CN109201078B - 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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CN109201078B
CN109201078B CN201710542132.0A CN201710542132A CN109201078B CN 109201078 B CN109201078 B CN 109201078B CN 201710542132 A CN201710542132 A CN 201710542132A CN 109201078 B CN109201078 B CN 109201078B
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metal element
reducing
inorganic oxide
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CN109201078A (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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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 CN201710542132.0A priority patent/CN109201078B/en
Priority to AU2018298192A priority patent/AU2018298192B2/en
Priority to US16/626,742 priority patent/US11529612B2/en
Priority to PCT/CN2018/094584 priority patent/WO2019007381A1/en
Priority to JP2020500124A priority patent/JP7114688B2/en
Priority to RU2020104054A priority patent/RU2772281C2/en
Priority to TW107123246A priority patent/TWI786147B/en
Priority to EP18827377.5A priority patent/EP3693085A4/en
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    • 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
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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 and a second metal element 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), and the second metal element is at least one selected from noble metal elements. The composition Fe and Co provided by the invention are jointly used as main metal elements, and the composition can be kept to have higher hydrothermal stability through further modification of at least one of noble metal elements, and has higher activity of reducing CO and NOx emission of regenerated flue gas.

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.
The auxiliary agent for reducing CO emission of regeneration flue gas is generally called CO auxiliaryA combustion promoter for noble metal carried CO is disclosed in CN1022843C, its active component is 1-1000ppm Pt or 50-1000ppm Pd, its carrier is composed of (1) cracking catalyst or its substrate microballon particles (99.5-50%) and (2) Al (0.5-50%)2O3、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 device3Emission, but use of COThe amount is large, the defect of high energy consumption exists, and the environment 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, 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, and the composition capable of reducing CO and NOx emission in flue gas treatmentAnd a fluid catalytic cracking process. 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 at least one of non-noble metal elements in the VIII group containing Fe and Co and 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 at least one of noble metal elements is further modified, so that the generation of nitrogen-containing compounds in an oxidation state is reduced, and the decomposition of nitrogen-containing compounds in a reduction state can be promoted.
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 reduced nitrides is obviously improved, the hydrothermal stability is better, and the requirements of the regenerator hydrothermal environment on the composition capable of reducing the emission of CO and NOx are met.
In view of this, according to a first aspect of the present invention, there is provided a composition capable of reducing CO and NOx emissions, the composition comprising: the inorganic oxide carrier and a first metal element and a second metal element 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), and the second metal element is at least one selected from 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 precursor of a first metal element 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 second 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 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 76 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 inorganic oxide carrier and a first metal element and a second metal element 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), and the second metal element is at least one selected from noble metal elements.
The content of the first metal element and the second metal element in the composition is selected in a wide range, and preferably, the content of the inorganic oxide carrier is 59.9 to 94.995 wt% based on the total amount of the composition, the content of the first metal element is 5 to 40 wt% in terms of oxide, and the content of the second metal element is 0.005 to 0.1 wt% in terms of element; further preferably, the content of the inorganic oxide support is 74.92 to 91.99 wt%, the content of the first metal element is 8 to 25 wt% in terms of oxide, and the content of the second metal element is 0.01 to 0.08 wt% in terms of element; still more preferably, the inorganic oxide support has a content of 83.93 to 89.95 wt% in terms of oxide, the first metal element has a content of 10 to 16 wt% in terms of element, and the second metal element has a content of 0.05 to 0.07 wt% in terms of element.
The first metal element of the present invention contains Fe and Co as long as Fe and Co are contained, and the present invention does not exclude that the first metal element further contains elements other than Fe and Co, such as Ni, among non-noble group VIII metal elements.
According to a most preferred embodiment of the present invention, the composition is composed of an inorganic oxide support and a first metal element and a second metal element supported on the inorganic oxide support, and the first metal element is only Fe and Co.
In the present invention, the first metal element isThe NH content of the composition can be increased by only containing Fe and Co3In 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: (0.4-2). 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 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 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 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, Fe, Co and Ru are used as the metal elements, and can be used in combination to a large extentEnhanced NH pairs with compositions 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 a particular embodiment of the invention, the composition comprises: alumina and Fe, Co and Ru loaded on the alumina, wherein the weight ratio of Fe to Co is 1: (0.4-2), the content of the alumina is 83.93-89.95 wt% based on the total weight of the composition, the total content of Fe and Co is 10-16 wt% calculated by oxide, 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 precursor of a first metal element 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 second 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 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 selection of the inorganic oxide carrier, the first metal element and the second metal element is as described above, and details are not repeated here.
