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

Abstract

The 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, the second metallic element, third metallic element and the 4th 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:(0.05-20).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 at least one of at least one of I A and/or Group IIA metal element, I B-VIIB race non-noble metal j element and precious 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 It is the preparation method and the composition obtained by this method that can reduce CO and NOx emission of CO and the composition of NOx emission, above-mentioned It can 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 discloses a kind of base metal composition for reducing regeneration fume from catalytic cracking NOx emission, and 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 contains There are rare earth element and one or more of non-noble metal j elements, preferably base metal is carried on y-type zeolite.US6165933 is public Opened it is a kind of reduce catalytic cracking process NOx emission the combustion-supporting composition of CO (auxiliary agent), the composition includes: (i) substantially Acidic metal oxide not zeolite-containing；(ii) alkali metal, alkaline-earth metal or their mixture；(iii) oxygen storage components and (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. Although this method can reduce NH in incomplete regen-eration FCC apparatus flue gas3Discharge, but the usage amount of CO is larger, there are energy consumption compared with High defect, and it is 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 side 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 emission, the above-mentioned combination that can reduce CO and NOx emission 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 emission Composition it is high to the catalyzed conversion of reduction-state nitride activity, preparation method is simple, in fluid catalytic cracking process, energy Enough it is effectively reduced CO and NOx emission in regeneration fume from catalytic cracking.
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 cooperates at least one of I A and/or Group IIA metal element, I B-VIIB race base metal At least one of element and at least one of precious metal element are used as active component, can be effectively reduced catalysis CO and NOx emission in cracking regenerated flue gas.Speculate its reason can be due to: Fe and Co passes through collectively as main metallic element At least one of at least one of I A and/or Group IIA metal element, I B-VIIB race non-noble metal j element and expensive The further modification of at least one of metallic element 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, before precious metal element dipping, will be sprayed The solid matter obtained after drying high-temperature process under carbon-containing atmosphere, can more efficiently reduce regeneration fume from catalytic cracking CO and NOx emission；Still more preferably, alkali process is carried out to the solid product obtained after precious metal impregnation, it can More efficiently reduce regeneration fume from catalytic cracking CO and NOx emission.Under above-mentioned preferable case, to can reduce CO and NOx The structure of the composition of discharge carries out further modulation and stabilization processes, makes it possible to reduce the composition of CO and NOx emission To NH3The catalyzed conversion activity of equal reduction-states nitride significantly improves, and has better hydrothermal stability, meets regenerator water Requirement of the thermal 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 Close object include: inorganic oxide carrier and load the first metallic element on an inorganic, the second metallic element, Third metallic element and the 4th metallic element, first metallic element are selected from group VIII non-noble metal j element, and described the One metallic element includes Fe and Co, and in terms of oxide, the weight ratio of Fe and Co are 1:(0.05-20), second metallic element Selected from least one of I A and/or Group IIA metal element, the third metallic element is selected from your non-gold of I B-VIIB race Belong at least one of element, the 4th metallic element is selected from least one of precious metal element.
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:
(1) by the presoma of inorganic oxide carrier, the first metallic element presoma, the second metallic element presoma, Three metallic element presomas and water are mixed with beating, and obtain slurries, and the slurries are spray-dried, and then carry out the first roasting It burns, obtains intermediate composition；
(2) to contain the solution of the 4th metallic element presoma as maceration extract, to intermediate composition obtained by step (1) It is impregnated, obtains solid product, then the solid product is dried and/or second roasts；
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；Third metallic element is selected from I B- At least one of VIIB race non-noble metal j element；4th metallic element is selected from least one of precious 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:(0.05-20).
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 reduce for the present invention is above-mentioned The composition of 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 In the preparation method for inventing the composition that can reduce CO and NOx emission provided, noble metal utilisation is high, production cost compared with It is low；Also, the CO and the composition of NOx emission provided by the invention of can reduce reduces CO and NOx row as fluid catalytic cracking Auxiliary agent is put, so that coke and dry gas yied are lower in FCC product.With the side FCC for using existing reduction CO and NOx emission auxiliary agent Method is compared, and using the FCC method of the composition provided by the invention that can reduce CO and NOx emission, can reduce CO and NOx row The composition dosage put is low, and it is higher to reduce CO and NOx discharge activity.
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 It reduces CO to compare with the composition D-3 of NOx emission, uses the composition provided by the invention that can reduce CO and NOx emission When, the concentration of emission of NOx is down to 34ppm by 264ppm in complete regenerated flue gas.
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, the second metallic element, third metallic element and the 4th gold medal of body and load on an inorganic Belong to element, first metallic element be selected from group VIII non-noble metal j element, and first metallic element include Fe and Co, in terms of oxide, the weight ratio of Fe and Co are 1:(0.05-20), second metallic element is selected from I A and/or Group IIA At least one of metallic element, the third metallic element are selected from least one of I B-VIIB race non-noble metal j element, 4th metallic element is selected from least one of precious metal element.
The present invention is in the composition, the first metallic element, the second metallic element, third metallic element and the 4th metal The range of choice of the content of element is wider, it is preferable that on the basis of the total amount of composition, the content of the inorganic oxide carrier For 10-90 weight %, in terms of oxide, the content of first metallic element is 0.5-50 weight %, the second metal member The content of element is 0.5-20 weight %, and the content of the third metallic element is 0.5-20 weight %, based on the element, the described 4th The content of metallic element is 0.001-0.15 weight %；It is further preferred that the content of the inorganic oxide carrier is 50-90 Weight %, in terms of oxide, the content of first metallic element is 3-30 weight %, and the content of second metallic element is 1-20 weight %, the content of the third metallic element are 1-10 weight %, based on the element, the content of the 4th metallic element For 0.005-0.1 weight %；It is further preferred that the content of the inorganic oxide carrier is 55-85 weight %, with oxidation Object meter, the content of first metallic element are 5-25 weight %, and the content of second metallic element is 5-15 weight %, institute The content for stating third metallic element is 2-8 weight %, and based on the element, the content of the 4th metallic element is 0.01-0.08 weight Measure %；Most preferably, the content of the inorganic oxide carrier is 66-85 weight %, in terms of oxide, first metal The content of element is 6-16 weight %, and the content of second metallic element is 5-12 weight %, the third metallic element Content is 3-8 weight %, and based on the element, the content of the 4th metallic element is 0.05-0.07 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.
