CN109201080A - It can reduce composition of CO and NOx emission and its preparation method and application and fluidized catalytic cracking method - Google Patents

It can reduce composition of CO and NOx emission and its preparation method and application and fluidized catalytic cracking method Download PDF

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Publication number
CN109201080A
CN109201080A CN201710543243.3A CN201710543243A CN109201080A CN 109201080 A CN109201080 A CN 109201080A CN 201710543243 A CN201710543243 A CN 201710543243A CN 109201080 A CN109201080 A CN 109201080A
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metallic element
presoma
weight
content
composition
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CN201710543243.3A
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CN109201080B (en
Inventor
宋海涛
姜秋桥
孙言
王鹏
田辉平
张杰潇
张万虹
李家兴
达志坚
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN201710543243.3A priority Critical patent/CN109201080B/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 EP18827377.5A priority patent/EP3693085A4/en
Priority to TW107123246A priority patent/TWI786147B/en
Priority to PCT/CN2018/094584 priority patent/WO2019007381A1/en
Priority to JP2020500124A priority patent/JP7114688B2/en
Priority to US16/626,742 priority patent/US11529612B2/en
Priority to AU2018298192A priority patent/AU2018298192B2/en
Priority to RU2020104054A priority patent/RU2772281C2/en
Publication of CN109201080A publication Critical patent/CN109201080A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/405—Limiting CO, NOx or SOx emissions
    • 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, this method comprises: the presoma of inorganic oxide carrier, the first metallic element presoma and water are mixed with beating by (1), obtain slurries, the slurries are spray-dried, then the first roasting is carried out, intermediate composition is obtained；(2) to contain the solution of the 4th metallic element presoma as maceration extract, intermediate composition obtained by step (1) is impregnated, solid product is obtained, alkali process is carried out to the solid product, be then dried and/or the second roasting.Using the hydrothermal stability with higher of composition made from method provided by the invention, and reduction regenerated gas CO with higher and NOx emission are active.

Description

It can reduce composition of CO and NOx emission and its preparation method and application and stream Fluidized catalytic cracking method
Technical field
The present invention relates to catalytic cracking fields, and in particular to can reduce the composition of CO and NOx emission, can reduce CO With the preparation method and the composition obtained by this method that can reduce CO and NOx emission, above-mentioned energy of the composition of NOx emission Enough reduce application and the fluidized catalytic cracking method of the composition of CO and NOx emission.
Background technique
The constantly soaring processing cost for having increased considerably refinery of crude oil price, on the one hand refinery passes through buys low price Poor oil reduces cost；On the other hand economic well-being of workers and staff is increased by deep processing mink cell focus.Catalytic cracking is as refinery's weight The important means of oil processing, there is very important status in refinery, is not only oil plant heavy oil balance, production clean fuel Main means, the even more focus of the energy efficiency of oil plant.Catalytic cracking is a kind of quickly urging for rapid catalyst deactivation Change reaction system, solves the problems, such as the main line of catalyst regeneration always catalytic cracking development.
During fluid catalytic cracking (FCC), feedstock oil and regenerated catalyst are catalyzed in riser Rapid contact Cracking reaction reacts and causes its inactivation in the coke laydown to catalyst of generation, and the catalyst of green coke inactivation enters after stripping Regenerator, the regeneration air entered with regenerator bottoms or the air rich in oxygen, which contact, carries out coke burning regeneration.Urging after regeneration Agent is recycled back to reactor and participates in catalytic cracking reaction again.According to the height of flue gas Excess oxygen content in regenerative process or CO oxygen Catalytic cracking unit can be divided into regeneration completely and incomplete regen-eration operation by the abundant degree changed.
In complete regenerative process, the nitrogenous compound in coke and coke generates CO under the action of regeneration air2And N2, The pollutants such as CO and NOx can be also generated simultaneously.It the use of catalyst aid is the important technique measure for controlling CO and NOx emission pollution.
Auxiliary agent for reducing regenerated gas CO discharge is commonly referred to as CO combustion adjuvant, such as CN1022843C discloses one kind Noble metals load-carbon oxide accelerator, active component are 1-1000ppm platinum or 50-1000ppm palladium, and carrier is by (1) The microsphere particle of 99.5~50% Cracking catalyst or its matrix and (2) 0.5-50%Al2O3, 0-20%RE2O3And 0-15% ZrO2Composition, (2) are the external coatings of (1) particle.