In the present invention, the precursor of alumina may be selected from various sols or gels of aluminum, or aluminum hydroxide. The aluminum hydroxide may be selected from at least one of gibbsite, surge dam, nordstrandite, diaspore, boehmite, and pseudoboehmite. Most preferably, the precursor of the alumina is pseudoboehmite.
According to the preparation method provided by the invention, preferably, before pulping, the precursor of the alumina is subjected to acidification peptization treatment, wherein the acidification peptization treatment can be carried out according to the conventional technical means in the field, and further preferably, the acid used in the acidification peptization treatment is hydrochloric acid.
The selection range of the acidification peptization conditions is wide, and preferably, the acidification peptization conditions comprise: the acid-aluminum ratio is 0.12-0.22: 1, the time is 20-40 min.
In the present invention, the aluminum acid ratio refers to a mass ratio of hydrochloric acid calculated as 36% by weight of concentrated hydrochloric acid to a precursor of alumina on a dry basis, unless otherwise specified.
The specific implementation mode of the acidification peptization treatment can be as follows: adding pseudo-boehmite into water, pulping, dispersing, adding hydrochloric acid, and acidifying for 30min at an aluminum-acid ratio of 0.18.
According to the present invention, the first metal element precursor and the second metal element precursor are respectively selected from water-soluble salts of the first metal element and the second 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 and the second metal element precursor is wide, and preferably, the amounts of the inorganic oxide support precursor, the first metal element precursor and the second metal element precursor are such that the inorganic oxide support is contained in the prepared composition in an amount of 59.9 to 94.995 wt%, the first metal element is contained in an amount of 5 to 40 wt% in terms of oxide, and the second metal element is contained in an amount of 0.005 to 0.1 wt% in terms of element, based on the total amount of the composition; further preferably, the content of the inorganic oxide support is 74.92 to 91.99 wt%, the content of the first metal element is 8 to 25 wt% in terms of oxide, and the content of the second metal element is 0.01 to 0.08 wt% in terms of element; still more preferably, the inorganic oxide support has a content of 83.93 to 89.95 wt% in terms of oxide, the first metal element has a content of 10 to 16 wt% in terms of element, and the second metal element has a content of 0.05 to 0.07 wt% in terms of element.
According to the preparation method of the composition capable of reducing CO and NOx emission, preferably, the 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 and the second metal element precursor calculated by the noble metal element is 59.9-94.995: 5-40: 0.005-0.1; further, may be 74.92-91.99: 8-25: 0.01-0.08; still further, it may be 83.93-89.95: 10-16: 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: (0.4-2).
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, there is no particular limitation on the method for mixing and beating the precursor of the inorganic oxide support, the first metal element precursor and water, and there is no limitation on the order of addition of the precursor of the inorganic oxide support and the first metal element precursor as well, as long as the precursor of the inorganic oxide support, the first metal element precursor and water are brought into contact 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 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 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 the diffraction peaks appeared at about 42.6 DEG and at about 45.0 DEG, which are attributed to the composition S-1 treated in a carbon-containing atmosphere and having a 2 theta of 42.6 DEG and 44.9 DEGIn which FeC (Fe) appears3C 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 second 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 (the second metal element) and the first metal element can be more tightly combined, the synergistic effect of the precious metal element and the first metal element can be more favorably exerted, and the NH emission of the composition capable of reducing CO and NOx emission can be more favorably improved3Catalytic 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 amount of the alkaline solution are selected in a wide range, for example, the concentration of the alkaline solution can be 0.01-10 mol/L, preferably 0.05-5 mol/L, and more preferably 0.5-2 mol/L, and the volume amount of the alkaline solution can be 1-10 times, preferably 1.5-5 times of 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 obtained, for example, according to an embodiment of the present invention, when the pore volume of the solid product obtained by the present invention is about 0.4 to 0.5m L/g, and the amount of the solid product treated is 100g, 0.5 to 2 mol/L of an aqueous ammonia solution 60 to 250m L 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 the emission of CO and NOx prepared by the preparation method contains at least one of Fe, Co and noble metal elements, and the metal elements are used in combination, so that the composition capable of reducing the emission of CO and NOx can reduce NH3The catalytic conversion activity of the iso-reduced nitrides is obviously improved, and the composition capable of reducing the emission of CO and NOx has better hydrothermal stability.
The invention also provides the application of the composition capable of reducing the emission of CO and NOx in the treatment of flue gas. The composition provided by the invention can be used for treating any flue gas with the requirement of reducing CO and NOx emission.
