CN102580728A - Catalyst and preparation method - Google Patents
Catalyst and preparation method Download PDFInfo
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- CN102580728A CN102580728A CN2011100075748A CN201110007574A CN102580728A CN 102580728 A CN102580728 A CN 102580728A CN 2011100075748 A CN2011100075748 A CN 2011100075748A CN 201110007574 A CN201110007574 A CN 201110007574A CN 102580728 A CN102580728 A CN 102580728A
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Abstract
The invention relates to a catalyst system, which comprises a first catalyzing composition containing homogenous solid mixture, wherein the homogenous solid mixture contains at least one catalyzing metal and at least one metal inorganic carrier. Holes of the solid mixture have an average aperture from 1 nanometer to 15 nanometers. The catalyzing metal comprises nano crystals.
Description
Technical field
Said system comprises the embodiment that relates to catalyst with technology.They also comprise the system implementation scheme that relates to the preparation catalyst and can comprise catalyst.
Background technology
The exhaust stream that combustion of fossil fuel (like heating furnace, baking oven and engine) produces comprises various potential unwanted combustion products, comprises nitrogen oxide (NO
x), unburned hydrocarbon (HC) and carbon monoxide (CO).NO
xThough, unstable on thermodynamics, there is not catalyst just can not spontaneously to decompose.Exhaust is flowed exhaust gas treatment device capable of using and is removed NO from the exhaust diffluence
x
The instance of exhaust gas treatment device comprises that catalytic converter (for example; Three usefulness catalyst, oxidation catalyst, SCR (SCR) catalyst etc.), discharge vaporization device, wash mill (for example; Hydrocarbon (HC), sulphur etc.), particulate filter/trap, absorber/absorber, plasma reactor (for example, non-thermal plasma reactor and hot plasma reactor) etc.Three usefulness catalyst (TWC catalyst) available CO and residual hydrocarbon reductive NO in the catalytic converter
xThe TWC catalyst can be in the concrete operations scope of poor and rich two kinds of fuel/air mixture conditions and concrete operations temperature range effectively.The graininess catalyst composition can make HC, CO and NO
xConversion can reach best.Conversion ratio can be depending on delivery temperature.Catalytic converter can operation under about 300 ℃ or higher rising catalyst temperature.Being heated to up to the time phase of firing temperature between the time to matrix when beginning (that is, " cold start-up ") at exhaust emissions is the duration of ignition.Firing temperature is at the catalyst temperature that transforms the place when the catalyst from 50 (50%) percent of the discharging of engine.The alternative method of available heatable catalyst makes catalyst temperature reach firing temperature.
But exhaust heatable catalytic converter from engine.This heating can help to make catalyst reach firing temperature.Exhaust is constant relatively through catalytic converter, until reaching firing temperature.In addition, the composition of engine exhaust is along with engine temperature is elevated to operating temperature and changes from cooling start temperature, and the TWC catalyst can work to the exhaust banks compound that under the normal engine operating temperature that raises, exists.
SCR (SCR) can comprise noble metal systems, base metal system or zeolites system.Noble metal catalyst can be operated in about 240 ℃ of extremely about 270 ℃ temperature ranges, but suppressed by the existence of sulfur dioxide.Base metal catalysts can be operated in about 310 ℃ of extremely about 500 ℃ temperature ranges, but can promote that oxidizing sulfur dioxide becomes sulfur trioxide.Zeolite can stand the highest 600 ℃ of temperature, but when flooding with base metal, can have the operating temperature of wide region.
Have ammonia and can in the turbogenerator of big combustion natural gas and poor combustion diesel engine, produce NO greater than 80% as the SCR system of reducing agent
xReduction efficiency.Yet, exist ammonia not need, and owing to incomplete distribution of reacting gas and incomplete ammonia consumption have some ammonia leakages.In addition, ammonia solution needs other storage tank, and under cold ambient temperature, experiences and freeze.
NO
xSCR also can accomplish with hydrocarbon.Under the excessive oxygen condition, can pass through some organic compounds selective reduction NO on several catalyst
x, said organic compound such as alkane, alkene and alcohol.In order in exhaust stream, to replenish hydrocarbon (HC), explored and in heavy stationary diesel engine, injected diesel oil or methyl alcohol.Yet, exceeding 300 ℃ to 400 ℃ temperature ranges, transformation efficiency possibly reduce.In addition, this technology possibly have HC to leak at catalyst, transportation and on-the-spot a large amount of hydrocarbon that store, and possibly discharge HC by normal pressure.The partial oxidation of hydrocarbon possibly discharge CO, unburned HC and particle.