Auxiliary agent for controlling flue gas NOx discharge commonly referred to as reduces NOx emission auxiliary agent or NOx reduction auxiliary agent, such as CN102371150A 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.It should Although method can reduce NH in incomplete regen-eration FCC apparatus flue gas3Discharge, but the usage amount of CO is larger, and it is higher that there are energy consumptions Defect, and be unfavorable for environmental protection.
US4755282 discloses NH in a kind of reduction partial regeneration or incomplete regen-eration FCC apparatus flue gas3The side of discharge Method.This method makes it maintain one in dilute phase bed by the way that ammonia decomposition catalyzer of the granularity at 10-40 μm is added into regenerator Fixed concentration, by NH3It is converted into N2And water.The active component of the ammonia decomposition catalyzer can be dispersed in inorganic oxide load Noble metal on body.
CN101024179A discloses the composition that NOx is restored used in a kind of FCC process, and the composition contains (i) base Acidic metal oxide, (ii) alkali metal, alkaline-earth metal and their mixture and (iii) storage oxygen group not zeolite-containing in sheet Point.The composition prepared with precious metal impregnation, to convert the vapour phase reduction nitrogen class in incomplete regen-eration catalytic cracking unit flue gas Substance reduces flue gas NOx discharge.
Currently, for controlling incomplete regen-eration device flue gas NH3With the auxiliary agent technical research and application report phase of NOx emission It is existing to be suitable for regeneration dress completely due to incomplete regen-eration device flue gas composition and complete regenerating unit significant difference to less The catalyst aid set, the application effect on incomplete regen-eration device are undesirable.Though assistant composition disclosed in above-mentioned technology It so being capable of NH in catalyzed conversion flue gas to a certain extent3Equal reduction-states nitride, but to NH in flue gas3Equal reduction-states nitride Catalyzed conversion activity it is still to be improved, to slow down NH3Deng the influence that deposition salt crust runs equipment, thus needs to develop and be applicable in In the flue gas pollutant emission reduction auxiliary agent of incomplete regen-eration device, flue gas NOx discharge is further decreased.
Summary of the invention
For in prior art regenerative process, NH3The lower defect of catalyzed conversion activity of equal reduction-states nitride, this hair The preparation 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 composition that can reduce CO and NOx emission Application and a kind of fluidized catalytic cracking method in fume treatment.CO and the NOx emission provided by the invention of can reduce Composition is high to the catalyzed conversion activity of reduction-state nitride, and preparation method is simple, is used in fluid catalytic cracking process, can 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 At least one of VIII group non-noble metal j element cooperation precious metal element is used as active component, and is prepared in composition Cheng Zhong carries out alkali process to obtained solid product after impregnating noble metal so that precious metal element (the 4th metallic element) and First metallic element can be combined closely, be conducive to the synergistic effect for playing the two, and being conducive to raising can reduce CO and NOx The composition of discharge is to NH3The catalyzed conversion activity and hydrothermal stability of equal reduction-states nitride.
Through further research, it has been found that in the preferred case, the group VIII non-noble metal j element containing Fe and Co is matched Close precious metal element and the second metallic element (at least one of I A and/or Group IIA metal element) and third metal member At least one of plain (at least one of I B-VIIB race non-noble metal j element) uses, and can more efficiently reduce and urge Change CO and NOx emission in cracking regenerated flue gas, thus it is speculated that its reason may be due in, I A and/or Group IIA metal element extremely A kind of at least one of few, I B-VIIB race non-noble metal j element and precious metal element have modified the first metal member jointly Element is more conducive to playing the synergistic effect between metal, advantageously reduces the generation of oxidation state nitrogenous compound, and can promote Into the decomposition of reduction-state nitrogenous compound.
Based on this, according to the first aspect of the invention, a kind of preparation side of composition for reducing CO and NOx emission is provided Method, this method comprises:
(1) presoma of inorganic oxide carrier, the first metallic element presoma and water are mixed with beating, obtain slurries, The slurries are spray-dried, the first roasting is then carried out, 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, alkali process is carried out to the solid product, be then 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；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 second aspect of the invention, providing one kind can reduce CO and NOx emission as made from above-mentioned preparation method Composition.
According to the third aspect of the invention we, the above-mentioned composition that can reduce CO and NOx emission is provided in fume treatment Application.