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:(0.1-10), further preferably 1:(0.3-3), it is still more preferably 1:(0.5-2).
In the present invention, in the case of no specified otherwise, Fe refers to Fe with Fe in terms of oxide2O3Meter, Co are 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, preferably before impregnating noble metal, is roasted under carbon-containing atmosphere It burns, so that part FeO is converted into cementite, 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 in the XRD spectrum of the composition, 2 θ be 42.6 °, There is diffraction maximum at 44.2 ° and 44.9 °.
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, group ia metal element includes but is not limited to Na and/or K；Group iia metallic element includes but unlimited In at least one of Mg, Ca, Sr and Ba.In the present invention, I B-VIIB race non-noble metal j element refers to the periodic table of elements In from group ib to the base metal of V Group IIB, including group ib base metal, group iib metal, Group IIIB metal, Group IVB metal, Group VB metal, vib metals and V Group IIB metal, specifically, I B-VIIB race base metal Element includes but is not limited at least one in Cu, Zn, Cd, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Re and rare earth element Kind；The rare earth element includes but is not limited at least one of La, Ce, Pr, Nd, Pm, Sm and Eu；The precious metal element Including at least one of Au, Ag, Pt, Os, Ir, Ru, Rh and Pd.
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.
The composition provided according to the present invention, the preferably described third metallic element be selected from Cu, Zn, Ti, Zr, V, Cr, Mo, W, at least one of Mn and rare earth element, preferably at least one of Zr, V, W, Mn, Ce and La, most preferably Mn.
The composition provided according to the present invention, preferably described 4th metallic element in Pt, Ir, Pd, Ru and Rh extremely Few one kind, most preferably Ru.
A kind of most preferred embodiment according to the present invention makes Fe, Co, Mg, Mn and Ru as active component cooperation With the composition that can reduce CO and NOx emission can be increased substantially to NH3The catalyzed conversion activity of equal reduction-states nitride, And the composition for making it possible to reduce 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, Mg, Mn and Ru, in terms of oxide, the weight ratio of Fe and Co are 1:(0.5-2), on the basis of the total amount of composition, oxygen The content for changing aluminium is 66-85 weight %, and in terms of oxide, the total content of Fe and Co are that the content of 6-16 weight %, Mg are 5-12 The content of weight %, Mn are that the content of 3-8 weight %, Ru are 0.05-0.07 weight %.
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 point 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:
(1) by the presoma of inorganic oxide carrier, the first metallic element presoma, the second metallic element presoma, Three metallic element presomas and water are mixed with beating, and obtain slurries, and the slurries are spray-dried, and then carry out the first roasting It burns, obtains intermediate composition；
(2) to contain the solution of the 4th metallic element presoma as maceration extract, to intermediate composition obtained by step (1) It is impregnated, obtains solid product, then the solid product is dried and/or second roasts；
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；Third metallic element is selected from I B- At least one of VIIB race non-noble metal j element；4th metallic element is selected from least one of precious 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:(0.05-20).
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 and the first metallic element, the second metal member The selection of element, third metallic element and the 4th metallic 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, the second metallic element presoma, third metallic element forerunner Body and the 4th metallic element presoma are respectively selected from the first metallic element, the second metallic element, third metallic element and the 4th gold medal Belong to the water soluble salt of element, such as nitrate, chloride, chlorate or sulfate, there is no particular limitation to this by the present invention.
Preparation method according to the present invention, to the first metallic element presoma, the second metallic element presoma, The range of choice of the dosage of third metallic element presoma and the 4th metallic element presoma is wider, it is preferable that the inorganic oxygen The presoma of compound carrier, the first metallic element presoma, the second metallic element presoma, third metallic element presoma and The dosage of four 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 10-90 weight %, and in terms of oxide, the content of first metallic element is 0.5-50 weight %, described The content of second metallic element is 0.5-20 weight %, and the content of the third metallic element is 0.5-20 weight %, with element Meter, the content of the 4th metallic element are 0.001-0.15 weight %；It is further preferred that the inorganic oxide carrier Content is 50-90 weight %, and in terms of oxide, the content of first metallic element is 3-30 weight %, second metal The content of element is 1-20 weight %, and the content of the third metallic element is 1-10 weight %, based on the element, the 4th gold medal The content for belonging to element is 0.005-0.1 weight %；It is further preferred that the content of the inorganic oxide carrier is 55-85 Weight %, 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 %, the content of the third metallic element are 2-8 weight %, based on the element, the content of the 4th metallic element For 0.01-0.08 weight %；Most preferably, the content of the inorganic oxide carrier is 66-85 weight %, in terms of oxide, The content of first metallic element is 6-16 weight %, and the content of second metallic element is 5-12 weight %, described the The content of three metallic elements is 3-8 weight %, and based on the element, the content of the 4th metallic element is 0.05-0.07 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, with Second metallic element presoma of I A and/or Group IIA metal element oxide meter, with I B-VIIB race non-noble metal j element The dosage quality of the third metallic element presoma of oxide meter and the 4th metallic element presoma in terms of precious metal element Than for 10-90:0.5-50:0.5-20:0.5-20:0.001-0.15；It is possible to further being 50-90:3-30:1-20:1- 10:0.005-0.1；Further, it can be 55-85:5-25:5-15:2-8:0.01-0.08, can also be 66-85:6- 16:5-12:3-8:0.05-0.07.