The invention also provides application of the composition capable of reducing CO and NOx emission in catalytic cracking regeneration flue gas treatment. The composition capable of reducing the emission of CO and NOx is particularly suitable for reducing the emission of CO and NOx in 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), 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; ruthenium chloride (RuCl)3) For analytical purity, the content of Ru is more than or equal to 37 percent, and the Ru is produced by new material GmbH of hundred million gold by the company of Japan; 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) 2.62kg of pseudo-boehmiteAdding stone into 14.2kg deionized water, pulping, dispersing, adding 238m L hydrochloric acid, acidifying for 15min to obtain aluminum-stone colloid, and adding ferric nitrate (calculated as Fe) calculated as metal oxide2O3Calculated as Co) 100g, cobalt nitrate (calculated as Co)2O3Calculated by the following method) 100g of the aluminum powder is added into 3500m L water and stirred until the aluminum powder is fully dissolved, the aluminum powder colloid is added into the water and stirred for 20min to obtain slurry, the slurry is sprayed and dried, 150g of particles obtained by spraying and drying (the average particle diameter is 65 μm, the particles with the particle diameter of 40-80 μm account for 60 percent, the same is applied below) are taken and transferred into a tube furnace, CO/N with the CO concentration of 10 volume percent is introduced at the flow rate of 100m L/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 700m L water, and RuCl with the mass content of 12.5 g/L calculated by metal elements is added3The solution 4.8m L was stirred for 20min and filtered to obtain a solid product, which was rinsed with 2 mol/L ammonia solution 80m L, dried (100 ℃, 4h) and calcined (400 ℃, 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, 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 232m L hydrochloric acid, acidifying for 15min to obtain an aluminum-aluminum colloid, adding 140g of ferric nitrate and 60g of cobalt nitrate in terms of metal oxide into 3500m L water, stirring until the ferric nitrate and the cobalt nitrate are fully dissolved, adding the aluminum-aluminum colloid into the water, stirring for 20min to obtain a 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 100m L/min2Treating the mixed gas at 500 ℃ for 3h to obtain a semi-finished product composition;
(2) 100g of the semi-finished product composition is weighed and added into 700m L water, and RuCl with the mass content of 12.5 g/L calculated by metal elements is added3The solution 4.4m L was stirred for 20min and filtered to obtain a solid product, which was rinsed with 2 mol/L ammonia 100m L, dried (100 ℃, 4h) and calcined (400 ℃, 2h) to obtain the 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 for pulping and dispersion, then adding 212m L hydrochloric acid for acidification for 15min to obtainAdding 100g of ferric nitrate and 200g of cobalt nitrate in terms of metal oxide into 4000m L of water, stirring until the ferric nitrate and the cobalt nitrate are fully dissolved, adding the aluminum colloid into the water, stirring for 20min to obtain slurry, carrying out spray drying on the slurry, transferring 150g of particles obtained by spray drying into a tube furnace, and introducing CO/N with the CO concentration of 10 volume percent at the flow rate of 100m L/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 700m L water, and RuCl with the mass content of 12.5 g/L calculated by metal elements is added3The solution 4m L was stirred for 20min and filtered to obtain a solid product, which was rinsed with 2 mol/L ammonia solution 80m L, dried (100 ℃, 4h) and calcined (400 ℃, 2h) 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. In the XRD spectrogram of the composition S-3 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-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 204m L hydrochloric acid, acidifying for 15min to obtain an aluminum-aluminum colloid, adding 200g of ferric nitrate and 120g of cobalt nitrate in terms of metal oxide into 3500m L water, stirring until the ferric nitrate and the cobalt nitrate are fully dissolved, adding the aluminum-aluminum colloid into the mixture, stirring for 20min to obtain slurry, spray-drying 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 100m L/min2Treating the mixed gas at 600 ℃ for 1.5h to obtain a semi-finished product composition;
(2) weighing 100g aboveThe semi-finished product composition is added into 700m L water, and RuCl with the mass content of 12.5 g/L calculated by metal elements is added3The solution 5.2m L was stirred for 20min and filtered to obtain a solid product, which was rinsed with 2 mol/L ammonia solution 80m L, dried (100 ℃, 4h) and calcined (400 ℃, 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. 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
The procedure of example 1 was followed except that the step of rinsing the solid product with an aqueous ammonia solution having a concentration of 2 mol/L of 80m L was not included 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. In the XRD spectrogram of the composition S-6 treated by the carbon-containing atmosphere, Al is arranged at about 45.5 DEG2O3And Co2AlO4And diffraction peaks of about 42.6 DEG and 45 DEGThe obvious diffraction peak appears around 0 degrees, which is attributed to the composition S-6 treated by the carbon-containing atmosphere, and FeC (Fe) appears at the 2 theta of 42.6 degrees and 44.9 degrees3C 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 50g and the amount of cobalt nitrate was 150g, 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
Composition S-8 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-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.