According to the fourth 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 fifth 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.
In the preparation method of the composition provided by the invention that can reduce CO and NOx emission, noble metal utilisation is high, raw Cost is relatively low for production；Also, the CO and the composition of NOx emission provided by the invention of can reduce reduces CO as fluid catalytic cracking With NOx emission auxiliary agent so that coke and dry gas yied are lower in FCC product.With use existing reduction CO and NOx emission auxiliary agent FCC method is compared, using the FCC method of the composition provided by the invention that can reduce CO and NOx emission, can reduce CO and The composition dosage of NOx emission is low, and reduction CO and NOx emission activity are higher.
For example, group made from the preparation method for the composition that can reduce CO and NOx emission that the embodiment of the present invention 3 provides Close object, in account for 0.8 weight % of total catalyst weight ratio and FCC major catalyst (Cat-A) blending uniformly after, through 800 DEG C, Catalytic cracking reaction-regeneration evaluation is carried out under 100% water vapour atmosphere after aging 12 hours, uses active component with the prior art The CO that can reduce of saturation dipping method preparation is compared with the composition D-3 of NOx emission, uses preparation method provided by the invention When the composition obtained that can reduce CO and NOx emission, the concentration of emission of NOx is down to by 264ppm in complete regenerated flue gas 36ppm。
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
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 preparation methods of composition that can reduce CO and NOx emission, this method comprises:
(1) presoma of inorganic oxide carrier, the first metallic element presoma and water are mixed with beating, obtain slurries, The slurries are spray-dried, the first roasting is then carried out, 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, alkali process is carried out to the solid product, be then 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；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.
Inorganic oxide carrier of the present invention can be selected from aluminium oxide, silica-alumina, zeolite, spinelle, kaolinite At least one of soil, diatomite, perlite and perovskite；Preferably, it is brilliant to be selected from aluminium oxide, point for the inorganic oxide carrier At least one of stone and perovskite, further preferably aluminium oxide.
The presoma of the aluminium oxide can various colloidal sols or gel or aluminium hydroxide selected from aluminium.The hydroxide Aluminium can be selected from least one of gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and boehmite. 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.
Preparation method according to the present invention, to the first metallic element presoma and the 4th metallic element presoma Dosage range of choice it is wider, it is preferable that the presoma of the inorganic oxide carrier, the first metallic element presoma and The dosage of 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 59.9-94.995 weight %, and in terms of oxide, the content of first metallic element is 5-40 weight %, Based on the element, the content of the 4th metallic element is 0.005-0.1 weight %；It is further preferred that the inorganic oxide The content of carrier is 74.92-91.99 weight %, and in terms of oxide, the content of first metallic element is 8-25 weight %, Based on the element, the content of the 4th metallic element is 0.01-0.08 weight %；It is further preferred that the inorganic oxide The content of object carrier is 83.93-89.95 weight %, and in terms of oxide, the content of first metallic element is 10-16 weight % is measured, 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 and The dosage mass ratio of the 4th metallic element presoma in terms of precious metal element is 59.9-94.995:5-40:0.005-0.1；Into One step, it can be 74.92-91.99:8-25:0.01-0.08；Further, can be 83.93-89.95:10-16: 0.05-0.07。
First metallic element of the present invention includes Fe and Co, as long as institute is not precluded in the present invention comprising Fe and Co It states in the first metallic element also containing the element in group VIII non-noble metal j element other than Fe and Co, such as Ni.
A kind of most preferred embodiment according to the present invention, first metallic element is only Fe and Co.
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:(0.4-2).
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.
, 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, the first metallic element presoma and the 4th metallic element presoma are respectively selected from the first metal The water soluble salt of element and the 4th metallic element, such as nitrate, chloride, chlorate or sulfate, the present invention do not have this It is special to limit.
In the present invention, the precious metal element includes at least one of Au, Ag, Pt, Os, Ir, Ru, Rh and Pd.
The preparation method provided according to the present invention, preferably described 4th metallic element is in Pt, Ir, Pd, Ru and Rh At least one, most preferably Ru.
According to the present invention, the presoma of inorganic oxide carrier, the first metallic element presoma and water are mixed to described There is no particular limitation for the method for mashing, suitable to the presoma of inorganic oxide carrier, the addition of the first metallic element presoma Sequence, as long as the presoma of inorganic oxide carrier, the first metallic element presoma and water are contacted, is then beaten also without restriction Slurry obtains slurries.