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:(0.1-10), into one Step is preferably 1:(0.3-3), it is still more preferably 1:(0.5-2).
, according to the invention it is preferred to which the solid content of slurries described in step (1) 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, third metallic element presoma and water are mixed with beating, and carries to inorganic oxide The presoma of body, the first metallic element presoma, the addition of the second metallic element presoma and third metallic element presoma are suitable Sequence is also without restriction, as long as by before the presoma of inorganic oxide carrier, the first metallic element presoma, the second metallic element Drive body and third metallic element presoma and water contact, it is preferable that first by the first metallic element presoma and third gold Belong to elemental precursor and be dissolved in water, presoma (the preferably acidified inorganic oxide load of inorganic oxide carrier is then added The presoma of body), the first solution is obtained, the second metallic element presoma is mixed with water, the second solution is obtained, finally by first Solution, 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 first roasting described in step (1) can effectively improve energy using conventional technical means in the art The composition of CO and NOx emission is enough reduced to NH3The catalyzed conversion activity of equal reduction-states nitride, but in order to further improve The composition of CO and NOx emission be can reduce to NH3The catalyzed conversion activity and hydrothermal stability of equal reduction-states nitride, preferably First roasting carries out under carbon-containing atmosphere.The present inventor is found surprisingly that in the course of the research, by described first Roasting carries out under carbon-containing atmosphere, and the composition that can enable to reduce CO and NOx emission is to NH3Equal reduction-states nitride Catalyzed conversion activity and hydrothermal stability the first obtained semi-finished product of roasting for significantly improving, and being carried out under carbon-containing atmosphere Composition is more advantageous to the load of subsequent precious metal element.Active raising and active component by oxide are converted into carbide And reduction-state is related, and the improvement of hydrothermal stability may further promote each active component in composition with high-temperature process Bonding, fusion and crosslinking it is related.From XRD comparison spectrogram in it can be seen that, occur after processing apparent cementite peak type with And the peak type of simple substance cobalt.Specifically, as shown in Figure 1, without carbon-containing atmosphere handle composition S-5 XRD spectra in There is the diffraction maximum of MgO at 43.0 ° or so places, have Al at 45.0 ° or so places2O3、Co2AlO4And MgAl2O4Diffraction maximum, and pass through In the XRD spectrogram of the composition S-1 of carbon-containing atmosphere processing, not only there is the diffraction maximum of MgO at 43.0 ° or so, at 45.0 ° or so There is Al2O3、Co2AlO4And MgAl2O4Diffraction maximum, and the diffraction maximum at 43.0 ° or so places and 45.0 ° or so places obviously becomes by force, And deviate to the left, it is attributed to the composition S-1 handled by carbon-containing atmosphere, is diffraction maximum, 2 θ occur at 42.6 °, 44.9 ° in 2 θ It is FeC (Fe for the diffraction maximum at 42.6 °, 44.9 °3C and Fe7C3) diffraction maximum.In addition, being compared with composition S-5, composition There is diffraction maximum at 44.2 ° in S-1, and 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 °, it is mainly used for illustrating Fe in composition With the existence form of Co.Outside 41 ° of -50 ° of ranges, there is also other diffraction maximums, for example, (2 θ are 37 °, 65 ° and 59 ° to FeO Place) and CoO (2 θ for 37 °, 65 ° and 31 ° at) diffraction maximum, the present invention is not further explained this.
The condition of a preferred embodiment of the invention, first roasting includes: to carry out under carbon-containing atmosphere, Temperature 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 first roasting, can carry out under normal pressure.Such as it can be (absolute pressure) is carried out under 0.01-1Mpa.
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, part inert gas, the indifferent gas can also be contained in the gas containing carbon elements Body can be various inert gases commonly used in the art, and the preferably described inert gas is in nitrogen, argon gas and helium At least one, 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 preferred reality of the invention Mode is applied, processing requirement can be not only better met, additionally it is possible to guarantee the safety of operator.
In the present invention, first roasting can carry out in roaster, and the roaster can be catalytic cracking catalysis Rotary roaster used in agent and auxiliary agent production.The gas of carbon elements in roaster with the solids in roaster Expect counter current contacting.
Preparation method according to the present invention, to dipping described in step (2), there is no particular limitation, can be according to this field Conventional technical means carries out, and can be saturation dipping, or excessive dipping, preferably excessive dipping.
Intermediate composition, can first be added to the water, then thereto by a kind of specific embodiment according to the present invention The solution of the 4th metallic element presoma is added, is stirred.
The present invention can be by being filtered the mixture obtained after dipping to obtain the solid product.The filtering can To be carried out according to conventional technical means in the art.
Preparation method according to the present invention, preferably this method further include: after step (2) described dipping, it is dry and/ Or before second roasts, alkali process is carried out to the solid product.Using the preferred embodiment of the present invention, in precious metal element Alkali process is carried out after dipping so that precious metal element (the 4th metallic element) and the first metallic element, the second metallic element and Third metallic element can be even closer combination, be more advantageous to the synergistic effect of performance, be more conducive to improve can The composition of CO and NOx emission is reduced to NH3The catalyzed conversion activity and hydrothermal stability of equal reduction-states nitride.
A kind of specific embodiment according to the present invention, the method for the alkali process may include: by the solid product It is mixed with beating with alkaline solution, or the solid product is eluted using alkaline solution.
The present invention is wider to the range of choice of the alkaline solution, and the preferably described alkaline solution is that nonmetalloid alkalinity is molten Liquid is still more preferably ammonium hydroxide and/or basic ammonium salts solution.The basic ammonium salts solution can be sal volatile, carbonic acid At least one of hydrogen ammonium salt solution and ammonium dibasic phosphate solution.The most preferably described alkaline solution of the present invention is ammonium hydroxide.
