CN109201058A - It can reduce CO and NOxComposition of discharge and its preparation method and application and fluidized catalytic cracking method - Google Patents

It can reduce CO and NOxComposition of discharge and its preparation method and application and fluidized catalytic cracking method Download PDF

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Publication number
CN109201058A
CN109201058A CN201710542174.4A CN201710542174A CN109201058A CN 109201058 A CN109201058 A CN 109201058A CN 201710542174 A CN201710542174 A CN 201710542174A CN 109201058 A CN109201058 A CN 109201058A
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composition
metallic element
weight
content
nox emission
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CN109201058B (en
Inventor
宋海涛
姜秋桥
王鹏
孙言
张杰潇
张万虹
李家兴
田辉平
达志坚
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN202010524206.XA priority Critical patent/CN111774078B/en
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201710542174.4A priority patent/CN109201058B/en
Priority to AU2018298192A priority patent/AU2018298192B2/en
Priority to TW107123246A priority patent/TWI786147B/en
Priority to EP18827377.5A priority patent/EP3693085A4/en
Priority to PCT/CN2018/094584 priority patent/WO2019007381A1/en
Priority to US16/626,742 priority patent/US11529612B2/en
Priority to JP2020500124A priority patent/JP7114688B2/en
Priority to RU2020104054A priority patent/RU2772281C2/en
Publication of CN109201058A publication Critical patent/CN109201058A/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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
    • B01D53/8646—Simultaneous elimination of the components
    • B01D53/865—Simultaneous elimination of the components characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

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Abstract

The present invention relates to catalytic cracking fields, disclose composition that can reduce CO and NOx emission and its preparation method and application and fluidized catalytic cracking method, the CO and the composition of NOx emission provided by the invention of can reduce includes: the first metallic element and the second metallic element of inorganic oxide carrier and load on an inorganic, and first metallic element includes Fe and Co, in terms of oxide, the weight ratio of Fe and Co are 1:(0.1-10).Composition Fe and Co provided by the invention is collectively as main metallic element, composition hydrothermal stability with higher, and reduction regenerated gas CO with higher and NOx emission activity can be kept by the further modification of at least one of I A and/or Group IIA metal element.

Description

It can reduce CO and NOxComposition of discharge and its preparation method and application and fluidisation Catalyst cracking method
Technical field
The present invention relates to catalytic cracking fields, and in particular to can reduce the composition of CO and NOx emission, can reduce CO With the preparation method and the composition obtained by this method that can reduce CO and NOx emission, above-mentioned energy of the composition of NOx emission Enough reduce application and the fluidized catalytic cracking method of the composition of CO and NOx emission.
Background technique
The constantly soaring processing cost for having increased considerably refinery of crude oil price, on the one hand refinery passes through buys low price Poor oil reduces cost；On the other hand economic well-being of workers and staff is increased by deep processing mink cell focus.Catalytic cracking is as refinery's weight The important means of oil processing, there is very important status in refinery, is not only oil plant heavy oil balance, production clean fuel Main means, the even more focus of the energy efficiency of oil plant.Catalytic cracking is a kind of quickly urging for rapid catalyst deactivation Change reaction system, solves the problems, such as the main line of catalyst regeneration always catalytic cracking development.
During fluid catalytic cracking (FCC), feedstock oil and regenerated catalyst are catalyzed in riser Rapid contact Cracking reaction reacts and causes its inactivation in the coke laydown to catalyst of generation, and the catalyst of green coke inactivation enters after stripping Regenerator, the regeneration air entered with regenerator bottoms or the air rich in oxygen, which contact, carries out coke burning regeneration.Urging after regeneration Agent is recycled back to reactor and participates in catalytic cracking reaction again.According to the height of flue gas Excess oxygen content in regenerative process or CO oxygen Catalytic cracking unit can be divided into regeneration completely and incomplete regen-eration operation by the abundant degree changed.
In complete regenerative process, the nitrogenous compound in coke and coke generates CO under the action of regeneration air2And N2, The pollutants such as CO and NOx can be also generated simultaneously.It the use of catalyst aid is the important technique measure for controlling CO and NOx emission pollution.
Auxiliary agent for reducing regenerated gas CO discharge is commonly referred to as CO combustion adjuvant, such as CN1022843C discloses one Kind noble metals load-carbon oxide accelerator, active component are 1-1000ppm platinum or 50-1000ppm palladium, and carrier is by (1) The microsphere particle of 99.5~50% Cracking catalyst or its matrix and (2) 0.5-50%Al2O3, 0-20%RE2O3And 0-15% ZrO2Composition, (2) are the external coatings of (1) particle.
Auxiliary agent for controlling flue gas NOx discharge commonly referred to as reduces NOx emission auxiliary agent or NOx reduction auxiliary agent, such as CN102371150A disclose it is a kind of for reducing regeneration fume from catalytic cracking NOx discharge base metal composition, described group The heap ratio for closing object is no more than 0.65 grams per milliliter, on the basis of the weight of the composition, containing in terms of oxide: (1) 50-99 The one or more selected from IIA, IIB, IVB and group vib of the inorganic oxide carrier of weight %, (2) 0.5-40 weight % are non- Precious metal element, and the rare earth element of (3) 0.5-30 weight %.The composition is used for fluid catalytic cracking, can significantly drop Low regenerated flue gas NOx emission.
There are also one kind can reduce the auxiliary agent of regenerated gas CO and NOx emission simultaneously, and it is combustion-supporting and reduce NOx row can to take into account CO Put, it is increasingly strict with environmental regulation, this analog assistant using more prevalent.For example, CN1688508A discloses a kind of drop The composition and its application, the composition of low fluid catalytic cracking flue gas NOx and CO discharge include copper and/or cobalt and load Body, the carrier are selected from hydrotalcite-based compound, spinelle, aluminium oxide, zinc titanate, zinc aluminate, zinc titanate/zinc aluminate. CN102371165A disclose it is a kind of for reducing FCC regenerated gas CO and the low heap of NOx emission than composition, the composition Containing rare earth element and one or more of non-noble metal j elements, preferably base metal is carried on y-type zeolite.US6165933 Disclose a kind of combustion-supporting composition of CO (auxiliary agent) for reducing catalytic cracking process NOx emission, the composition includes: (i) is basic On acidic metal oxide not zeolite-containing；(ii) alkali metal, alkaline-earth metal or their mixture；(iii) oxygen storage components (iv) palladium, the preferred silica-alumina of inorganic oxide carrier, the storage oxygen transition metal oxide preferably aoxidize Cerium.US7045056 disclose it is a kind of for and meanwhile reduce the composition of catalytic cracking process flue gas CO and NOx emission, described group It closes object to contain: a kind of (i) inorganic oxide carrier；(ii) oxide of cerium；(iii) a kind of lanthanide oxide except cerium, Wherein the weight ratio of (ii) and (iii) is at least 1.66:1；(iv) optionally a kind of IB and Group IIB transition metal oxide, with And (v) at least one precious metal element.CN105363444A discloses one kind for reducing FCC regenerated gas CO and NOx emission Composition and preparation method thereof, the composition contains in terms of oxide: (1) rare earth element of 0.5-30 weight %, (2) The precious metal element of 0.01-0.15 weight %, and the inorganic oxide for being substantially free of alkali and alkaline earth metal ions of (3) surplus carry Body；In preparation method, the composition after introducing noble metal is handled before dry and/or roasting through alkaline solution, disclosed in Composition can be controlled effectively caused by capable of effectively avoiding because of regenerated gas CO excessive concentration " after-burning " for fluid catalytic cracking The concentration of emission of CO and NOx in preparation, regeneration flue gas significantly reduces flue gas NOx discharge, and it is unfavorable not cause substantially to FCC product distribution It influences.