Possibly have a kind of catalyst, under the operating condition of certain temperature range and those conditions that are different from present utilization, said catalyst can realize that discharging reduces.
Summary of the invention
In one embodiment, the present invention provides a kind of antigravity system.This antigravity system comprises first catalyst composition that comprises the homogeneous solid mixture, and said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier.The hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers.Said catalytic metal comprises nanocrystal.
In another embodiment, the present invention provides a kind of antigravity system.This antigravity system comprises first catalyst composition that comprises the homogeneous solid mixture, and said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier.The hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers.Said catalytic metal comprises nanocrystal.This antigravity system also comprises at least a catalytic metal (promoting metal) that helps.Said antigravity system also comprises second catalyst composition.Second catalyst composition comprises (i) zeolite, or (ii) places first catalytic specie on first matrix.First catalytic specie comprises the element that is selected from tungsten, titanium and vanadium.
In going back another embodiment, the present invention provides a kind of method.Said method comprising the steps of: the nanocrystal that at least a catalytic metal is provided; Nanocrystal is incorporated at least a metal inorganic carrier; And formation comprises first catalyst composition of homogeneous solid mixture; Said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier; Wherein the hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers, and wherein catalytic metal comprises nanocrystal.
In another embodiment again, the present invention provides a kind of gas extraction system, and said gas extraction system comprises the fuel delivery system that is configured to fuel is transported to engine; Be configured to receive the exhaust circulation road of exhaust stream from engine; Be configured to reducing agent is transported to the reducing agent induction system in exhaust circulation road; With the antigravity system that places the exhaust circulation road.Said antigravity system comprises: first catalyst composition that comprises the homogeneous solid mixture; Said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier; Wherein the hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers, and wherein catalytic metal is the nanocrystal form.
In another embodiment again; The present invention provides a kind of antigravity system; Said antigravity system comprises first catalyst composition that comprises the homogeneous solid mixture, and said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier, and wherein the hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers; Wherein catalytic metal comprises nanocrystal, and wherein nanocrystal has the size distribution less than about 20%.Catalytic metal exists to be equal to or less than about 6% mole amount based on the homogeneous solid mixture weight.
Description of drawings
Through reading following detailed description and with reference to accompanying drawing, of the present invention these with understandings that will improve of other characteristics, aspect and advantage, wherein similar element represented in similar character in whole accompanying drawings, wherein:
Fig. 1 is a sketch map of describing antigravity system assembling in the stove;
Fig. 2 is a sketch map of describing antigravity system assembling in the stove;
Fig. 3 is a sketch map of describing antigravity system assembling in the stove;
Fig. 4 comprises the sketch map of the gas extraction system of antigravity system assembling for describing according to one embodiment of the invention;
Fig. 5 comprises the sketch map of the gas extraction system of antigravity system assembling for describing according to one embodiment of the invention;
Fig. 6 comprises the sketch map of the gas extraction system of antigravity system assembling for describing according to one embodiment of the invention;
Fig. 7 comprises the sketch map of the gas extraction system of antigravity system assembling for describing according to one embodiment of the invention;
Fig. 8 comprises the sketch map of the gas extraction system of antigravity system assembling for describing according to one embodiment of the invention;
Fig. 9 comprises the sketch map of the gas extraction system of antigravity system assembling for describing according to one embodiment of the invention;
Figure 10 is the transmission electron microscope photo (TEM) according to the silver-colored nanocrystal of one embodiment of the invention;
Figure 11 is the TEM according to the silver-colored nanocrystal of one embodiment of the invention;
Figure 12 is the TEM according to the silver-colored nanocrystal of one embodiment of the invention;
Figure 13 is the TEM according to the silver-colored nanocrystal of one embodiment of the invention;
Figure 14 is the energy dispersion X-ray spectrum (EDS) according to the silver-colored nanocrystal of one embodiment of the invention;
Figure 15 is according to the ultraviolet-visible of the silver-colored nanocrystal of one embodiment of the invention (UV-Vis) spectrum;
Figure 16 is the TEM according to the homogeneous solid mixture of the argentiferous of one embodiment of the invention;
Figure 17 is the TEM according to the homogeneous solid mixture of the argentiferous of one embodiment of the invention;
Figure 18 is the TEM according to the homogeneous solid mixture of the argentiferous of one embodiment of the invention;
Figure 19 is the EDS according to the homogeneous solid mixture of the argentiferous of one embodiment of the invention;
Figure 20 is the NO that describes according to one embodiment of the invention
xThe block diagram that transforms;
Figure 21 is the CO that describes according to one embodiment of the invention
2The block diagram that transforms;
Figure 22 is according to one embodiment of the invention, different temperatures, in the presence of catalyst NO
xThe figure that transforms;
Figure 23 is according to one embodiment of the invention, different temperatures, in the presence of catalyst NO
xThe figure that transforms;
Figure 24 is according to one embodiment of the invention, different temperatures, in the presence of catalyst NO
xThe figure that transforms; With
Figure 25 is according to one embodiment of the invention, different temperatures, in the presence of catalyst NO
xThe figure that transforms.