Example 9
The procedure of example 1 was followed except that the CO/N concentration of 10 vol% was replaced with an ethane/nitrogen mixed gas having an ethane concentration of 10 vol%2The gases were mixed to give composition S-9.
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. In the XRD spectrogram of the composition S-9 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-9 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-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.
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
Preparing a comparative composition according to the method described in US6800586, impregnating alumina microspheres with 34.4 g of dried γ -alumina microsphere carrier, using a solution prepared from 10.09g of cerium nitrate, 2.13g of lanthanum nitrate and 18m L of water, drying at 120 ℃ and calcining at 600 ℃ for 1 hour after impregnation, then impregnating with a solution prepared from 2.7g of copper nitrate and 18m L of water, drying at 120 ℃ and calcining at 600 ℃ for 1 hour to obtain a composition D-3, and in the composition D-3, based on the total amount of the composition D-3, calculated as oxides, RE (beta-hydroxy-substituted phenol) is added2O3In an amount of12% by weight, the content of CuO being 2.3% by weight (RE stands for a lanthanide metal element).
TABLE 1
Figure BDA0001342091020000221
Figure BDA0001342091020000231
Note: the first metal element content is calculated by oxide and the second metal element content 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, performing in-situ coke-burning regeneration, wherein the flow rate of the regeneration air is 200m L/min, the regeneration time is 15min, the regeneration initial temperature is the same as the reaction temperature, collecting the flue gas in the regeneration process, and after the regeneration is finished, according to CO, performing in-situ coke-burning 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 BDA0001342091020000241
TABLE 3
Figure BDA0001342091020000242
Figure BDA0001342091020000251
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
Numbering NOx concentration, ppm CO concentration, vol%
Example 1 S-1 111 0.36
Comparative example 1 D-1 227 0.34
Comparative example 2 D-2 211 0.37
Comparative example 3 D-3 264 0.48
Example 2 S-2 115 0.35
Example 3 S-3 76 0.34
Example 4 S-4 72 0.33
Example 5 S-5 114 0.35
Example 6 S-6 116 0.36
Example 7 S-7 109 0.36
Example 8 S-8 116 0.35
Example 9 S-9 111 0.35
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 1500mL/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
Figure BDA0001342091020000261
Figure BDA0001342091020000271
As can be seen from the data in Table 5, the composition capable of reducing CO and NOx emission provided by the invention 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 the comparative example3And NOx emission performance, and the composition which can reduce CO and NOx emission after aging is used in the evaluation process, and the composition which can reduce CO and NOx emission after aging removes CO and NH3And the NOx activity is still higher, therefore, the composition capable of reducing the emission of CO and NOx provided by the invention has better hydrothermal stability.
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 the comparison of example 1 with examples 7 and 8, 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 9, the treatment with the preferred carbonaceous atmosphere of the invention results in a further improvement in the properties of the composition which reduces 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 (41)

1. 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 subjected to incomplete regeneration, 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 can reduce NH3CO and NOXDischarging of (3);
the composition capable of reducing CO and NOx emissions comprises: the inorganic oxide carrier and a first metal element and a second metal element 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 noble metal elements;
the content of the inorganic oxide carrier is 59.9-94.995 wt% based on the total amount of the composition, the content of the first metal element is 5-40 wt% calculated by oxide, and the content of the second metal element is 0.005-0.1 wt% calculated by element.
2. The method of claim 1, wherein the second metal element is Ru.
3. The method according to claim 1, wherein the inorganic oxide support is contained in an amount of 74.92-91.99 wt% in terms of oxide, the first metal element is contained in an amount of 8-25 wt% in terms of element, and the second metal element is contained in an amount of 0.01-0.08 wt% in terms of element, based on the total amount of the composition.
4. The method according to claim 3, wherein the inorganic oxide support is contained in an amount of 83.93 to 89.95 wt% in terms of oxide, the first metal element is contained in an amount of 10 to 16 wt%, and the second metal element is contained in an amount of 0.05 to 0.07 wt% in terms of element, based on the total amount of the composition.
5. The method of claim 1, wherein the weight ratio of Fe to Co, calculated as oxides, is 1: (0.1-10).
6. The method of claim 5, wherein the weight ratio of Fe to Co, calculated as oxides, is 1 (0.3-3).
7. The method of claim 6, wherein the weight ratio of Fe to Co, calculated as oxides, is 1: (0.4-2).
8. The method of any one of claims 1-7, 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.
9. The method of claim 8, wherein the composition has an XRD pattern with diffraction peaks at 42.6 °, 44.2 ° and 44.9 ° 2 θ.