During incomplete regen-eration, since Excess oxygen content is low in flue gas, CO concentration is high, NOx in regenerator outlet flue gas Concentration is very low, and reduction-state nitride such as NH3, HCN isoconcentration it is higher.These reduction-state nitride are downstream flowed with flue gas It is dynamic, in the CO boiler for recovering energy, if being substantially oxidized, generate NOx；If not being substantially oxidized, remaining NH3 Etc. easily causing downstream scrubber effluent ammonia nitrogen exceeded, or with the SO in flue gasxReaction generate ammonium salt precipitation cause remaining pot or its Its flue gas equipment for after-treatment (such as SCR) salt crust, influences device long-term operation.Thus, incomplete regen-eration process is helped using catalysis Agent catalyzed conversion NH in a regenerator3Equal substances, can reduce NOx emission in flue gas, extend the device cycle of operation.
US5021144 discloses NH in a kind of reduction incomplete regen-eration FCC apparatus flue gas3The method of discharge, this method are Excessive CO combustion adjuvant is added in a regenerator, additional amount is 2-3 times of the minimum additional amount that can prevent dilute phase bed tail from firing.It should Although method can reduce NH in incomplete regen-eration FCC apparatus flue gas3Discharge, but the usage amount of CO is larger, and it is higher that there are energy consumptions Defect, and be unfavorable for environmental protection.
US4755282 discloses NH in a kind of reduction partial regeneration or incomplete regen-eration FCC apparatus flue gas3The side of discharge Method.This method makes it maintain one in dilute phase bed by the way that ammonia decomposition catalyzer of the granularity at 10-40 μm is added into regenerator Fixed concentration, by NH3It is converted into N2And water.The active component of the ammonia decomposition catalyzer can be dispersed in inorganic oxide load Noble metal on body.
CN101024179A discloses the composition that NOx is restored used in a kind of FCC process, and the composition contains (i) base Acidic metal oxide, (ii) alkali metal, alkaline-earth metal and their mixture and (iii) storage oxygen group not zeolite-containing in sheet Point.The composition prepared with precious metal impregnation, to convert the vapour phase reduction nitrogen class in incomplete regen-eration catalytic cracking unit flue gas Substance reduces flue gas NOx discharge.
Currently, for controlling incomplete regen-eration device flue gas NH3With the auxiliary agent technical research and application report phase of NOx emission It is existing to be suitable for regeneration dress completely due to incomplete regen-eration device flue gas composition and complete regenerating unit significant difference to less The catalyst aid set, the application effect on incomplete regen-eration device are undesirable.Though assistant composition disclosed in above-mentioned technology It so being capable of NH in catalyzed conversion flue gas to a certain extent3Equal reduction-states nitride, but to NH in flue gas3Equal reduction-states nitride Catalyzed conversion activity it is still to be improved, to slow down NH3Deng the influence that deposition salt crust runs equipment, thus needs to develop and be applicable in In the flue gas pollutant emission reduction auxiliary agent of incomplete regen-eration device, flue gas NOx discharge is further decreased.
Summary of the invention
For in prior art regenerative process, NH3The lower defect of catalyzed conversion activity of equal reduction-states nitride, this hair The preparation of the bright composition that the new composition that can reduce CO and NOx emission of one kind is provided, can reduce CO and NOx emission Method and the composition obtained by this method that can reduce CO and NOx discharge, the above-mentioned group that can reduce CO and NOx emission Close application and a kind of fluidized catalytic cracking method of the object in fume treatment.It is provided by the invention to can reduce CO and NOx row The composition put is high to the catalyzed conversion activity of reduction-state nitride, and preparation method is simple, is used in fluid catalytic cracking process, CO and NOx emission in regeneration fume from catalytic cracking can be effectively reduced, CO and the NOx emission provided by the invention of can reduce Composition is especially suitable for incomplete regen-eration fume treatment process.
The present inventor has found in the course of the research, using inorganic oxide as carrier, by containing Fe and Co VIII group non-noble metal j element cooperation at least one of I A and/or Group IIA metal element is used as active component, can It is effectively reduced CO and NOx emission in regeneration fume from catalytic cracking.Speculate its reason can be due to: Fe and Co are collectively as master Metallic element generates certain synergistic effect, further through the further of at least one of I A and/or Group IIA metal element Modification, advantageously reduces the generation of oxidation state nitrogenous compound, and can promote the decomposition of reduction-state nitrogenous compound.
Through further research, it has been found that in the preferred case, after spray drying, the solids that will be obtained after spray drying Matter high-temperature process under carbon-containing atmosphere can more efficiently reduce regeneration fume from catalytic cracking CO and NOx emission.Above-mentioned excellent In the case of choosing, further modulation and stabilization processes are carried out to the structure for the composition that can reduce CO and NOx emission, are made it possible to The composition of CO and NOx emission is enough reduced to NH3The catalyzed conversion activity of equal reduction-states nitride significantly improves, and has more preferable Hydrothermal stability, meet requirement of the regenerator thermal and hydric environment to the composition that can reduce CO and NOx emission.
Based on this, according to the first aspect of the invention, a kind of composition that can reduce CO and NOx emission, the group are provided Closing object includes: inorganic oxide carrier and load the first metallic element on an inorganic and the second metal member Element, first metallic element is selected from group VIII non-noble metal j element, and first metallic element includes Fe and Co, with oxygen The weight ratio of compound meter, Fe and Co are 1:(0.1-10), second metallic element is selected from I A and/or Group IIA metal element At least one of.
According to the second aspect of the invention, a kind of preparation method of composition can reduce CO and NOx emission is provided, it should Method includes:
The presoma of inorganic oxide carrier, the first metallic element presoma, the second metallic element presoma and water are mixed Mashing is closed, slurries is obtained, the slurries is spray-dried, are then roasted；
Wherein, the first metallic element be selected from group VIII non-noble metal j element, and first metallic element include Fe and Co；Second metallic element is selected from least one of I A and/or Group IIA metal element；
Wherein, in the first metallic element presoma, the dosage of the presoma of the presoma and Co of Fe makes, combination obtained In object, in terms of oxide, the weight ratio of Fe and Co are 1:(0.1-10).
According to the third aspect of the invention we, providing one kind can reduce CO and NOx emission as made from above-mentioned preparation method Composition.
According to the fourth aspect of the invention, the above-mentioned composition that can reduce CO and NOx emission is provided in fume treatment Application.
According to the fifth aspect of the invention, provide the above-mentioned composition that can reduce CO and NOx emission catalytic cracking again Application in raw fume treatment.
According to the sixth aspect of the invention, a kind of fluidized catalytic cracking method is provided, this method comprises: by hydrocarbon ils and catalysis Then agent haptoreaction regenerates the catalyst after haptoreaction, the catalyst includes catalytic cracking catalyst and energy The composition of CO and NOx emission are enough reduced, the composition that can reduce CO and NOx emission can drop for the present invention is above-mentioned The composition of low CO and NOx emission.
The composition provided by the invention that can reduce CO and NOx emission, can be in regenerator as assistant for calalytic cracking Higher hydrothermal stability, reduction regenerated gas CO with higher and NOx emission activity are kept in thermal and hydric environment.In addition, this The preparation method of the composition that can reduce CO and NOx emission provided, easy to operate, lower production costs are provided.With use The existing CO that reduces is compared with the FCC method of NOx discharge auxiliary agent, uses the group provided by the invention that can reduce CO and NOx emission The FCC method of object is closed, the composition dosage that can reduce CO and NOx emission is low, and reduction CO and NOx emission activity are higher.