The specific embodiment
Said system comprises the embodiment that relates to catalyst and uses thereof and preparation with technology.Other embodiments relate to the goods that comprise catalyst and catalyst composition, but said catalyst and catalyst composition electronation are producing the NO that exists in the discharging during the burning (for example, in heating furnace, baking oven, engine and locomotive, burning)
x
Embodiment of the present invention described herein have solved the shortcoming of this area existence of being mentioned.Through using the NO in the antigravity system reduction exhaust that comprises at least the first catalyst composition
x, antigravity system described herein satisfies above-mentioned needs.First catalyst composition uses the homogeneous solid mixture; Said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier; Wherein the hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers, and wherein catalytic metal comprises nanocrystal.First catalyst composition makes the NO in the exhaust
xChange into nitrogenous chemical substance, for example ammonia.Said antigravity system also can comprise and helps catalytic metal.Said antigravity system also can comprise second catalyst composition.Second catalyst composition comprises that (i) places first catalytic specie or the (ii) zeolite on first matrix, and they both can use by the ammonia of the first catalyzed combination deposits yields or type ammonia product as NO
xReducing agent is with other NO in the further reduction exhaust
xIn certain embodiments, said antigravity system can comprise the 3rd catalyst composition, and the 3rd catalyst composition comprises second catalytic specie that places on second matrix.Second catalytic specie can be selected from platinum, palladium, ruthenium, osmium and iridium.Antigravity system described herein can further utilize hydrocarbon reducing agent, for example diesel oil.Is can be easy to obtain having on the wooden handcart of diesel engine (board vehicle) with diesel oil as an advantage of reducing agent.In certain embodiments, can use core ductant to reduce the firing temperature of catalyst with the hydrocarbon reducing agent.
Catalyst changes from nonexpendable material in reaction for causing chemical reaction rate.Powder is the material that comprises the fine dispersion solid particle.The piece material can be for having the ceramic block of many passages, and can through pushed away dyestuff produce structure clay, adhesive and additive extrude preparation.As in whole specification of this paper and claim, using, any quantitative expression modified in available approximate language, and these express the tolerable change, and do not cause the change of related basic function.Therefore, by term for example " pact " numerical value of modifying be not limited to specified exact value.In some cases, approximate language is for measuring the accuracy that numerical value can be equivalent to instrument.Similarly, " not containing " can use with projects combo, and can comprise non-substantial amount or trace, although still can think not contain the project of being modified.
One or more specific embodiments of the present invention is below described.For making great efforts to provide the simple and clear description of these embodiments, all characteristics in actual the enforcement possibly all not described in specification.Should understand; In the exploitation of any this type of actual embodiment; As in any engineering or the planned design, must make the concrete decision of many enforcements, to reach developer's objectives; Conform to the industry relevant limit as relevant with system, this can change to another embodiment from an embodiment.In addition, it will be appreciated that this development effort maybe be complicated and consuming time, but still be routine to those skilled in the art with design, assembling and manufacturing of disclosure benefit.
When introducing the element of different embodiments of the present invention, article " ", " this ", " being somebody's turn to do " and " said " have one or more elements with expression.Word " comprises ", " comprising " and " having " will be comprising property, and expression can have the other element that is different from listed element.In addition, " top ", " bottom ", " ... on ", " ... under " and the modification of these words use for ease, but do not need any concrete orientation of element, unless otherwise indicated.Word used herein " place ... on " or " be deposited on ... on " or " place ... between " be meant direct contact and have the fixing of insertion layer indirectly betwixt or arrange.
In one embodiment, the present invention provides a kind of antigravity system.Said antigravity system comprises the homogeneous solid mixture, and said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier.The hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers.Catalytic metal comprises nanocrystal.