A preferred embodiment of the invention, this method further include: step (1) is described be mixed with beating during Introduce the second metallic element presoma and/or third metallic element presoma；Second metallic element be selected from I A and/or At least one of Group IIA metal element, the third metallic element in I B-VIIB race non-noble metal j element at least It is a kind of.
The second metal precursor is introduced in pulping process can be improved the performance of composition, and is introduced in pulping process Three metal precursors can also be improved the performance of composition, but introduce the second metallic element presoma and third metallic element simultaneously Presoma is more advantageous to the performance for further increasing composition.
Therefore, preparation method according to the present invention, in step (1), it is preferable that can be by the forerunner of inorganic oxide carrier Body, the first metallic element presoma, the second metallic element presoma and water are mixed with beating, and are also possible to inorganic oxide carrier Presoma, the first metallic element presoma, third metallic element presoma and water be mixed with beating, step (1) of the present invention is more excellent It selects the presoma of inorganic oxide carrier, the first metallic element presoma, the second metallic element presoma, third metallic element Presoma and water are mixed with beating.This kind of preferred embodiment is more advantageous to and plays the first metallic element, the second metallic element, the The synergistic effect of three metallic elements and the 4th metallic element is more advantageous to the performance for improving composition.
The present invention is wider to the range of choice of the dosage of the second metallic element presoma, third metallic element presoma.
A kind of specific embodiment according to the present invention, this method further include: step (1) is described be mixed with beating during The second metallic element presoma and third metallic element presoma are introduced, specifically, step (1) includes: to carry inorganic oxide The presoma of body, the first metallic element presoma, the second metallic element presoma, third metallic element presoma and water mixing are beaten Slurry, obtains slurries, the slurries is spray-dried, and then carries out the first roasting, obtains intermediate composition.
A preferred embodiment of the invention, the presoma of the inorganic oxide carrier, the first metallic element Presoma, the second metallic element presoma, third metallic element presoma and the 4th metallic element presoma dosage make, make In the composition obtained, on the basis of the total amount of composition, the content of the inorganic oxide carrier is 10-90 weight %, with oxygen Compound meter, the content of first metallic element are 0.5-50 weight %, and the content of second metallic element is 0.5-20 weight % is measured, the content of the third metallic element is 0.5-20 weight %, and based on the element, the content of the 4th metallic element is 0.001-0.15 weight %；It is further preferred that the content of the inorganic oxide carrier is 50-90 weight %, with oxide Meter, the content of first metallic element are 3-30 weight %, and the content of second metallic element is 1-20 weight %, described The content of third metallic element is 1-10 weight %, and based on the element, the content of the 4th metallic element is 0.005-0.1 weight Measure %；It is further preferred that the content of the inorganic oxide carrier is 55-85 weight %, and in terms of oxide, described first The content of metallic element is 5-25 weight %, and the content of second metallic element is 5-15 weight %, the third metal member The content of element is 2-8 weight %, and based on the element, the content of the 4th metallic element is 0.01-0.08 weight %；Most preferably The content on ground, the inorganic oxide carrier is 66-85 weight %, and in terms of oxide, the content of first metallic element is 6-16 weight %, the content of second metallic element are 5-12 weight %, and the content of the third metallic element is 3-8 weight % is measured, based on the element, the content of the 4th metallic element is 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 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.
The present invention, to described by the presoma of inorganic oxide carrier, the first metallic element presoma, the second metallic element There is no particular limitation for the method that presoma, third metallic element presoma and water are mixed with beating, to inorganic oxide carrier Presoma, the first metallic element presoma, the addition sequence of the second metallic element presoma and third metallic element presoma are same Sample does not limit, as long as by the presoma of inorganic oxide carrier, the first metallic element presoma, the second metallic element presoma It is contacted with third metallic element presoma and water, it is preferable that first by the first metallic element presoma and third metal member Plain presoma is dissolved in water, then be added inorganic oxide carrier presoma (preferably acidified inorganic oxide carrier Presoma), the first solution is obtained, the second metallic element presoma is mixed with water, obtains the second solution, it is finally molten by first Liquid, the mixing of the second solution, then mashing obtains slurries.
In the present invention, 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 of Cu, Zn, Cd, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Re and rare earth element； 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 includes At least one of Au, Ag, Pt, Os, Ir, Ru, Rh and Pd.