For example, the composition that can reduce CO and NOx emission that the embodiment of the present invention 3 provides, by accounting for total catalyst weight After ratio and FCC major catalyst (Cat-A) blending uniformly of 0.8 weight %, through aging 12 under 800 DEG C, 100% water vapour atmosphere The evaluation of catalytic cracking reaction-regeneration is carried out after hour, with the prior art using active component saturation dipping method preparation can CO is reduced to compare with the composition D-3 of NOx emission, when using the composition provided by the invention that can reduce CO and NOx emission, The concentration of emission of NOx is down to 49ppm by 109ppm in incomplete regen-eration flue gas under aerobic conditions.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the XRD spectrum that can reduce the composition of CO and NOx emission made from embodiment 1 and embodiment 5.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of composition that can reduce CO and NOx emission, the composition includes: that inorganic oxide carries The first metallic element and the second metallic element of body and load on an inorganic, first metallic element are selected from Group VIII non-noble metal j element, and first metallic element includes Fe and Co, in terms of oxide, the weight ratio of Fe and Co are 1:(0.1-10), second metallic element is selected from least one of I A and/or Group IIA metal element.
For the present invention in the composition, the range of choice of the content of the first metallic element and the second metallic element is wider, Preferably, on the basis of the total amount of composition, the content of the inorganic oxide carrier is 50-90 weight %, with oxide Meter, the content of first metallic element are 3-30 weight %, and the content of second metallic element is 1-20 weight %；Into one Preferably, the content of the inorganic oxide carrier is 60-90 weight % to step, in terms of oxide, first metallic element Content is 5-25 weight %, and the content of second metallic element is 5-15 weight %；It is further preferred that the inorganic oxygen The content of compound carrier is 72-85 weight %, and in terms of oxide, the content of first metallic element is 10-16 weight %, The content of second metallic element is 5-12 weight %.
First metallic element of the present invention includes Fe and Co, and the present invention, which is not precluded in first metallic element, also to be contained There are the element in group VIII non-noble metal j element other than Fe and Co, such as Ni.It is according to the present invention a kind of most preferably real Apply mode, first metallic element and second of the composition by inorganic oxide carrier and load on an inorganic Metallic element, and first metallic element is only Fe and Co.
In the present invention, as long as composition can be improved to NH containing Fe and Co in the first metallic element3Equal reduction-states nitridation The catalyzed conversion activity of object, in order to further play the synergistic effect of Fe and Co, it is preferable that in terms of oxide, Fe and Co's Weight ratio is 1:(0.3-3), further preferably 1:(0.4-2).
In the present invention, in the case of no specified otherwise, Fe refers to Fe with Fe in terms of oxide2O3Meter, Co is in terms of oxide Refer to Co with Co2O3Meter.
A preferred embodiment of the invention, the Fe in the composition are at least partly deposited in the form of cementite , it is preferable that the cementite is Fe3C and/or Fe7C3.There is no particular limitation for existing amount of the present invention to cementite, only The performance that can reduce the composition of CO and NOx emission can be effectively improved by partially carbonized iron occur.
A preferred embodiment of the invention, the Co in the composition are at least partly deposited in the form of simple substance cobalt ?.There is no particular limitation for existing amount of the present invention to simple substance cobalt, as long as occurring that part simple substance cobalt can effectively improve can Reduce the performance of the composition of CO and NOx emission.
It should be noted that metallic element is mostly with oxidation state in composition in the existing composition for reducing CO and NOx emission Form exists.Composition of the present invention during the preparation process, is preferably roasted under carbon-containing atmosphere, so that part FeO turns Cementite is turned to, part CoO is converted into simple substance cobalt.
The presence of cementite and/or simple substance cobalt can make composition preferably promote the decomposition of reduction-state nitrogenous compound, The generation of nitrogen oxides is reduced, and nitrogen oxides can be promoted to be reduced to a certain extent.
The composition provided according to the present invention, it is preferable that be 42.6 °, 44.2 ° in 2 θ in the XRD spectrum of the composition With 44.9 ° at have diffraction maximum.
Specifically, the diffraction maximum of 2 θ to be at 42.6 ° and 44.9 ° be cementite；2 θ are at 44.2 ° be simple substance cobalt diffraction Peak.
A preferred embodiment of the invention, in the XRD spectrum of composition provided by the invention, 2 θ are 44.9 ° It is the diffraction maximum at 42.6 ° that the diffraction maximum at place, which is better than 2 θ,.
The composition provided according to the present invention, the inorganic oxide carrier can be various nothings commonly used in the art Machine oxide carrier, for example, selected from aluminium oxide, silica-alumina, zeolite, spinelle, kaolin, diatomite, perlite and At least one of perovskite.In the present invention, the spinelle can be common various spinelles, such as can be magnalium point At least one of spar, gahnite and titanium aluminate.
A preferred embodiment of the invention, the inorganic oxide carrier are selected from aluminium oxide, spinelle and calcium At least one of titanium ore, further preferably aluminium oxide.
In the present invention, the aluminium oxide can be selected from gama-alumina, δ-aluminium oxide, η-aluminium oxide, ρ-aluminium oxide, κ-oxygen Change at least one of aluminium and χ-aluminium oxide, there is no particular limitation to this by the present invention.
The aluminium oxide can be originated from the various colloidal sols or gel or aluminium hydroxide of aluminium.The aluminium hydroxide can select From at least one of gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and boehmite.It is preferred that described Alumina source is from boehmite.
Above-mentioned inorganic oxide carrier is commercially available, and can also be prepared using existing method.
In the present invention, the group ia metal element includes but is not limited to Na and/or K；The Group IIA metallic element Including but not limited at least one of Mg, Ca, Sr and Ba；.
The composition provided according to the present invention, preferably described second metallic element in Na, K, Mg and Ca at least one Kind, further preferably K and/or Mg, most preferably Mg.
A kind of most preferred embodiment according to the present invention, is used cooperatively Fe, Co and Mg as metallic element, can be big Amplitude improves the composition that can reduce CO and NOx emission to NH3The catalyzed conversion activity of equal reduction-states nitride, and make it possible to The composition for enough reducing CO and NOx emission has more excellent hydrothermally stable performance.
A kind of specific embodiment according to the present invention, the composition include: aluminium oxide and load on alumina Fe, Co and Mg, in terms of oxide, the weight ratio of Fe and Co are 1:(0.4-2), on the basis of the total amount of composition, aluminium oxide Content is 72-85 weight %, and in terms of oxide, the total content of Fe and Co are that the content of 10-16 weight %, Mg are 5-12 weight Measure %.
In the present invention, it can reduce each component content in CO and the composition of NOx emission and be all made of X ray fluorescence spectra Analysis method (petrochemical analysis method (RIPP experimental method), Yang Cui is surely equal to be compiled, and Science Press's nineteen ninety publishes) measures.
The present invention also provides a kind of preparation methods of composition that can reduce CO and NOx emission, this method comprises:
The presoma of inorganic oxide carrier, the first metallic element presoma, the second metallic element presoma and water are mixed Mashing is closed, slurries is obtained, the slurries is spray-dried, are then roasted；
Wherein, the first metallic element be selected from group VIII non-noble metal j element, and first metallic element include Fe and Co；Second metallic element is selected from least one of I A and/or Group IIA metal element；
Wherein, in the first metallic element presoma, the dosage of the presoma of the presoma and Co of Fe makes, combination obtained In object, in terms of oxide, the weight ratio of Fe and Co are 1:(0.1-10).
In the present invention, the presoma of the inorganic oxide carrier includes that can obtain inorganic oxygen by subsequent calcination process The various substances of compound carrier, there is no particular limitation to this by the present invention.
The preparation method provided according to the present invention, the inorganic oxide carrier, the first metallic element and the second metal member The selection of element is as described above, details are not described herein.
In the present invention, the presoma of aluminium oxide can various colloidal sols selected from aluminium or gel or aluminium hydroxide.The hydrogen Aluminium oxide can be in gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and boehmite at least It is a kind of.The presoma of the most preferably described aluminium oxide is boehmite.