The present invention is wider to the concentration of the alkaline solution and the range of choice of dosage, for example, the alkaline solution is dense Degree can be 0.01-10mol/L, preferably 0.05-5mol/L, further preferably 0.5-2mol/L；The alkaline solution Volumetric usage can be 1-10 times, preferably 1.5-5 times of the solid product pore volume.
Those skilled in the art can select the concentration of alkaline solution according to the pore volume of the solid product specifically obtained And dosage, for example, a kind of specific embodiment according to the present invention, when the pore volume of obtained solid product of the present invention is about When 0.4-0.5mL/g, when the amount of the solid product of processing is 100g, the ammonia spirit 60- of 0.5-2mol/L can be selected 250mL。
Only solid product can be dried in step (2) of the present invention, the second roasting only can also be carried out to solid product It burns, the second roasting is carried out after the solid product can also be dried, there is no particular limitation to this by the present invention, preferably right The solid product carries out the second roasting after being dried.The condition that the present invention roasts the drying and second is not special It limits, can be carried out according to conventional technical means in the art.For example, it is 60-150 DEG C that dry condition, which may include: temperature, Time is 2-10h.
There is no particular limitation for condition of the present invention to second roasting, and second roasting can be in air or inertia It is carried out in atmosphere (such as nitrogen), the present invention is not particularly limited this, and the condition of second roasting may include: temperature It is 300-550 DEG C, time 1-10h.
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, I A and/ Or at least one of at least one of Group IIA metal element, I B-VIIB race non-noble metal j element and precious metal element At least one of, above-mentioned metallic element is used cooperatively, and makes it possible to reduce the composition of CO and NOx emission to NH3Deng reduction The catalyzed conversion activity of state nitride significantly improves, and the composition for making it possible to reduce CO and NOx emission has preferably 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 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 %.
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, carry out structure determination, Cu target, K α radiation, solid probe, tube voltage 40kV, tube current 40mA.
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 to analyze pure, potassium permanganate [KMnO4] it is that analysis is pure, magnesia [MgO] is that analysis is pure, by Chinese medicines group The production of chemical reagent Co., Ltd；Ruthenic chloride (RuCl3) it is to analyze pure, Ru content >=37%, grinding hundred million gold medal new material shares has The production of limit company；Boehmite is technical grade product, and 64 weight % of alumina content, pore volume is 0.31 ml/g, Shandong Chinalco's production；Hydrochloric acid, concentration are 36.5 weight %, analyze pure, Beijing Chemical Plant's production；Ammonium hydroxide, concentration 25-28%, Analyze it is pure, Beijing Chemical Plant production, used after dilution；Carbon monoxide, concentration are 10 volume %, and nitrogen does Balance Air, Beijing helium Pu Bei divides gas industry Co., Ltd to produce；Catalytic cracking catalyst industrial products (Cat-A, catalyst trade mark CGP-1), Na2O Content 0.24 weight %, RE2O3Content 3.2 weight %, Al2O3Content 48.0 weight %, 67 microns of average grain diameter, Sinopec The production of catalyst Co., Ltd.
Embodiment 1
(1) 2.62kg boehmite is added to be beaten in 14.2kg deionized water and is dispersed, 238mL salt is then added Acid acidification 15min, obtains aluminium stone colloid, by the ferric nitrate in terms of metal oxide (with Fe2O3Meter, similarly hereinafter) 60g, cobalt nitrate (with Co2O3Meter, similarly hereinafter) 60g, KMnO4(in terms of MnO, similarly hereinafter) 100g is added stirring in 3500mL water and dissolves to abundant, by aluminium stone glue Body is added thereto, and is stirred 15min, is obtained the first solution；100gMgO is added in 300g water, is added after stirring 10min to the In one solution, after stirring 20min, slurries is obtained, the slurries are spray-dried, the particle 150g for taking spray drying to obtain (average grain diameter is 65 μm, and partial size is that 40-80 μm of particle accounts for 60%, similarly hereinafter) is transferred in tube furnace, with the stream of 100mL/min Amount is passed through the CO/N that CO concentration is 10 volume %2Mixed gas handles 1.5h at 600 DEG C, obtains intermediate composition；
(2) it weighs the above-mentioned intermediate composition of 100g to be added in 700mL water, the quality with elemental metal is then added Content is the RuCl of 12.5g/L3Solution 4.8mL stirs 20min, is filtered to obtain solid product, is 2mol/L with concentration Ammonia spirit 80mL elute solid product, through drying (100 DEG C, 4h), roasting (400 DEG C, 2h) obtain 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 is as shown in Figure 1, as can be seen from Figure 1, at carbon-containing atmosphere There is the diffraction maximum of MgO in the XRD spectra of the composition S-5 of reason at 43.0 ° or so places, has Al at 45.0 ° or so places2O3、 Co2AlO4And MgAl2O4Diffraction maximum, and pass through carbon-containing atmosphere processing composition S-1 XRD spectrogram in, not only exist 43.0 ° or so the diffraction maximums for having a MgO, have Al at 45.0 ° or so2O3、Co2AlO4And MgAl2O4Diffraction maximum, and 43.0 ° of left sides The diffraction maximum at right place and 45.0 ° or so places obviously becomes by force, and deviates to the left, is attributed to the composition S- handled by carbon-containing atmosphere 1, it is diffraction maximum occur at 42.6 °, 44.9 ° in 2 θ, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) Diffraction maximum.In addition, comparing with composition S-5, there is diffraction maximum at 44.2 ° in composition S-1, and 2 θ are the diffraction maximum at 44.2 ° For the diffraction maximum of simple substance cobalt.
It should be noted that Fig. 1 only lists the XRD spectra within the scope of 41 ° -50 °, it is mainly used for illustrating Fe in composition With the existence form of Co.Outside 41 ° of -50 ° of ranges, there is also other diffraction maximums, for example, (2 θ are 37 °, 65 ° and 59 ° to FeO Place) and CoO (2 θ be 37 °, 65 ° and 31 ° at) diffraction maximum, the diffraction of diffraction maximum and FeC and simple substance Co outside 41 ° of -50 ° of ranges Peak is unrelated, and the present invention does not do further spectrum elucidation to this.