The preparation method 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 preparation method 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 second metallic element presoma, third metallic element presoma are respectively selected from the second metallic element, third gold 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.
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, the present invention be not special to this Restriction.
A preferred embodiment of the invention, it is 400-1000 DEG C that the condition of first roasting, which includes: temperature, 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 in 0.01- (absolute pressure) is carried out under 1Mpa.
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.
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 is right before dry and/or the second roasting after step (2) described dipping The solid product carries out alkali process.Alkali process is carried out after precious metal element dipping, so that precious metal element (the 4th metal member Element) and the first metallic element and optionally the second metallic element, third metallic element can be even closer combination, more favorably In playing the synergistic effect between metallic element, it is more conducive to improving the composition that can reduce CO and NOx emission to NH3Deng The catalyzed conversion activity and hydrothermal stability of reduction-state 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 0.4- When 0.5mL/g, when the amount of the solid product of processing is 100g, the ammonia spirit 60-250mL of 0.5-2mol/L can be selected.
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, when Between be 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.
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, this method comprises:
(1) presoma of aluminium oxide, the presoma of Fe, the presoma of Co, the presoma of Mg, the presoma of Mn and water are mixed Mashing is closed, slurries is obtained, the slurries is spray-dried, the first roasting is then carried out, obtains intermediate composition；
(2) using contain Ru presoma solution as maceration extract, intermediate composition obtained by step (1) is soaked Stain obtains solid product, carries out alkali process to the solid product, is then dried and/or second roasts；
Wherein, the presoma and Ru of the presoma of aluminium oxide, the presoma of Fe, the presoma of Co, the presoma of Mg, Mn The dosage of presoma make, in composition obtained, in terms of oxide, the weight ratio of Fe and Co are 1:(0.4-2), with combination On the basis of the total amount of object, the content of aluminium oxide is 66-85 weight %, and in terms of oxide, the total content of Fe and Co are 6-16 weight % is measured, the content of Mg is that the content of 5-12 weight %, Mn are 3-8 weight %, and based on the element, the content of Ru is 0.05-0.07 weight Measure %.
The present invention also provides the compositions that can reduce CO and NOx emission as made from above-mentioned preparation method.
It can reduce as made from above-mentioned preparation method and contain Fe and Co and noble metal in CO and the composition of NOx emission At least one of element preferably also contains at least one of I A and/or Group IIA metal element and/or I B-VIIB race At least one of non-noble metal j element, above-mentioned metallic element are used cooperatively, and make it possible to reduce the composition of CO and NOx emission To NH3The catalyzed conversion activity of equal reduction-states nitride significantly improves, and makes it possible to reduce the composition of CO and NOx emission With preferable hydrothermal stability.
The present invention also provides application of the above-mentioned composition that can reduce CO and NOx emission in fume treatment.This hair The composition of bright offer can be used for handling any required flue gas for reducing CO and NOx emission.
The present invention also provides the above-mentioned compositions that can reduce CO and NOx emission in regeneration fume from catalytic cracking processing Application.The above-mentioned composition that can reduce CO and NOx emission is especially suitable for reducing complete regenerated flue gas and incomplete regen-eration The discharge of CO and NOx in flue gas.
The 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, structure determination, Cu target, K α radiation, solid probe, tube voltage 40kV, tube current 40mA are carried out.
It is raw materials used in embodiment and comparative example: cobalt nitrate [Co (NO3)2·6H2O] it is to analyze pure, ferric nitrate [Fe (NO3)3·9H2O] it is 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；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, in The production of Effect of Catalysis In Petrochemistry agent Co., Ltd of state.
Embodiment 1
(1) 2.62kg boehmite is added to be beaten in 14.2kg deionized water and is dispersed, 238mL hydrochloric acid is then added It is acidified 15min, aluminium stone colloid is obtained, by the ferric nitrate in terms of metal oxide (with Fe2O3Meter, similarly hereinafter) 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 air, 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's with concentration Ammonia spirit 80mL elutes solid product, obtains composition S-1 through drying (100 DEG C, 4h), roasting (400 DEG C, 2h).
Each component assay result is listed in table 1 in composition S-1.