The preparation method provided according to the present invention, it is preferable that before mashing, acidification glue is carried out to the presoma of aluminium oxide Molten processing, the acidification peptization processing can be carried out according to conventional technical means in the art, it is further preferred that the acidification glue The molten acid used that handles is hydrochloric acid.
The present invention is wider to the range of choice of the condition of the acidification peptization processing, it is preferable that the acidification peptization processing Condition include: acid-aluminum ratio be 0.12-0.22:1, time 20-40min.
In the present invention, in the case of no specified otherwise, the acid-aluminum ratio refers to the hydrochloric acid in terms of the concentrated hydrochloric acid of 36 weight % With the mass ratio of the presoma of the aluminium oxide in terms of butt.
The specific embodiment of the acidification peptization processing can be with are as follows: boehmite is added to the water mashing dispersion, so Hydrochloric acid is added afterwards and is acidified 30min, acid-aluminum ratio 0.18.
According to the present invention, the first metallic element presoma and the second metallic element presoma are respectively selected from the first metal The water soluble salt of element and the second metallic element, such as nitrate, chloride, chlorate or sulfate, the present invention do not have this It is special to limit.
Preparation method according to the present invention, to the first metallic element presoma and the second metallic element presoma Dosage range of choice it is wider, it is preferable that the presoma of the inorganic oxide carrier, the first metallic element presoma and The dosage of two metallic element presomas makes, in composition obtained, on the basis of the total amount of composition, and the inorganic oxide The content of carrier is 50-90 weight %, and in terms of oxide, the content of first metallic element is 3-30 weight %, described the The content of two metallic elements is 1-20 weight %；It is further preferred that the content of the inorganic oxide carrier is 60-90 weight % is measured, in terms of oxide, the content of first metallic element is 5-25 weight %, and the content of second metallic element is 5- 15 weight %；It is further preferred that the content of the inorganic oxide carrier is 72-85 weight %, and in terms of oxide, institute The content for stating the first metallic element is 10-16 weight %, and the content of second metallic element is 5-12 weight %.
The preparation method of the composition provided by the invention that can reduce CO and NOx emission, it is preferable that in terms of oxide The presoma of inorganic oxide carrier, the first metallic element presoma in terms of group VIII non-noble metal j element oxide and The dosage mass ratio of the second metallic element presoma in terms of I A and/or Group IIA metal element oxide is 50-90:3-30: 1-20；It can also be 72-85:10-16:5-12 further it is possible to further be 60-90:5-25:5-15.
In the present invention, the first metallic element presoma is including at least the presoma of Fe and the presoma of Co.
A preferred embodiment of the invention, in the first metallic element presoma, before the presoma and Co of Fe The dosage for driving body makes, and in composition obtained, in terms of oxide, the weight ratio of Fe and Co are preferably 1:(0.3-3), further Preferably 1:(0.4-2).
, according to the invention it is preferred to which the solid content of the slurries is 8-30 weight %.
According to the present invention, to described by the presoma of inorganic oxide carrier, the first metallic element presoma, the second metal There is no particular limitation for the method that elemental precursor and water are mixed with beating, presoma, the first metal to inorganic oxide carrier The addition sequence of elemental precursor and the second metallic element presoma is also without restriction, as long as by before inorganic oxide carrier Drive body, the first metallic element presoma and the second metallic element presoma and water contact, it is preferable that first by the first metal Elemental precursor is dissolved in water, and presoma (the preferably acidified inorganic oxide carrier of inorganic oxide carrier is then added Presoma), obtain the first solution, the second metallic element presoma mixed with water, obtains the second solution, it is finally molten by first Liquid, the mixing of the second solution, then mashing obtains slurries.
In the present invention, the spray drying can be carried out according to conventional technical means in the art, and the present invention does not have this Special to limit, the average grain diameter for the particle that the condition of preferably spray drying obtains spray drying is 60-75 μm, partial size point Cloth range is mainly at 20-100 μm, it is further preferred that the condition of spray drying to be spray-dried in obtained particle, partial size 50% or more is accounted for for 40-80 μm of particle.
According to the present invention, the roasting can be effectively improved using conventional technical means in the art can reduce CO and NOx The composition of discharge is to NH3The catalyzed conversion activity of equal reduction-states nitride, but in order to further improve can reduce CO and The composition of NOx emission is to NH3The catalyzed conversion activity and hydrothermal stability of equal reduction-states nitride, the preferably described roasting are containing It is carried out under carbon atmosphere.The present inventor is found surprisingly that in the course of the research, and the roasting is carried out under carbon-containing atmosphere, It can enable to reduce the composition of CO and NOx emission to NH3The catalyzed conversion activity and hydro-thermal of equal reduction-states nitride are steady Roasting that is qualitative to significantly improve, and carrying out under carbon-containing atmosphere is more advantageous between each active metal component of modulation and carrier Relationship.Active raising is converted into carbide by oxide with active component and reduction-state is related, and hydrothermal stability It is related that improvement may further promote the bonding of each active component, fusion and crosslinking in composition with carbon containing high-temperature process.From XRD is compared in spectrogram and be can see, and occurs the peak type of apparent cementite peak type and simple substance cobalt after processing.Specifically, such as Shown in Fig. 1, there is the diffraction maximum of MgO at 43.0 ° or so places in the XRD spectra of the composition S-5 handled without carbon-containing atmosphere, There is Al at 45.0 ° or so places2O3、Co2AlO4And MgAl2O4Diffraction maximum, and pass through the composition S-1 of carbon-containing atmosphere processing In XRD spectra, not only there is the diffraction maximum of MgO at 43.0 ° or so, has Al at 45.0 ° or so2O3、Co2AlO4And MgAl2O4's Diffraction maximum, and the diffraction maximum at 43.0 ° or so places and 45.0 ° or so places deviates to the left, and the diffraction maximum at 5.0 ° or so places obviously becomes By force, it is attributed to the composition S-1 handled by carbon-containing atmosphere, is diffraction maximum occur at 42.6 °, 44.9 ° in 2 θ, 2 θ are 42.6 °, Diffraction maximum at 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, comparing with composition S-5, composition S-1 exists Occurs diffraction maximum at 44.2 °, 2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance cobalt.
It should be noted that Fig. 1 only lists the XRD spectra within the scope of 41 ° -50 °, be mainly used for illustrating in composition Fe and The existence form of Co.Outside 41 ° of -50 ° of ranges, there is also other diffraction maximums, for example, FeO (2 θ are at 37 °, 65 ° and 59 °) With the diffraction maximum of CoO (2 θ are at 37 °, 65 ° and 31 °), the present invention is not further explained this.
A preferred embodiment of the invention, the condition of the roasting include: to carry out under carbon-containing atmosphere, temperature It is 400-1000 DEG C, preferably 450-650 DEG C, further preferably 500-650 DEG C, time 0.1-10h, preferably 1-3h.
There is no particular limitation for pressure of the present invention to the roasting, can carry out under normal pressure.Such as it can be in 0.01- (absolute pressure) is carried out under 1Mpa.
In the present invention, the carbon-containing atmosphere is provided by the gas containing carbon elements, and the gas of the carbon elements is excellent Gas of the choosing selected from the carbon elements with reproducibility, at least one of further preferably CO, methane and ethane are optimal It is selected as CO.
According to the present invention, partial air and/or inert gas, institute can also be contained in the gas containing carbon elements State inert gas can for various inert gases commonly used in the art, the preferably described inert gas be selected from nitrogen, argon gas and At least one of helium, further preferably nitrogen.