Embodiment 2
(1) 2.53kg boehmite is added to be beaten in 13.7kg deionized water and is dispersed, 229mL salt is then added Acid acidification 15min, obtains aluminium stone colloid, by ferric nitrate 100g, cobalt nitrate 60g, KMnO in terms of metal oxide4(with MnO Meter) 60g is added stirring in 3500mL water and is added thereto aluminium stone colloid to abundant dissolution, stirs 15min, obtain the first solution； 160gMgO is added in 480g water, is added after stirring 10min into the first solution, after stirring 20min, obtains slurries, it will The slurries are spray-dried, and the particle 150g for taking spray drying to obtain is transferred in tube furnace, with the flow of 100mL/min It is passed through the CO/N that CO concentration is 10 volume %2Mixed gas handles 3h at 500 DEG C, obtains intermediate composition；
(2) it weighs the above-mentioned intermediate composition of 100g to be added in 700mL water, the quality with elemental metal is then added Content is the RuCl of 12.5g/L3Solution 4.4mL stirs 20min, is filtered to obtain solid product, is 2mol/L with concentration Ammonia spirit 100mL elute solid product, through drying (100 DEG C, 4h), roasting (400 DEG C, 2h) obtain 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 is obvious to become strong, and deviate to the left, it is attributed to the composition S-2 handled by carbon-containing atmosphere, is to occur at 42.6 °, 44.9 ° in 2 θ Diffraction maximum, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, with composition S-5 phase Occurs diffraction maximum at 44.2 ° than, composition S-2,2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance cobalt.
Embodiment 3
(1) 2.09kg boehmite is added to be beaten in 11.3kg deionized water and is dispersed, 190mL salt is then added Acid acidification 15min, obtains aluminium stone colloid, by ferric nitrate 100g, cobalt nitrate 200g, KMnO in terms of metal oxide4(with MnO Meter) 160g is added stirring in 4000mL water and is added thereto aluminium stone colloid to abundant dissolution, stirs 15min, it is molten to obtain first Liquid；200gMgO is added in 600g water, is added after stirring 10min into the first solution, after stirring 20min, obtains slurries, The slurries are spray-dried, the particle 150g for taking spray drying to obtain is transferred in tube furnace, with the stream of 100mL/min Amount is passed through the CO/N that CO concentration is 10 volume %2Mixed gas handles 1h at 650 DEG C, obtains intermediate composition；
(2) it weighs the above-mentioned intermediate composition of 100g to be added in 700mL water, the quality with elemental metal is then added Content is the RuCl of 12.5g/L3Solution 4mL stirs 20min, is filtered to obtain solid product, is 2mol/L's with concentration Ammonia spirit 80mL elutes solid product, obtains composition S-3 through drying (100 DEG C, 4h), roasting (400 DEG C, 2h).
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 is obvious to become strong, and deviate to the left, it is attributed to the composition S-3 handled by carbon-containing atmosphere, is to occur at 42.6 °, 44.9 ° in 2 θ Diffraction maximum, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, with composition S-5 phase Occurs diffraction maximum at 44.2 ° than, composition S-3,2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance cobalt.
Embodiment 4
(1) 2.09kg boehmite is added to be beaten in 11.3kg deionized water and is dispersed, 190mL salt is then added Acid acidification 15min, obtains aluminium stone colloid, by ferric nitrate 200g, cobalt nitrate 120g, KMnO in terms of metal oxide4(with MnO Meter) 100g is added stirring in 3500mL water and is added thereto aluminium stone colloid to abundant dissolution, stirs 15min, it is molten to obtain first Liquid；240gMgO is added in 720g water, is added after stirring 10min into the first solution, after stirring 20min, obtains slurries, The slurries are spray-dried, the particle 150g for taking spray drying to obtain is transferred in tube furnace, with the stream of 100mL/min Amount is passed through the CO/N that CO concentration is 10 volume %2Mixed gas handles 1.5h at 600 DEG C, obtains intermediate composition；
(2) it weighs the above-mentioned intermediate composition of 100g to be added in 700mL water, the quality with elemental metal is then added Content is the RuCl of 12.5g/L3Solution 5.2mL stirs 20min, is filtered to obtain solid product, is 2mol/L with concentration Ammonia spirit 80mL elute solid product, through drying (100 DEG C, 4h), roasting (400 DEG C, 2h) obtain 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 is obvious to become strong, and deviate to the left, it is attributed to the composition S-4 handled by carbon-containing atmosphere, is to occur at 42.6 °, 44.9 ° in 2 θ Diffraction maximum, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, with composition S-5 phase Occurs diffraction maximum at 44.2 ° than, composition S-4,2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance 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, is composed from XRD Figure (as shown in Figure 1) can be seen that, be at 42.6 °, 44.2 ° and 44.9 ° without obvious diffraction maximum in 2 θ, it was demonstrated that Fe in composition S-5 Exist in the form of an oxide with Co.
Embodiment 6
It according to the method for embodiment 1, does not include the ammonia spirit for being 2mol/L with concentration in step (2) unlike 80mL elutes the step of solid product, and directly solid product is dried, roasts, obtains 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 is obvious to become strong, and deviate to the left, it is attributed to the composition S-6 handled by carbon-containing atmosphere, is to occur at 42.6 °, 44.9 ° in 2 θ Diffraction maximum, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, with composition S-5 phase Occurs diffraction maximum at 44.2 ° than, composition S-6,2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance cobalt.
Embodiment 7
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 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 is obvious to become strong, and deviate to the left, it is attributed to the composition S-7 handled by carbon-containing atmosphere, is to occur at 42.6 °, 44.9 ° in 2 θ Diffraction maximum, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, with composition S-5 phase Occurs diffraction maximum at 44.2 ° than, composition S-7,2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance cobalt.