Embodiment 2
(1) 2.53kg boehmite is added to be beaten in 13.7kg deionized water and is dispersed, 229mL hydrochloric acid is then added It is acidified 15min, aluminium stone colloid is obtained, by ferric nitrate 100g, cobalt nitrate 60g, KMnO in terms of metal oxide4(in terms of MnO) 60g is added stirring in 3500mL water and is added thereto aluminium stone colloid to abundant dissolution, stirs 15min, obtain the first solution；It will 160g MgO is added in 480g water, is added after stirring 10min into the first solution, after stirring 20min, slurries is obtained, by institute It states slurries to be spray-dried, the particle 150g for taking spray drying to obtain is transferred in tube furnace, logical with the flow of 100mL/min Enter air, handles 3h at 500 DEG C, obtain 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's with concentration Ammonia spirit 100mL elutes solid product, obtains composition S-2 through drying (100 DEG C, 4h), roasting (400 DEG C, 2h).
Each component assay result is listed in table 1 in composition S-2.
Embodiment 3
(1) 2.09kg boehmite is added to be beaten in 11.3kg deionized water and is dispersed, 190mL hydrochloric acid is then added It is acidified 15min, aluminium stone colloid is obtained, by ferric nitrate 100g, cobalt nitrate 200g, KMnO in terms of metal oxide4(in terms of MnO) 160g is added stirring in 4000mL water and is added thereto aluminium stone colloid to abundant dissolution, stirs 15min, obtain the first solution；It will 200g MgO is added in 600g water, is added after stirring 10min into the first solution, after stirring 20min, slurries is obtained, by institute It states slurries to be spray-dried, the particle 150g for taking spray drying to obtain is transferred in tube furnace, logical with the flow of 100mL/min Enter air, handles 1h at 650 DEG C, obtain 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, the ammonia for being 2mol/L with concentration Aqueous solution 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.
Embodiment 4
(1) 2.09kg boehmite is added to be beaten in 11.3kg deionized water and is dispersed, 190mL hydrochloric acid is then added It is acidified 15min, aluminium stone colloid is obtained, by ferric nitrate 200g, cobalt nitrate 120g, KMnO in terms of metal oxide4(in terms of MnO) 100g is added stirring in 3500mL water and is added thereto aluminium stone colloid to abundant dissolution, stirs 15min, obtain the first solution；It will 240gMgO is added in 720g water, is added after stirring 10min into the first solution, after stirring 20min, is obtained slurries, will be described Slurries are spray-dried, and the particle 150g for taking spray drying to obtain is transferred in tube furnace, are passed through with the flow of 100mL/min Air 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's with concentration Ammonia spirit 80mL elutes solid product, obtains composition S-4 through drying (100 DEG C, 4h), roasting (400 DEG C, 2h).
Each component assay result is listed in table 1 in composition S-4.
Embodiment 5
(1) 2.62kg boehmite is added to be beaten in 14.2kg deionized water and is dispersed, 238mL hydrochloric acid is then added It is acidified 15min, obtains aluminium stone colloid, ferric nitrate 100g, the cobalt nitrate 100g in terms of metal oxide are added in 3500mL water Aluminium stone colloid is added thereto to abundant dissolution, stirs 15min, obtain the first solution by stirring；100g MgO is added to 360g In water, it is added after stirring 10min into the first solution, after stirring 20min, obtains slurries, the slurries are spray-dried, The particle 150g (average grain diameter is 65 μm, and partial size is that 40-80 μm of particle accounts for 60%, similarly hereinafter) for taking spray drying to obtain is transferred to In tube furnace, air is passed through with the flow of 100mL/min, 1.5h is handled 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's with concentration Ammonia spirit 80mL elutes solid product, obtains composition S-5 through drying (100 DEG C, 4h), roasting (400 DEG C, 2h).
Each component assay result is listed in table 1 in composition S-5.
Embodiment 6
(1) 2.62kg boehmite is added to be beaten in 14.2kg deionized water and is dispersed, 238mL hydrochloric acid is then added It is acidified 15min, aluminium stone colloid is obtained, by ferric nitrate 100g, cobalt nitrate 100g, KMnO in terms of metal oxide4(in terms of MnO, Similarly hereinafter) 100g is added stirring in 3500mL water and is added thereto aluminium stone colloid to abundant dissolution, after stirring 20min, is starched The slurries are spray-dried by liquid, and (average grain diameter is 65 μm to the particle 150g for taking spray drying to obtain, partial size 40-80 μm particle account for 60%, similarly hereinafter) be transferred in tube furnace, air is passed through with the flow of 100mL/min, is handled at 600 DEG C 1.5h 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's with concentration Ammonia spirit 80mL elutes solid product, obtains composition S-6 through drying (100 DEG C, 4h), roasting (400 DEG C, 2h).