A preferred embodiment of the invention, the carbon-containing atmosphere are mentioned by the mixed gas containing CO and nitrogen For, and the volumetric concentration of CO is preferably 1-20% in carbon-containing atmosphere, further preferably 4-10%.Using of the invention preferred Embodiment can not only better meet processing requirement, additionally it is possible to guarantee the safety of operator.
In the present invention, the roasting can carry out in roaster, the roaster can be catalytic cracking catalyst and Rotary roaster used in auxiliary agent production.The gas of carbon elements is inverse with the solid material in roaster in roaster Stream contact.
The present invention also provides the compositions that can reduce CO and NOx emission as made from above-mentioned preparation method.
Can reduce as made from above-mentioned preparation method in CO and the composition of NOx emission containing Fe and Co, IA and/or At least one of Group IIA metal element, above-mentioned metallic element are used cooperatively, and make it possible to reduce the combination of CO and NOx emission Object is to NH3The catalyzed conversion activity of equal reduction-states nitride significantly improves, and makes it possible to reduce the combination of CO and NOx emission Object has preferable hydrothermal stability.
The present invention also provides application of the above-mentioned composition that can reduce CO and NOx emission in fume treatment.This hair The composition of bright offer can be used for handling any required flue gas for reducing CO and NOx emission.
The present invention also provides the above-mentioned compositions that can reduce CO and NOx emission in regeneration fume from catalytic cracking processing Application.The above-mentioned composition that can reduce CO and NOx emission is especially suitable for reducing complete regenerated flue gas and incomplete regen-eration The discharge of CO and NOx in flue gas, the composition provided by the invention that can reduce CO and NOx emission are more applicable for reducing endless The discharge of CO and NOx in full regenerated flue gas.Therefore, the present invention provides the above-mentioned compositions that can reduce CO and NOx emission to exist Application in catalytic cracking incomplete regen-eration fume treatment.
The present invention also provides a kind of fluidized catalytic cracking methods, this method comprises: by hydrocarbon ils and catalyst haptoreaction, Then the catalyst after haptoreaction is regenerated, the catalyst include catalytic cracking catalyst and can reduce CO and The composition of NOx emission, the composition that can reduce CO and NOx emission can reduce CO and NOx row for the present invention is above-mentioned The composition put.
The fluidized catalytic cracking method provided according to the present invention, it is preferable that on the basis of the total amount of catalyst, it is described can Reduce the content of the composition of CO and NOx emission for 0.05-5 weight %, further preferably 0.1-3 weight %, further Preferably 0.5-2.5 weight %.
The fluidized catalytic cracking method provided according to the present invention, it is preferable that by hydrocarbon ils and catalyst haptoreaction, then will Catalyst after haptoreaction carries out incomplete regen-eration, it is further preferred that oxygen in the flue gas that the incomplete regen-eration generates Concentration be not more than 0.5 volume %.
There is no particular limitation to the hydrocarbon ils by the present invention, can be the processed conventionally various hydrocarbon ils in catalytic cracking field, Such as vacuum gas oil (VGO), reduced crude, decompression residuum, deasphalted oil, wax tailings or hydrotreating oil.
There is no particular limitation to the catalytic cracking catalyst by the present invention, can be in existing catalytic cracking catalyst One or more, can be commercially available or prepare according to existing method.
It is provided by the invention to can reduce CO and the composition of NOx emission can be a kind of independent particle, it is also possible to As catalyst cracking particles part of the whole.It is preferred that the combination provided by the invention that can reduce CO and NOx emission Object is used cooperatively as a kind of independent particle with catalyst cracking particles.
In the present invention, in the case of no specified otherwise, the ppm refers to volumetric concentration.
In fluidized catalytic cracking method of the present invention, the method for the catalyst regeneration does not have compared with existing regeneration method There are particular/special requirement, including partial regeneration, incomplete regen-eration and complete regenerative operation mode.The regeneration method can be found in Chen Junwu Chief editor, Sinopec publishing house page 1234 page -1343 of " catalytic cracking process and the engineering " published in 2005.It is preferred that regeneration temperature Degree is 650 DEG C -730 DEG C.
Below by way of the specific embodiment implementation process that the present invention will be described in detail and generated beneficial effect, it is intended to help Where reader more clearly understands Spirit Essence of the invention, but any restriction cannot be constituted to practical range of the invention.
It can reduce constituent content in CO and the composition of NOx emission in following embodiment and be all made of X ray fluorescence spectra (XRF) method measures, and referring specifically to petrochemical analysis method (RIPP experimental method), Yang Cui is waited surely and compiled, Science Press 1990 Year publishes.The composition of CO and NOx emission be can reduce in embodiment using X-ray diffractometer (Siemens company D5005 type) XRD spectra is obtained, structure determination, Cu target, K α radiation, solid probe, tube voltage 40kV, tube current 40mA are carried out.
It is raw materials used in embodiment and comparative example: cobalt nitrate [Co (NO3)2·6H2O] it is to analyze pure, ferric nitrate [Fe (NO3)3·9H2O] it is that analysis is pure, magnesia [MgO] is that analysis is pure, is produced by Sinopharm Chemical Reagent Co., Ltd.；It is quasi- Boehmite is technical grade product, and 64 weight % of alumina content, pore volume is 0.31 ml/g, Shandong Aluminium Industrial Corp's production； Hydrochloric acid, concentration are 36.5 weight %, analyze pure, Beijing Chemical Plant's production；Carbon monoxide, concentration are 10 volume %, and nitrogen does flat Weigh gas, the production of Beijing Hai Pubeifen gas industry Co., Ltd；Catalytic cracking catalyst industrial products (Cat-A, the catalyst trade mark CGP-1), Na2O content 0.24 weight %, RE2O3Content 3.2 weight %, Al2O348.0 weight % of content, average grain diameter 67 are micro- Rice, the production of Sinopec catalyst Co., Ltd.
Embodiment 1
(1) 2.62kg boehmite is added to be beaten in 14.2kg deionized water and is dispersed, 238mL hydrochloric acid is then added It is acidified 15min, aluminium stone colloid is obtained, by the ferric nitrate in terms of metal oxide (with Fe2O3Meter, similarly hereinafter) 100g, cobalt nitrate (with Co2O3Meter, similarly hereinafter) 100g is added stirring in 3500mL water and is added thereto aluminium stone colloid to abundant dissolution, stirs 15min, obtain To the first solution；100g MgO is added in 360g water, is added after stirring 10min into the first solution, stirs 20min Afterwards, slurries are obtained, the slurries are spray-dried, (average grain diameter is 65 μm to the particle 100g for taking spray drying to obtain, grain Diameter is that 40-80 μm of particle accounts for 60%, similarly hereinafter) it is transferred in tube furnace, CO concentration is passed through as 10 bodies with the flow of 100mL/min The CO/N of product %2Mixed gas handles 1.5h at 600 DEG C, obtains composition S-1.
Each component assay result is listed in table 1 in composition S-1.
XRD analysis is carried out to composition S-1, XRD spectra as shown in Figure 1, as can be seen from Figure 1,
There is the diffraction maximum of MgO at 43.0 ° or so places in the XRD spectra of the composition S-5 handled without carbon-containing atmosphere, There is Al at 45.0 ° or so places2O3、Co2AlO4And MgAl2O4Diffraction maximum, and pass through the composition S-1 of carbon-containing atmosphere processing In XRD spectra, not only there is the diffraction maximum of MgO at 43.0 ° or so, has Al at 45.0 ° or so2O3、Co2AlO4And MgAl2O4's Diffraction maximum, and the diffraction maximum at 43.0 ° or so places and 45.0 ° or so places deviates to the left, and the diffraction maximum at 5.0 ° or so places obviously becomes By force, it is attributed to the composition S-1 handled by carbon-containing atmosphere, is diffraction maximum occur at 42.6 °, 44.9 ° in 2 θ, 2 θ are 42.6 °, Diffraction maximum at 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, comparing with composition S-5, composition S-1 exists Occurs diffraction maximum at 44.2 °, 2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance cobalt.