Embodiment 8
According to the method for embodiment 1, unlike, in terms of metal oxide, with the CeCl of phase homogenous quantities2Replace KMnO4, 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 is obvious to become strong, and deviate to the left, it is attributed to the composition S-8 handled by carbon-containing atmosphere, is to occur at 42.6 °, 44.9 ° in 2 θ Diffraction maximum, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, with composition S-5 phase Occurs diffraction maximum at 44.2 ° than, composition S-8,2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance cobalt.
Embodiment 9
According to the method for embodiment 1, unlike, the dosage of the ferric nitrate in terms of metal oxide is 30g, cobalt nitrate Dosage is 90g, 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 is obvious to become strong, and deviate to the left, it is attributed to the composition S-9 handled by carbon-containing atmosphere, is to occur at 42.6 °, 44.9 ° in 2 θ Diffraction maximum, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, with composition S-5 phase Occurs diffraction maximum at 44.2 ° than, composition S-9,2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance cobalt.
Embodiment 10
According to the method for embodiment 1, unlike, the dosage of the ferric nitrate in terms of metal oxide is 90g, cobalt nitrate Dosage is 30g, obtains composition S-10.
Each component assay result is listed in table 1 in composition S-10.The XRD analysis result and embodiment of composition S-10 1 is similar.In the XRD spectra of composition S-10 by carbon-containing atmosphere processing, not only there is the diffraction maximum of MgO at 43.0 ° or so, There is Al at 45.0 ° or so2O3、Co2AlO4And MgAl2O4Diffraction maximum, and the diffraction at 43.0 ° or so places and 45.0 ° or so places Peak obviously becomes by force, and deviates to the left, is attributed to the composition S-10 handled by carbon-containing atmosphere, is at 42.6 °, 44.9 ° in 2 θ There is diffraction maximum, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, and composition S-5 is compared, and diffraction maximum occurs at 44.2 ° in composition S-10, and 2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance cobalt.
Embodiment 11
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-11.
Each component assay result is listed in table 1 in composition S-11.The XRD analysis result and embodiment of composition S-11 1 is similar.In the XRD spectra of composition S-11 by carbon-containing atmosphere processing, not only there is the diffraction maximum of MgO at 43.0 ° or so, There is Al at 45.0 ° or so2O3、Co2AlO4And MgAl2O4Diffraction maximum, and the diffraction at 43.0 ° or so places and 45.0 ° or so places Peak obviously becomes by force, and deviates to the left, is attributed to the composition S-11 handled by carbon-containing atmosphere, is at 42.6 °, 44.9 ° in 2 θ There is diffraction maximum, 2 θ are that the diffraction maximum at 42.6 °, 44.9 ° is FeC (Fe3C and Fe7C3) diffraction maximum.In addition, and composition S-5 is compared, and diffraction maximum occurs at 44.2 ° in composition S-11, and 2 θ are the diffraction maximum that diffraction maximum at 44.2 ° is simple substance 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: in terms of oxide, unit is attached most importance to for the first metallic element, the second metallic element and third metal element content % is measured, based on the element, unit is weight % to the 4th metal element content.
Test example 1
This test example is used to reduce CO and NOx in complete regenerated flue gas to the composition that above-described embodiment and comparative example provide The effect of discharge and influence to FCC product distribution.
The composition that CO and NOx emission will be reduced uniformly (can reduce with catalytic cracking catalyst (Cat-A) blending CO and the composition of NOx emission account for 0.8 weight of the composition and catalytic cracking catalyst total amount that can reduce CO and NOx emission Measure %), 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 fluidized bed unit, the catalyst dress through aging The amount of filling out is 9g, and reaction temperature is 500 DEG C, and agent oil weight ratio is 6, and raw material oil nature is shown in Table 2.Gaseous product passes through on-line chromatograph point Analysis obtains cracked gas composition；Product liquid carries out offline chromatography and obtains gasoline, diesel oil and heavy oil yield.Through N after reaction2 10min is stripped, coke burning regeneration in situ is carried out, regeneration air flow is 200mL/min, reproduction time 15min, regenerates initial temperature Same reaction temperature.The flue gas in regenerative process is collected, according to CO after regeneration ending2Infrared spectrum analyser integral calculation coke yield, FCC product distribution is obtained after all product yield normalizings, is shown in Table 3, and in table 3, conversion ratio refers to dry gas, liquefied gas, gasoline and coke The sum of yield.Using the concentration of NOx and CO in Testo350Pro flue gas analyzer measurement flue gas, it the results are shown in Table 4.
Table 2
Table 3
Product distribution Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 3
Dry gas, weight % 1.72 1.70 1.72 1.71 1.73
Liquefied gas, weight % 19.27 19.39 19.57 19.50 19.20
Coke, weight % 7.16 7.15 7.22 7.22 7.29
Gasoline, weight % 49.66 49.62 49.48 49.26 49.44
Diesel oil, weight % 15.16 15.10 14.87 15.26 15.27
Heavy oil, weight % 7.03 7.04 7.13 7.06 7.06
Conversion ratio, % 77.81 77.86 77.99 77.69 77.66
From table 3 it can be seen that the composition cooperation catalytic cracking catalysis provided by the invention that can reduce CO and NOx emission Agent uses, so that coke and dry gas yied are lower in FCC product.
Table 4
As can be seen from Table 4, using the composition provided by the invention that can reduce CO and NOx emission for being catalyzed Cracking process has preferably reduction CO and NOx emission compared with the composition that can reduce CO and NOx emission that comparative example provides Performance, and be the composition that can reduce CO and NOx emission after aging, can drop after aging used in evaluation procedure Low CO and the composition of NOx emission still are able to that the discharge of CO and NOx is effectively reduced, therefore, provided by the invention to can reduce CO and the composition of NOx emission have 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 The effect of CO and NOx emission in incomplete regen-eration flue gas.
