO and NOx emissions after aging, and compositions capable of reducing CO and NOx emissions after aging remove CO and NH3The activity is still higher, 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 2 and 3, the composition capable of reducing the emission of CO and NOx provided by the invention is suitable for incomplete regeneration under aerobic and anaerobic conditions, and has better regeneration flue gas treatment capacity. In particular, as can be seen from the comparison of example 1 with example 5, the performance of the composition capable of reducing the emission of CO and NOx is further improved by carrying out the calcination in a carbonaceous atmosphere, which is preferred according to the invention; as can be seen from the comparison of example 1 with examples 6 and 7, the preferred Fe to Co mass ratio according to the invention allows a further improvement in the performance of the composition capable of reducing CO and NOx emissions; as can be seen from a comparison of example 1 with example 8, the treatment with the preferred carbonaceous atmosphere of the invention results in a further improvement in the performance of the composition which reduces CO and NOx emissions; as can be seen from the comparison of example 1 with comparative examples 1 to 3, the present invention enables the composition performance capable of reducing CO and NOx emissions to be greatly improved by using Fe and Co in combination.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (27)

1. A fluid catalytic cracking process, the process comprising: the hydrocarbon oil is in contact reaction with a catalyst, and then the catalyst after the contact reaction is subjected to incomplete regeneration, wherein the catalyst comprises a catalytic cracking catalyst and a composition capable of reducing CO and NOx emission, the composition capable of reducing CO and NOx emission consists of an inorganic oxide carrier and Fe and Co loaded on the inorganic oxide carrier, the content of the inorganic oxide carrier is 84-90 wt% based on the total amount of the composition, and the total content of Fe and Co is 10-16 wt% based on the total amount of the oxide;
the composition capable of reducing CO and NOx emissionsCan reduce NH3CO and NOXAnd (4) discharging.
2. The fluid catalytic cracking process of claim 1, wherein the weight ratio of Fe to Co, calculated as oxides, is 1: (0.1-10).
3. The fluid catalytic cracking process of claim 2, wherein the weight ratio of Fe to Co, calculated as oxides, is 1: (0.3-3).
4. The fluid catalytic cracking process of claim 3, wherein the weight ratio of Fe to Co, calculated as oxides, is 1: (0.4-2).
5. The fluid catalytic cracking process of any one of claims 1 to 4, wherein 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.
6. The fluid catalytic cracking process of claim 5, wherein the composition has an XRD pattern with diffraction peaks at 42.6 °, 44.2 ° and 44.9 ° 2 θ.
7. The fluid catalytic cracking process of any one of claims 1 to 4, wherein the inorganic oxide support is selected from at least one of alumina, silica-alumina, zeolites, spinels, kaolin, diatomaceous earth, perlite and perovskites.
8. The fluid catalytic cracking process of claim 7, wherein the inorganic oxide support is selected from at least one of alumina, spinel, and perovskite.
9. The fluid catalytic cracking process of claim 8, wherein the inorganic oxide support is alumina.
10. A fluid catalytic cracking process, the process comprising: the method comprises the steps of carrying out contact reaction on hydrocarbon oil and a catalyst, and then carrying out incomplete regeneration on the catalyst after the contact reaction, wherein the catalyst comprises a catalytic cracking catalyst and a composition capable of reducing CO and NOx emission, and the preparation method of the composition capable of reducing CO and NOx emission comprises the following steps:
mixing and pulping a precursor of an inorganic oxide carrier, a precursor of Fe, a precursor of Co and water to obtain slurry, carrying out spray drying on the slurry, and then roasting;
wherein, the precursors of the inorganic oxide carrier, the Fe precursor and the Co precursor are used in such amounts that, based on the total amount of the composition, the content of the inorganic oxide carrier is 84-90 wt%, and the total content of Fe and Co calculated by oxide is 10-16 wt%;
the composition capable of reducing CO and NOx emission can reduce NH3CO and NOXAnd (4) discharging.
11. The fluid catalytic cracking process of claim 10, wherein the torrefying conditions comprise: under the atmosphere containing carbon, the temperature is 400-1000 ℃, and the time is 0.1-10 h.
12. The fluid catalytic cracking process of claim 11, wherein the torrefying conditions comprise: the temperature is 450-650 ℃, and the time is 1-3 h.
13. The fluidized catalytic cracking process of claim 11, wherein the carbon-containing atmosphere is provided by an elemental carbon-containing gas selected from at least one of CO, methane, and ethane.
14. The fluid catalytic cracking process of claim 13, wherein the elemental carbon-containing gas is CO.
15. The fluid catalytic cracking process of claim 14, wherein the carbon-containing atmosphere has a volume concentration of CO of 1-20%.
16. The fluid catalytic cracking process of claim 15, wherein the carbon-containing atmosphere has a volume concentration of CO of 4-10%.
17. The fluid catalytic cracking process of any one of claims 10-16, 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: (0.1-10).
18. The fluid catalytic cracking process of claim 17, 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: (0.3-3).
19. The fluid catalytic cracking process of claim 18, 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: (0.4-2).
20. The fluid catalytic cracking process of any one of claims 10-16, wherein the inorganic oxide support is selected from at least one of alumina, silica-alumina, zeolites, spinels, kaolin, diatomaceous earth, perlite, and perovskites.
21. The fluid catalytic cracking process of claim 20, wherein the inorganic oxide support is selected from at least one of alumina, spinel, and perovskite.
22. The fluid catalytic cracking process of claim 21, wherein the inorganic oxide support is alumina.
23. The fluid catalytic cracking process of claim 22, wherein the precursor of alumina is subjected to an acidifying peptization treatment prior to mixing and beating.
24. The fluid catalytic cracking process of claim 23, wherein the acid used in the acidification peptization process is hydrochloric acid, and the conditions of the acidification peptization process comprise: the acid-aluminum ratio is 0.12-0.22: 1, the time is 20-40 min;
the aluminum acid ratio refers to the weight ratio of hydrochloric acid calculated as 36 wt% of concentrated hydrochloric acid to the precursor of alumina on a dry basis.
25. The fluid catalytic cracking process of any one of claims 10-16, wherein the Fe and Co precursors are selected from water soluble salts of Fe and Co, respectively.
26. The fluid catalytic cracking process of claim 1 or 10, 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.
27. The fluid catalytic cracking process of claim 26, wherein the composition capable of reducing CO and NOx emissions is present in an amount of 0.1 to 3 wt.%, based on the total amount of catalyst.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102371165A (en) * 2010-08-26 2012-03-14 中国石油化工股份有限公司 Low-bulk-density composition for reducing discharge of regenerated flue gases CO and NOx during FCC (Fluid Catalytic Cracking)
CN104302392A (en) * 2012-08-27 2015-01-21 三井金属矿业株式会社 Exhaust gas purifying catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102371165A (en) * 2010-08-26 2012-03-14 中国石油化工股份有限公司 Low-bulk-density composition for reducing discharge of regenerated flue gases CO and NOx during FCC (Fluid Catalytic Cracking)
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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