It should be noted that Fig. 1 only lists the XRD spectra within the scope of 41 ° -50 °, be mainly used for illustrating in composition Fe and The existence form of Co.Outside 41 ° of -50 ° of ranges, there is also other diffraction maximums, for example, FeO (2 θ are at 37 °, 65 ° and 59 °) With the diffraction maximum of CoO (2 θ be 37 °, 65 ° and 31 ° place), the diffraction maximum of diffraction maximum and FeC and simple substance Co outside 41 ° of -50 ° of ranges Unrelated, the present invention does not do further spectrum elucidation to this.
Embodiment 2
(1) 2.56kg boehmite is added to be beaten in 13.9kg deionized water and is dispersed, 232mL hydrochloric acid is then added It is acidified 15min, obtains aluminium stone colloid, ferric nitrate 140g, the cobalt nitrate 60g in terms of metal oxide are added in 3500mL water Aluminium stone colloid is added thereto to abundant dissolution, stirs 15min, obtain the first solution by stirring；160gMgO is added to 480g In water, it is added after stirring 10min into the first solution, after stirring 20min, obtains slurries, the slurries are spray-dried, The particle 100g for taking spray drying to obtain is transferred in tube furnace, is passed through CO concentration with the flow of 100mL/min as 10 volume % CO/N2Mixed gas obtains composition S-2.
Each component assay result is listed in table 1 in composition S-2.The XRD analysis result and embodiment 1 of composition S-2 It is similar.In the XRD spectra of composition S-2 by carbon-containing atmosphere processing, not only there is the diffraction maximum of MgO at 43.0 ° or so, 45.0 ° or so have Al2O3、Co2AlO4And MgAl2O4Diffraction maximum, and the diffraction maximum at 43.0 ° or so places and 45.0 ° or so places It deviates to the left, and the diffraction maximum at 5.0 ° or so places obviously becomes the composition S-2 for being attributed to handle by force by carbon-containing atmosphere, 2 θ is diffraction maximum occur at 42.6 °, 44.9 °, and 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction Peak.In addition, comparing with composition S-5, there is diffraction maximum at 44.2 ° in composition S-2, and 2 θ are that the diffraction maximum at 44.2 ° is single The diffraction maximum of matter cobalt.
Embodiment 3
(1) 2.34kg boehmite is added to be beaten in 12.7kg deionized water and is dispersed, 212mL hydrochloric acid is then added It is acidified 15min, obtains aluminium stone colloid, ferric nitrate 100g, the cobalt nitrate 200g in terms of metal oxide are added in 4000mL water Aluminium stone colloid is added thereto to abundant dissolution, stirs 15min, obtain the first solution by stirring；200gMgO is added to 600g In water, it is added after stirring 10min into the first solution, after stirring 20min, obtains slurries, the slurries are spray-dried, The particle 100g for taking spray drying to obtain is transferred in tube furnace, is passed through CO concentration with the flow of 100mL/min as 10 volume % CO/N2Mixed gas handles 1h at 650 DEG C, obtains composition S-3.
Each component assay result is listed in table 1 in composition S-3.The XRD analysis result and embodiment 1 of composition S-3 It is similar.In the XRD spectra of composition S-3 by carbon-containing atmosphere processing, not only there is the diffraction maximum of MgO at 43.0 ° or so, 45.0 ° or so have Al2O3、Co2AlO4And MgAl2O4Diffraction maximum, and the diffraction maximum at 43.0 ° or so places and 45.0 ° or so places It deviates to the left, and the diffraction maximum at 5.0 ° or so places obviously becomes the composition S-3 for being attributed to handle by force by carbon-containing atmosphere, in 2 θ To there is diffraction maximum at 42.6 °, 44.9 °, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction Peak.In addition, comparing with composition S-5, there is diffraction maximum at 44.2 ° in composition S-3, and 2 θ are that the diffraction maximum at 44.2 ° is single The diffraction maximum of matter cobalt.
Embodiment 4
(1) 2.25kg boehmite is added to be beaten in 12.2kg deionized water and is dispersed, 204mL hydrochloric acid is then added It is acidified 15min, obtains aluminium stone colloid, ferric nitrate 200g, the cobalt nitrate 120g in terms of metal oxide are added in 3500mL water Aluminium stone colloid is added thereto to abundant dissolution, stirs 15min, obtain the first solution by stirring；240g MgO is added to 720g In water, it is added after stirring 10min into the first solution, after stirring 20min, obtains slurries, the slurries are done by spraying Dry, the particle 100g for taking spray drying to obtain is transferred in tube furnace, is passed through CO concentration with the flow of 100mL/min as 10 bodies The CO/N of product %2Mixed gas handles 1.5h at 600 DEG C, obtains composition S-4.
Each component assay result is listed in table 1 in composition S-4.The XRD analysis result and embodiment 1 of composition S-4 It is similar.In the XRD spectra of composition S-4 by carbon-containing atmosphere processing, not only there is the diffraction maximum of MgO at 43.0 ° or so, 45.0 ° or so have Al2O3、Co2AlO4And MgAl2O4Diffraction maximum, and the diffraction maximum at 43.0 ° or so places and 45.0 ° or so places It deviates to the left, and the diffraction maximum at 5.0 ° or so places obviously becomes the composition S-4 for being attributed to handle by force by carbon-containing atmosphere, 2 θ is diffraction maximum occur at 42.6 °, 44.9 °, and 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction Peak.In addition, comparing with composition S-5, there is diffraction maximum at 44.2 ° in composition S-4, and 2 θ are that the diffraction maximum at 44.2 ° is single The diffraction maximum of matter cobalt.
Embodiment 5
According to the method for embodiment 1, unlike, the CO/N for being 10 volume % by CO concentration2Mixed gas replaces with sky Gas obtains composition S-5.
Each component assay result is listed in table 1 in composition S-5.XRD analysis is carried out to composition S-5, from XRD spectra (as shown in Figure 1) can be seen that, 2 θ be 42.6 °, 44.2 ° and 44.9 ° at without obvious diffraction maximum, it was demonstrated that in composition S-5 Fe and Co exists in the form of an oxide.
Embodiment 6
According to the method for embodiment 1, unlike, in terms of metal oxide, MgO is replaced with the CaO of phase homogenous quantities, is obtained To composition S-6.
Each component assay result is listed in table 1 in composition S-6.The XRD analysis result and embodiment 1 of composition S-6 It is similar.In the XRD spectra of composition S-6 by carbon-containing atmosphere processing, not only there is the diffraction maximum of MgO at 43.0 ° or so, 45.0 ° or so have Al2O3、Co2AlO4And MgAl2O4Diffraction maximum, and the diffraction maximum at 43.0 ° or so places and 45.0 ° or so places It deviates to the left, and the diffraction maximum at 5.0 ° or so places obviously becomes the composition S-6 for being attributed to handle by force by carbon-containing atmosphere, 2 θ is diffraction maximum occur at 42.6 °, 44.9 °, and 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction Peak.In addition, comparing with composition S-5, there is diffraction maximum at 44.2 ° in composition S-6, and 2 θ are that the diffraction maximum at 44.2 ° is single The diffraction maximum of matter cobalt.
Embodiment 7
According to the method for embodiment 1, unlike, the dosage of the ferric nitrate in terms of metal oxide is 50g, cobalt nitrate Dosage be 150g, obtain composition S-7.