The composition and above-mentioned catalytic cracking catalyst (Cat-A) blending that CO and NOx emission will be reduced uniformly (can The composition for reducing CO and NOx emission accounts for the 2.2 of the composition and catalytic cracking catalyst total amount that can reduce CO and NOx emission 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 5.
Table 5
Number NOx concentration, ppm NH3Concentration, ppm CO concentration, volume %
Embodiment 1 S-1 58 59 2.89
Comparative example 1 D-1 115 151 2.87
Comparative example 2 D-2 107 147 2.92
Comparative example 3 D-3 109 321 3.15
Embodiment 2 S-2 52 58 2.81
Embodiment 3 S-3 35 1 2.7
Embodiment 4 S-4 27 3 2.7
Embodiment 5 S-5 62 63 2.87
Embodiment 6 S-6 75 62 2.91
Embodiment 7 S-7 69 76 2.88
Embodiment 8 S-8 65 72 2.9
Embodiment 9 S-9 58 62 2.91
Embodiment 10 S-10 61 63 2.88
Embodiment 11 S-11 57 60 2.88
As can be seen from Table 5, using the composition provided by the invention that can reduce CO and NOx emission for being catalyzed Cracking process incomplete regen-eration process has preferably drop compared with the composition that can reduce CO and NOx emission that comparative example provides Low CO, NH3It and is the group that can reduce CO and NOx emission after aging used in evaluation procedure with NOx emission performance Object is closed, composition removing CO, NH that can reduce CO and NOx emission after aging3It is still higher with NOx activity, therefore, this hair The can reduce CO and the composition of NOx emission of bright offer have preferable hydrothermal stability.
It can be seen that the composition provided by the invention that can reduce CO and NOx emission from table 4 and 5 data of table while fitting For regenerating completely and incomplete regen-eration, there is preferable regenerated flue gas processing capacity.Particularly, from embodiment 1 and embodiment 5 Comparison carries out under carbon-containing atmosphere as can be seen that roasting using currently preferred first, makes it possible to reduce CO and NOx row The composition properties put further increase；It compares from embodiment 1 with embodiment 6 as can be seen that being soaked using currently preferred The mode of alkali process is carried out after stain noble metal, the composition properties for making it possible to reduce CO and NOx emission further increase；From reality Example 1 and embodiment 7, the comparison of embodiment 8 are applied as can be seen that use currently preferred metallic element, make it possible to reduce CO and The composition properties of NOx emission further increase；From embodiment 1 and embodiment 9, the comparison of embodiment 10 as can be seen that using this Preferred Fe and Co mass ratio are invented, the composition properties for making it possible to reduce CO and NOx emission further increase；From implementation Example 1 is compared can be seen that with embodiment 11 and be handled using the present invention preferably carbon-containing atmosphere, makes it possible to reduce CO and NOx The composition properties of discharge further increase；From embodiment 1 and comparative example 1-3 comparison as can be seen that the present invention by by Fe and Co is used cooperatively, and the composition properties for making it possible to reduce CO and NOx emission increase substantially.
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 (18)

1. a kind of composition that can reduce CO and NOx emission, which is characterized in that the composition includes: inorganic oxide carrier And the first metallic element, the second metallic element, third metallic element and the 4th metal of load on an inorganic Element, first metallic element are selected from group VIII non-noble metal j element, and first metallic element includes Fe and Co, with The weight ratio of oxide meter, Fe and Co are 1:(0.05-20), second metallic element is selected from I A and/or Group IIA metal member At least one of element, the third metallic element are selected from least one of I B-VIIB race non-noble metal j element, and described the Four metallic elements are selected from least one of precious metal element.
2. composition according to claim 1, wherein on the basis of the total amount of composition, the inorganic oxide carrier Content be 10-90 weight %, in terms of oxide, the content of first metallic element is 0.5-50 weight %, described second The content of metallic element is 0.5-20 weight %, and the content of the third metallic element is 0.5-20 weight %, based on the element, institute The content for stating the 4th metallic element is 0.001-0.15 weight %；
Preferably, the content of the inorganic oxide carrier is 50-90 weight %, in terms of oxide, first metallic element Content be 3-30 weight %, the content of second metallic element is 1-20 weight %, the content of the third metallic element For 1-10 weight %, based on the element, the content of the 4th metallic element is 0.005-0.1 weight %；
It is further preferred that the content of the inorganic oxide carrier is 55-85 weight %, and in terms of oxide, first gold medal The content for belonging to element is 5-25 weight %, and the content of second metallic element is 5-15 weight %, the third metallic element Content be 2-8 weight %, based on the element, the content of the 4th metallic element is 0.01-0.08 weight %.
3. composition according to claim 1 or 2, wherein in terms of oxide, the weight ratio of Fe and Co are 1:(0.1- 10), preferably 1:(0.3-3), further preferably 1:(0.5-2).
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；
The third metallic element is selected from least one of Cu, Zn, Ti, Zr, V, Cr, Mo, W, Mn and rare earth element, preferably At least one of Zr, V, W, Mn, Ce and La, most preferably Mn；
4th metallic element is selected from least one of Pt, Ir, Pd, Ru and Rh, most preferably Ru.
7. a kind of preparation method for the composition that can reduce CO and NOx emission, which is characterized in that this method comprises:
(1) by the presoma of inorganic oxide carrier, the first metallic element presoma, the second metallic element presoma, third gold Belong to elemental precursor and water is mixed with beating, obtain slurries, the slurries are spray-dried, then carries out the first roasting, obtain To intermediate composition；
(2) to contain the solution of the 4th metallic element presoma as maceration extract, intermediate composition obtained by step (1) is carried out Dipping, obtains solid product, is then dried to the solid product and/or second roasts；
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；Third metallic element is selected from I B-VIIB race At least one of non-noble metal j element；4th metallic element is selected from least one of precious 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:(0.05-20).