Each component assay result is listed in table 1 in composition S-6.
Embodiment 7
(1) 2.62kg boehmite is added to be beaten in 14.2kg deionized water and is dispersed, 238mL hydrochloric acid is then added It is acidified 15min, obtains aluminium stone colloid, ferric nitrate 100g, the cobalt nitrate 100g in terms of metal oxide are added in 3500mL water Stirring is dissolved to abundant, and aluminium stone colloid is added thereto, and is stirred 20min, is obtained slurries, the slurries are spray-dried, The particle 150g (average grain diameter is 65 μm, and partial size is that 40-80 μm of particle accounts for 60%, similarly hereinafter) for taking spray drying to obtain is transferred to In tube furnace, air is passed through with the flow of 100mL/min, 1.5h is handled 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's with concentration Ammonia spirit 80mL elutes solid product, obtains composition S-7 through drying (100 DEG C, 4h), roasting (400 DEG C, 2h).
Each component assay result is listed in table 1 in composition S-7.
Embodiment 8
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-8.
Each component assay result is listed in table 1 in composition S-8.
Embodiment 9
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-9.
Each component assay result is listed in table 1 in composition S-9.
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 5 Embodiment 6 Embodiment 7 Comparative example 3
Dry gas, weight % 1.70 1.71 1.71 1.71 1.73
Liquefied gas, weight % 19.29 19.24 19.27 19.26 19.20
Coke, weight % 7.20 7.19 7.18 7.19 7.29
Gasoline, weight % 49.66 49.68 49.55 49.58 49.44
Diesel oil, weight % 15.08 15.14 15.21 15.22 15.27
Heavy oil, weight % 7.07 7.03 7.09 7.03 7.06
Conversion ratio, % 77.87 77.83 77.70 77.74 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 Can, and be the composition that can reduce CO and NOx emission after aging, can reduce after aging used in evaluation procedure 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 There is preferable hydrothermal stability with the composition of NOx emission.
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 62 63 2.87
Comparative example 1 D-1 118 154 2.86
Comparative example 2 D-2 110 151 2.91
Comparative example 3 D-3 109 321 3.15
Embodiment 2 S-2 55 60 2.80
Embodiment 3 S-3 39 5 2.70
Embodiment 4 S-4 30 8 2.70
Embodiment 5 S-5 54 75 2.77
Embodiment 6 S-6 72 91 2.75
Embodiment 7 S-7 74 55 2.71
Embodiment 8 S-8 61 65 2.90
Embodiment 9 S-9 65 66 2.87
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 combination that can reduce CO and NOx emission after aging used in evaluation procedure with NOx emission performance Object, composition removing CO, NH that can reduce CO and NOx emission after aging3Still higher with NOx activity, therefore, the present invention mentions The can reduce CO and the composition of NOx emission supplied has 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 1-4 and embodiment 5-7 comparison as can be seen that using currently preferred metallic element as active group Divide and be used cooperatively, the composition properties for making it possible to reduce CO and NOx emission further increase；From embodiment 1 and embodiment 8, The comparison of embodiment 9 makes it possible to reduce the group of CO and NOx emission as can be seen that using currently preferred Fe and Co mass ratio Closing physical property can be further improved；From embodiment 1 and comparative example 1-3 comparison as can be seen that the present invention is by making Fe and Co cooperation With 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 (13)

1. a kind of preparation method for the composition that can reduce CO and NOx emission, which is characterized in that this method comprises:
(1) presoma of inorganic oxide carrier, the first metallic element presoma and water are mixed with beating, obtain slurries, by institute It states slurries to be spray-dried, then carries out the first roasting, obtain 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, carries out alkali process to the solid product, is then dried 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 Four metallic elements are 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).
2. preparation method according to claim 1, wherein the method for the alkali process include: by the solid product with Alkaline solution is mixed with beating, or elutes the solid product using alkaline solution；
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.