Each component assay result is listed in table 1 in composition S-7.The XRD analysis result and embodiment 1 of composition S-7 It is similar.In the XRD spectra of composition S-7 by carbon-containing atmosphere processing, not only there is the diffraction maximum of MgO at 43.0 ° or so, 45.0 ° or so have Al2O3、Co2AlO4And MgAl2O4Diffraction maximum, and the diffraction maximum at 43.0 ° or so places and 45.0 ° or so places It deviates to the left, and the diffraction maximum at 5.0 ° or so places obviously becomes the composition S-7 for being attributed to handle by force by carbon-containing atmosphere, in 2 θ To there is diffraction maximum at 42.6 °, 44.9 °, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction Peak.In addition, comparing with composition S-5, there is diffraction maximum at 44.2 ° in composition S-7, and 2 θ are that the diffraction maximum at 44.2 ° is single The diffraction maximum of matter cobalt.
Embodiment 8
According to the method for embodiment 1, unlike, the dosage of the ferric nitrate in terms of metal oxide is 150g, cobalt nitrate Dosage be 50g, obtain composition S-8.
Each component assay result is listed in table 1 in composition S-8.The XRD analysis result and embodiment 1 of composition S-8 It is similar.In the XRD spectra of composition S-8 by carbon-containing atmosphere processing, not only there is the diffraction maximum of MgO at 43.0 ° or so, 45.0 ° or so have Al2O3、Co2AlO4And MgAl2O4Diffraction maximum, and the diffraction maximum at 43.0 ° or so places and 45.0 ° or so places It deviates to the left, and the diffraction maximum at 5.0 ° or so places obviously becomes the composition S-8 for being attributed to handle by force by carbon-containing atmosphere, 2 θ is diffraction maximum occur at 42.6 °, 44.9 °, and 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction Peak.In addition, comparing with composition S-5, there is diffraction maximum at 44.2 ° in composition S-8, and 2 θ are that the diffraction maximum at 44.2 ° is single The diffraction maximum of matter cobalt.
Embodiment 9
According to the method for embodiment 1, it unlike, is replaced with ethane/nitrogen mixed gas that ethane concentration is 10 volume % Change the CO/N that concentration is 10 volume %2Mixed gas obtains composition S-9.
Each component assay result is listed in table 1 in composition S-9.The XRD analysis result and embodiment 1 of composition S-9 It is similar.In the XRD spectra of composition S-9 by carbon-containing atmosphere processing, not only there is the diffraction maximum of MgO at 43.0 ° or so, 45.0 ° or so have Al2O3、Co2AlO4And MgAl2O4Diffraction maximum, and the diffraction maximum at 43.0 ° or so places and 45.0 ° or so places It deviates to the left, and the diffraction maximum at 5.0 ° or so places obviously becomes the composition S-9 for being attributed to handle by force by carbon-containing atmosphere, 2 θ is diffraction maximum occur at 42.6 °, 44.9 °, and 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction Peak.In addition, comparing with composition S-5, there is diffraction maximum at 44.2 ° in composition S-9, and 2 θ are that the diffraction maximum at 44.2 ° is single The diffraction maximum of matter cobalt.
Comparative example 1
According to the method for embodiment 1, unlike, in terms of metal oxide, nitric acid is replaced with the ferric nitrate of phase homogenous quantities Cobalt obtains composition D-1.
Each component assay result is listed in table 1 in composition D-1.
Comparative example 2
According to the method for embodiment 1, unlike, in terms of metal oxide, nitric acid is replaced with the cobalt nitrate of phase homogenous quantities Iron obtains composition D-2.
Each component assay result is listed in table 1 in composition D-2.
Comparative example 3
Comparative composition is prepared referring to US6800586 the method.The gama-alumina microsphere carrier of 34.4 grams of drying is taken, The solution oxide impregnation aluminium microballoon being made into 10.09g cerous nitrate, 2.13g lanthanum nitrate and 18mL water, after dipping through 120 DEG C of drying, After 600 DEG C roast 1 hour, then the solution dipping being made into 2.7g copper nitrate and 18mL water, through 120 DEG C of drying, 600 DEG C of roastings 1 Hour obtains composition D-3.In composition D-3, on the basis of composition D-3 total amount, in terms of oxide, RE2O3Content be 12 The content of weight %, CuO are 2.3 weight % (RE represents lanthanide element).
Table 1
Note: for each component content in terms of oxide, unit is weight %.
Test example 1
This test example is used to reduce the composition that can reduce CO and NOx emission that above-described embodiment and comparative example provide Under aerobic conditions in incomplete regen-eration flue gas CO and NOx emission effect.
The composition and above-mentioned catalytic cracking catalyst (Cat-A) that CO and NOx emission will be reduced blend uniformly (energy The composition for enough reducing CO and NOx emission accounts for the composition and catalytic cracking catalyst total amount that can reduce CO and NOx emission 2.2 weight %) catalytic cracking reaction-regeneration evaluation is carried out after aging 12h under 800 DEG C, 100% water vapour atmosphere.
The catalytic cracking reaction-regeneration evaluation carries out on small fixed simulated flue gas drop NOx device, through aging Loaded catalyst is 10g, and reaction temperature is 650 DEG C, and feed gas volume flow is 1500mL/min.Unstripped gas contains 3.7 bodies The CO of product %, the oxygen of 0.5 volume %, the NH of 800ppm3, surplus N2.Gaseous product is analyzed by online infrared spectrum analyser, NH after being reacted3, NOx and CO concentration, be as a result listed in table 2.
Table 2
Number NOx concentration, ppm NH3Concentration, ppm CO concentration, volume %
Embodiment 1 S-1 71 103 2.81
Comparative example 1 D-1 154 218 2.76
Comparative example 2 D-2 141 216 2.85
Comparative example 3 D-3 109 321 3.15
Embodiment 2 S-2 73 105 2.8
Embodiment 3 S-3 49 67 2.72
Embodiment 4 S-4 48 64 2.71
Embodiment 5 S-5 75 107 2.79
Embodiment 6 S-6 79 112 2.8
Embodiment 7 S-7 72 109 2.83
Embodiment 8 S-8 77 111 2.78
Embodiment 9 S-9 70 105 2.8
As can be seen from Table 2, using the composition provided by the invention that can reduce CO and NOx emission for being catalyzed Cracking process incomplete regen-eration process (aerobic conditions), the composition tool that can reduce CO and NOx emission provided compared with comparative example Having preferably reduces CO, NH3It and is that can reduce CO and NOx after aging used in evaluation procedure with NOx emission performance The composition of discharge, composition removing CO, NH that can reduce CO and NOx emission after aging3It is still higher with NOx activity, because This, the CO and the composition of NOx emission provided by the invention of can reduce has preferable hydrothermal stability.
Test example 2
This test example is used to reduce the composition that can reduce CO and NOx emission that above-described embodiment and comparative example provide Under oxygen free condition in incomplete regen-eration flue gas CO and NOx emission effect.
According to the method for test example 1, the difference is that, unstripped gas contains the CO of 3.7 volume %, the NH of 800ppm3, surplus For N2.NH after being reacted3, NOx and CO concentration, be as a result listed in table 3.
Table 3
Number NOx concentration, ppm NH3Concentration, ppm CO concentration, volume %
Embodiment 1 S-1 0 182 3.69
Comparative example 1 D-1 0 386 3.69
Comparative example 2 D-2 0 381 3.7
Comparative example 3 D-3 0 423 3.7
Embodiment 2 S-2 0 186 3.7
Embodiment 3 S-3 0 117 3.67
Embodiment 4 S-4 0 113 3.69
Embodiment 5 S-5 0 188 3.67
Embodiment 6 S-6 0 197 3.67
Embodiment 7 S-7 0 185 3.67
Embodiment 8 S-8 0 189 3.67
Embodiment 9 S-9 0 183 3.68
From table 3 it can be seen that even if handling incomplete regen-eration flue gas under anaerobic, it is provided by the invention to can reduce CO and the composition of NOx emission have compared with the composition that CO and NOx is discharged that can reduce that comparative example provides and preferably reduce CO And NH3Emission performance, and be the composition that can reduce CO and NOx emission after aging, aging used in evaluation procedure The composition removing CO and NH that can reduce CO and NOx emission afterwards3Activity is still higher, therefore, provided by the invention to drop Low CO and the composition of NOx emission have preferable hydrothermal stability.