10. The process of any one of claims 1-7, wherein the inorganic oxide support is selected from at least one of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite, and perovskite.
11. The method of claim 10, wherein the inorganic oxide support is selected from at least one of alumina, spinel, and perovskite.
12. The method of claim 11, wherein the inorganic oxide support is alumina.
13. 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 subjected to incomplete regeneration, 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 can reduce NH3CO and NOXDischarging of (3);
the preparation method of the composition capable of reducing CO and NOx emission comprises the following steps:
(1) mixing and pulping a precursor of an inorganic oxide carrier, a precursor of a first metal element 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 second 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 selected from at least one of 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 precursors of the inorganic oxide carrier, the first metal element precursor and the second metal element precursor are used in such amounts that the content of the inorganic oxide carrier is 59.9 to 94.995 wt% based on the total amount of the composition, the content of the first metal element is 5 to 40 wt% in terms of oxide, and the content of the second metal element is 0.005 to 0.1 wt% in terms of element in the prepared composition.
14. The method of claim 13, wherein the second metal element is Ru.
15. The method of claim 13, wherein the conditions of the first firing comprise: under the atmosphere containing carbon, the temperature is 400-1000 ℃, and the time is 0.1-10 h.
16. The method of claim 15, wherein the conditions of the first firing comprise: the temperature is 450-650 ℃, and the time is 1-3 h.
17. The method of claim 15, wherein the carbon-containing atmosphere is provided by an elemental carbon-containing gas selected from at least one of CO, methane, and ethane.
18. The method of claim 17, wherein the carbon-containing atmosphere is provided by a gas containing an elemental carbon, the elemental carbon-containing gas being CO.
19. The method of claim 18, wherein the carbon-containing atmosphere has a concentration of CO in the range of 1-20% by volume.
20. The method of claim 19, wherein the carbon-containing atmosphere has a concentration of CO of 4-10% by volume.
21. The method of claim 15, wherein 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.
22. The method of claim 21, wherein the alkali treatment method comprises: and mixing the solid product with an alkaline solution for pulping, or leaching the solid product by using the alkaline solution.
23. The method of claim 22, wherein the alkaline solution is a non-metallic alkaline solution.
24. The method of claim 23, wherein the alkaline solution is ammonia and/or an alkaline ammonium salt solution.
25. The method of claim 22, wherein the concentration of the alkaline solution is 0.01-10 mol/L.
26. The method of claim 25, wherein the concentration of the alkaline solution is 0.05-5 mol/L.
27. The method of claim 22, wherein the alkaline solution is used in an amount of 1 to 10 times the pore volume of the solid product.
28. The method of claim 27, wherein the alkaline solution is used in an amount of 1.5 to 5 times the pore volume of the solid product.
29. The method according to any one of claims 13 to 28, wherein the inorganic oxide support is present in an amount of 74.92 to 91.99 wt.% in terms of oxide, the first metallic element is present in an amount of 8 to 25 wt.% in terms of element, and the second metallic element is present in an amount of 0.01 to 0.08 wt.% in terms of element.
30. The method of claim 29, wherein the inorganic oxide support is present in an amount of 83.93 to 89.95 wt.% as oxide, the first metallic element is present in an amount of 10 to 16 wt.% as element, and the second metallic element is present in an amount of 0.05 to 0.07 wt.% as element.
31. The method of any one of claims 13-28, 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).
32. The method as claimed in claim 31, 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).
33. The method of claim 32, 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).
34. The method of any one of claims 13-28, wherein the inorganic oxide support is selected from at least one of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite, and perovskite.
35. The method of claim 34, wherein the inorganic oxide support is selected from at least one of alumina, spinel, and perovskite.
36. The method of claim 35, wherein the inorganic oxide support is alumina.
37. The method of claim 36, wherein the precursor of alumina is subjected to an acidified peptization treatment prior to pulping.
38. The method of claim 37, wherein the acid used in the acidification peptization process is hydrochloric acid, and the conditions of the acidification peptization process comprise: acid-aluminum ratio of 0.12-0.22: 1, the time is 20-40 min.
39. The method of any one of claims 13-28, wherein the first and second metallic element precursors are selected from water soluble salts of first and second metallic elements, respectively.
40. The fluid catalytic cracking process of claim 1 or 13, 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.
41. The fluid catalytic cracking process of claim 40, 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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