8. preparation method according to claim 7, wherein it is described first roasting condition include: under carbon-containing atmosphere into Row, temperature 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 this method further include: after step (2) described dipping, Before dry and/or the second roasting, alkali process is carried out to the solid product；
Preferably, the method for the alkali process includes: and is mixed with beating the solid product with alkaline solution, or using alkalinity Solution elutes the solid product；
Preferably, the alkaline solution is nonmetalloid alkaline solution, preferably ammonium hydroxide and/or basic ammonium salts solution；
Preferably, the concentration of the alkaline solution is 0.01-10mol/L, preferably 0.05-5mol/L；
Preferably, the volumetric usage of the alkaline solution is 1-10 times, preferably 1.5-5 times of the solid product pore volume.
10. the preparation method according to any one of claim 7-9, wherein the forerunner of the inorganic oxide carrier Body, the first metallic element presoma, the second metallic element presoma, third metallic element presoma and the 4th metallic element forerunner The dosage of body makes, and in composition obtained, on the basis of the total amount of composition, the content of the inorganic oxide carrier is 10-90 weight %, in terms of oxide, the content of first metallic element is 0.5-50 weight %, second metallic element Content be 0.5-20 weight %, the content of the third metallic element is 0.5-20 weight %, based on the element, the 4th gold medal The content for belonging to element is 0.001-0.15 weight %；
Preferably, the content of the inorganic oxide carrier is 50-90 weight %, in terms of oxide, first metallic element Content be 3-30 weight %, the content of second metallic element is 1-20 weight %, the content of the third metallic element For 1-10 weight %, based on the element, the content of the 4th metallic element is 0.005-0.1 weight %；
It is further preferred that the content of the inorganic oxide carrier is 55-85 weight %, and in terms of oxide, first gold medal The content for belonging to element is 5-25 weight %, and the content of second metallic element is 5-15 weight %, the third metallic element Content be 2-8 weight %, based on the element, the content of the 4th metallic element is 0.01-0.08 weight %.
11. preparation method according to any one of claims of claim 7-10, 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:(0.1-10), preferably 1:(0.3- 3), further preferably 1:(0.5-2).
12. the preparation method according to any one of claim 7-11, 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。
13. the preparation method according to any one of claim 7-12, 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；
Third metallic element be selected from least one of Cu, Zn, Ti, Zr, V, Cr, Mo, W, Mn and rare earth element, preferably Zr, V, at least one of W, Mn, Ce and La, most preferably Mn；
4th metallic element is selected from least one of Pt, Ir, Pd, Ru and Rh, most preferably Ru；
The first metallic element presoma, the second metallic element presoma, third metallic element presoma and the 4th metal member Plain presoma is respectively selected from the water solubility of the first metallic element, the second metallic element, third metallic element and the 4th metallic element Salt.
14. can reduce the combination of CO and NOx emission made from the preparation method as described in any one of claim 7-13 Object.
15. can reduce the composition of CO and NOx emission described in any one of claim 1-6 and 14 in fume treatment Application.
16. can reduce described in any one of claim 1-6 and 14 composition of CO and NOx emission catalytic cracking again Application in raw fume treatment.
17. 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 14 Enough reduce the composition of CO and NOx emission.
18. fluidized catalytic cracking method according to claim 17, 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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CN111939889A (en) * 2019-05-17 2020-11-17 中国石油化工股份有限公司 Renewable NO oxidation catalyst and preparation method and application thereof
CN111939890A (en) * 2019-05-17 2020-11-17 中国石油化工股份有限公司 Low-temperature NO oxidation catalyst, preparation method thereof and application thereof in low-temperature flue gas treatment
CN115140736A (en) * 2022-05-16 2022-10-04 中南大学 Multi-component composite ferrite modified activated carbon, preparation method thereof and application thereof in desulfurization and denitrification
CN115414944A (en) * 2022-08-29 2022-12-02 武汉科林化工集团有限公司 Preparation method of catalyst for producing isopropanol by acetone hydrogenation

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

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CN101331103A (en) * 2005-10-14 2008-12-24 赢创德固赛有限责任公司 Mixed oxide catalysts for the catalytic gas-phase oxidation of olefins and processes for producing them
CN102371150A (en) * 2010-08-26 2012-03-14 中国石油化工股份有限公司 Composition for reducing discharge of NOx in regeneration flue gas of fluid catalytic cracking (FCC)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111939889A (en) * 2019-05-17 2020-11-17 中国石油化工股份有限公司 Renewable NO oxidation catalyst and preparation method and application thereof
CN111939890A (en) * 2019-05-17 2020-11-17 中国石油化工股份有限公司 Low-temperature NO oxidation catalyst, preparation method thereof and application thereof in low-temperature flue gas treatment
CN111939889B (en) * 2019-05-17 2023-02-21 中国石油化工股份有限公司 Renewable NO oxidation catalyst, preparation method and application thereof
CN111939890B (en) * 2019-05-17 2023-02-21 中国石油化工股份有限公司 Low-temperature NO oxidation catalyst, preparation method thereof and application thereof in low-temperature flue gas treatment
CN115140736A (en) * 2022-05-16 2022-10-04 中南大学 Multi-component composite ferrite modified activated carbon, preparation method thereof and application thereof in desulfurization and denitrification
CN115140736B (en) * 2022-05-16 2023-09-19 中南大学 Multicomponent composite ferrite modified activated carbon, preparation method thereof and application thereof in desulfurization and denitrification
CN115414944A (en) * 2022-08-29 2022-12-02 武汉科林化工集团有限公司 Preparation method of catalyst for producing isopropanol by acetone hydrogenation
CN115414944B (en) * 2022-08-29 2023-11-07 武汉科林化工集团有限公司 Preparation method of catalyst for producing isopropanol by acetone hydrogenation

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