It can be seen that the composition provided by the invention that can reduce CO and NOx emission from table 2 and 3 data of table to be suitable for Incomplete regen-eration under aerobic and oxygen free condition has preferable regenerated flue gas processing capacity.Particularly, from embodiment 1 and in fact The comparison of example 5 is applied as can be seen that carrying out under carbon-containing atmosphere using currently preferred roasting, makes it possible to reduce CO and NOx row The composition properties put further increase；From embodiment 1 and the comparison of embodiment 6 as can be seen that using currently preferred metal Element, the composition properties for making it possible to reduce CO and NOx emission further increase；From embodiment 1 and embodiment 7, embodiment 8 Comparison makes it possible to reduce the composition properties of CO and NOx emission as can be seen that using currently preferred Fe and Co mass ratio It further increases；It compares can be seen that with embodiment 9 from embodiment 1 and be handled using the present invention preferably carbon-containing atmosphere, made The composition properties that CO and NOx emission must be can reduce further increase；It can from embodiment 1 and comparative example 1-3 comparison Out, by the way that Fe and Co to be used cooperatively, the composition properties for making it possible to reduce CO and NOx emission increase substantially the present invention.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (17)

1. a kind of composition that can reduce CO and NOx emission, which is characterized in that the composition includes: inorganic oxide carrier And load the first metallic element and the second metallic element on an inorganic, first metallic element are selected from the VIII group non-noble metal j element, and first metallic element includes Fe and Co, in terms of oxide, the weight ratio of Fe and Co are 1: (0.1-10), second metallic element are selected from least one of I A and/or Group IIA metal element.
2. composition according to claim 1, wherein on the basis of the total amount of composition, the inorganic oxide carrier Content be 50-90 weight %, in terms of oxide, the content of first metallic element is 3-30 weight %, second gold medal The content for belonging to element is 1-20 weight %；
Preferably, the content of the inorganic oxide carrier is 60-90 weight %, in terms of oxide, first metallic element Content be 5-25 weight %, the content of second metallic element is 5-15 weight %；
It is further preferred that the content of the inorganic oxide carrier is 72-85 weight %, and in terms of oxide, first gold medal The content for belonging to element is 10-16 weight %, and the content of second metallic element is 5-12 weight %.
3. composition according to claim 1 or 2, wherein in terms of oxide, the weight ratio of Fe and Co are 1:(0.3-3), Preferably 1:(0.4-2).
4. composition described in any one of -3 according to claim 1, wherein
Fe in the composition exists at least partly in the form of cementite；
Co in the composition exists at least partly in the form of simple substance cobalt；
It preferably, is to have diffraction maximum at 42.6 °, 44.2 ° and 44.9 ° in 2 θ in the XRD spectrum of the composition.
5. composition described in any one of -4 according to claim 1, wherein the inorganic oxide carrier is selected from oxidation At least one of aluminium, silica-alumina, zeolite, spinelle, kaolin, diatomite, perlite and perovskite；
Preferably, the inorganic oxide carrier is selected from least one of aluminium oxide, spinelle and perovskite, further preferably For aluminium oxide.
6. composition described in any one of -5 according to claim 1, wherein
Second metallic element is selected from least one of Na, K, Mg and Ca, preferably K and/or Mg, most preferably Mg.
7. a kind of preparation method for the composition that can reduce CO and NOx emission, which is characterized in that this method comprises:
The presoma of inorganic oxide carrier, the first metallic element presoma, the second metallic element presoma and water are mixed and beaten Slurry, obtains slurries, the slurries is spray-dried, are then roasted；
Wherein, the first metallic element is selected from group VIII non-noble metal j element, and first metallic element includes Fe and Co；The Two metallic elements are selected from least one of I A and/or Group IIA metal element；
Wherein, in the first metallic element presoma, the dosage of the presoma of the presoma and Co of Fe makes, composition obtained In, in terms of oxide, the weight ratio of Fe and Co are 1:(0.1-10).
8. preparation method according to claim 7, wherein the condition of the roasting includes: to carry out under carbon-containing atmosphere, temperature Degree be 400-1000 DEG C, preferably 450-650 DEG C, time 0.1-10h, preferably 1-3h；
Preferably, the carbon-containing atmosphere is provided by the gas containing carbon elements, and the gas of the carbon elements is selected from CO, methane At least one of with ethane, preferably CO；
Preferably, the volumetric concentration of CO is 1-20%, preferably 4-10% in carbon-containing atmosphere.
9. preparation method according to claim 7 or 8, wherein the presoma of the inorganic oxide carrier, the first metal The dosage of elemental precursor and the second metallic element presoma makes, in composition obtained, on the basis of the total amount of composition, The content of the inorganic oxide carrier is 50-90 weight %, and in terms of oxide, the content of first metallic element is 3-30 Weight %, the content of second metallic element are 1-20 weight %；
Preferably, the content of the inorganic oxide carrier is 60-90 weight %, in terms of oxide, first metallic element Content be 5-25 weight %, the content of second metallic element is 5-15 weight %；
It is further preferred that the content of the inorganic oxide carrier is 72-85 weight %, and in terms of oxide, first gold medal The content for belonging to element is 10-16 weight %, and the content of second metallic element is 5-12 weight %.
10. the preparation method according to any one of claim 7-9, wherein the presoma of the presoma and Co of Fe Dosage makes, and in composition obtained, in terms of oxide, the weight ratio of Fe and Co are 1:(0.3-3), preferably 1:(0.4-2).
11. preparation method according to any one of claims of claim 7-10, wherein the inorganic oxide carrier is selected from oxygen Change at least one of aluminium, silica-alumina, zeolite, spinelle, kaolin, diatomite, perlite and perovskite；It is preferred that Ground, the inorganic oxide carrier are selected from least one of aluminium oxide, spinelle and perovskite, further preferably aoxidize Aluminium；
Preferably, before mashing, acidification peptization processing is carried out to the presoma of aluminium oxide, it is further preferred that the acidification The acid that peptization processing uses is hydrochloric acid, and the condition of the acidification peptization processing includes: acid-aluminum ratio 0.12-0.22:1, time 20- 40min。
12. the preparation method according to any one of claim 7-11, wherein the second metallic element is selected from Na, K, Mg At least one of with Ca, preferably K and/or Mg, most preferably Mg；
The first metallic element presoma and the second metallic element presoma are respectively selected from the first metallic element and the second metal The water soluble salt of element.
13. can reduce the combination of CO and NOx emission made from the preparation method as described in any one of claim 7-12 Object.
14. can reduce the composition of CO and NOx emission described in any one of claim 1-6 and 13 in fume treatment Application.
15. can reduce described in any one of claim 1-6 and 13 composition of CO and NOx emission catalytic cracking again Application in raw fume treatment.
16. a kind of fluidized catalytic cracking method, this method comprises: by hydrocarbon ils and catalyst haptoreaction, then by haptoreaction Catalyst afterwards is regenerated, and the catalyst includes catalytic cracking catalyst and the composition that can reduce CO and NOx emission, It is characterized in that, the CO and the composition of NOx emission of can reduce is energy described in any one of claim 1-6 and 13 Enough reduce the composition of CO and NOx emission.
17. fluidized catalytic cracking method according to claim 16, wherein on the basis of the total amount of catalyst, the energy The content for enough reducing the composition of CO and NOx emission is 0.05-5 weight %, preferably 0.1-3 weight %.
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