3. preparation method according to claim 1 or 2, wherein the presoma of the inorganic oxide carrier, the first metal The dosage of elemental precursor and the 4th metallic element presoma makes, in composition obtained, on the basis of the total amount of composition, The content of the inorganic oxide carrier is 59.9-94.995 weight %, in terms of oxide, the content of first metallic element For 5-40 weight %, based on the element, the content of the 4th metallic element is 0.005-0.1 weight %；
Preferably, the content of the inorganic oxide carrier is 74.92-91.99 weight %, in terms of oxide, first gold medal The content for belonging to element is 8-25 weight %, and based on the element, the content of the 4th metallic element is 0.01-0.08 weight %；
It is further preferred that the content of the inorganic oxide carrier is 83.93-89.95 weight %, it is described in terms of oxide The content of first metallic element is 10-16 weight %, and based on the element, the content of the 4th metallic element is 0.05-0.07 weight Measure %.
4. preparation method described in any one of -3 according to claim 1, wherein the use of the presoma of the presoma and Co of Fe Amount so that, in composition obtained, in terms of oxide, the weight ratio of Fe and Co is 1:(0.1-10), preferably 1:(0.3-3), Further preferably 1:(0.4-2).
5. preparation method described in any one of -4 according to claim 1, wherein
The first metallic element presoma and the 4th metallic element presoma are respectively selected from the first metallic element and the 4th metal The water soluble salt of element；
Preferably, the 4th metallic element is selected from least one of Pt, Ir, Pd, Ru and Rh, most preferably Ru.
6. according to claim 1, preparation method described in any one of 2,4 and 5, wherein this method further include: in step (1) described be mixed with beating introduces the second metallic element presoma and/or third metallic element presoma in the process；Second gold medal Belong to element and be selected from least one of I A and/or Group IIA metal element, the third metallic element is selected from I B-VIIB race At least one of non-noble metal j element.
7. preparation method according to claim 6, wherein the presoma of the inorganic oxide carrier, the first metal member Plain presoma, the second metallic element presoma, third metallic element presoma and the 4th metallic element presoma dosage make, In composition obtained, on the basis of the total amount of composition, the content of the inorganic oxide carrier is 10-90 weight %, with Oxide meter, the content of first metallic element are 0.5-50 weight %, and the content of second metallic element is 0.5-20 The content of weight %, the third metallic element are 0.5-20 weight %, and based on the element, the content of 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 %.
8. preparation method according to claim 6 or 7, wherein the second metallic element in Na, K, Mg and Ca at least One kind, 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；
The second metallic element presoma, third metallic element presoma are respectively selected from the second metallic element, third metal member The water soluble salt of element.
9. preparation method described in any one of -8 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 presoma； Preferably, the inorganic oxide carrier is selected from least one of aluminium oxide, spinelle and perovskite, further preferably oxygen Change 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。
10. can reduce the combination of CO and NOx emission made from the preparation method as described in any one of claim 1-9 Object.
11. application of the composition described in any one of claim 10 that can reduce CO and NOx emission in fume treatment.
12. the composition described in any one of claim 10 that can reduce CO and NOx emission is in regeneration fume from catalytic cracking processing Using.
13. 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 that the CO and NOx described in any one of claim 10 that can reduce is arranged The composition put.
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TW107123246A TWI786147B (en) 2017-07-05 2018-07-05 Composition capable of reducing CO and NOx emissions, its preparation method and application, and fluidized catalytic cracking method
PCT/CN2018/094584 WO2019007381A1 (en) 2017-07-05 2018-07-05 Composition capable of reducing co and nox emissions, preparation method therefor and use thereof, and fluid catalytic cracking method
JP2020500124A JP7114688B2 (en) 2017-07-05 2018-07-05 COMPOSITION CAPABLE OF REDUCING CO AND NOx EMISSIONS, PRODUCTION METHOD AND USE THEREOF, AND FLUID CATALYTIC Cracking Process
EP18827377.5A EP3693085A4 (en) 2017-07-05 2018-07-05 Composition capable of reducing co and nox emissions, preparation method therefor and use thereof, and fluid catalytic cracking method
US16/626,742 US11529612B2 (en) 2017-07-05 2018-07-05 Composition capable of reducing CO and NOx emissions, preparation method therefor and use thereof, and fluid catalytic cracking method
AU2018298192A AU2018298192B2 (en) 2017-07-05 2018-07-05 Composition capable of reducing CO and NOx emissions, preparation method therefor and use thereof, and fluid catalytic cracking method
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