In one embodiment, nanocrystal has the size distribution (PSD) less than about 20%.In another embodiment, nanocrystal has the PSD less than about 15%.In going back another embodiment, nanocrystal has the PSD less than about 10%.In one embodiment, PSD can use transmission electron microscopy (TEM) to measure.TEM is a kind of technology, and wherein the electron beam transmission is through ultra-thin sample, its through the time with the sample interaction.The mutual use of being passed through sample by electronic transmission forms image, and the image amplification also focuses on the image device, like fluorescent screen, focuses on the film layer, is perhaps detected by sensor, like the charge-coupled device (CCD) camera.Because the little de Broglie wavelength of electronics, TEM can be to form images than the remarkable higher resolution ratio of light microscope.This makes the user of instrument can check small details, even the same with single-row atom little, and this is littler tens thousand of times than the minimum distinguishable object in the light microscope.TEM forms main analytical method in physics and biological certain limit scientific domain.At less magnifying power, the TEM image comparison is the absorption owing to electronics in the material, because the thickness and the composition of material.Than high power, complex wave interacts and regulates the intensity of image, needs to observe the analysis expert of image.Electronics phase transfer and the conventional modulation that absorbs in the imaging of basis that the pattern that is used alternatingly allows tem observation chemical characteristic, crystal orientation, electronic structure and sample to induce.
In one embodiment, the catalytic metal of nanocrystal form comprises transition metal.The suitable transition metal that can be used as catalytic metal can comprise the combination of silver, platinum, gold, palladium, iron, nickel, cobalt, gallium, indium, ruthenium, rhodium, osmium, iridium or at least two kinds of aforementioned metal.In one embodiment, catalytic metal comprises silver.
In one embodiment, the metal inorganic carrier of formation homogeneous solid mixture has the hole.The porous metals inorganic carrier is the product of reaction solution, solvent, modifier and template (templating agent).A kind of method comprises mixed reaction solution and template, to form gel; And the calcining gel, with form can the bearing catalyst composition the porous metals inorganic carrier.In one embodiment, the metal inorganic carrier can be through the U.S. Patent application 20090074641 described method preparations of common pending trial, and said application is attached among this paper in full by reference.Use like this paper, do not have other modifier, porous refers to that material comprises the hole in the aperture with about 1 nanometer to about 15 nanometers.In one embodiment, comprising the homogeneous solid carrier of the catalytic specie of metal inorganic carrier and nanocrystal form can be in the preparation of two steps.First step described herein comprises preparation solution, and this solution is included in the catalytic specie nanocrystal in the solvent.Second step is included in the metal inorganic preparing carriers process, and the solution that in solvent, comprises the catalytic specie nanocrystal is mixed with the metal inorganic precursor carrier, causes forming the homogeneous solid mixture.
In one embodiment, control is also selected the average pore size of metal inorganic carrier, to alleviate or to eliminate poisoning.Poisoning possibly influence catalytic capability, and can caused poisoning by the aromatic substances that exists in reducing agent or the exhaust stream.Compare with the general γ phase alumina of baseline of flooding with silver, porous mass as herein described has more resistance to the poisoning that is caused by the reducing agent that contains aromatic substances.
In different embodiments, the catalytic metal of nanocrystal form can be less than or equal to about 6% mole amount based on the homogeneous solid mixture weight and be present in first catalyst composition.The amount of one skilled in the art will understand that is selected can be based on final operation parameter, economic consideration, required effectiveness etc.In one embodiment, the catalytic metal that in first catalyst composition, exists is about 2% mole to about 6% mole based on the homogeneous solid mixture weight.In another embodiment, the catalytic metal that in first catalyst composition, exists is about 2.5% mole to about 4.5% mole based on the homogeneous solid mixture weight.In going back another embodiment, the catalytic metal that in first catalyst composition, exists is about 3% mole to about 4% mole based on the homogeneous solid mixture weight.
In one embodiment, the metal inorganic carrier can comprise inorganic substances.Phrase used herein " metal inorganic carrier " is meant that the carrier that comprises inorganic substances, said material part comprise the atom or the cation of one or more metallic elements.The inorganic substances that are fit to can comprise for example oxide, carbide, nitride, hydroxide, carbonitride, oxynitride, boride, silicate or boron-carbide.In one embodiment, inorganic oxide can have the hydroxide coating.In one embodiment, inorganic oxide can be metal oxide.Metal oxide can have the hydroxide coating.Other metal inorganic things that are fit to can comprise one or more metal carbides, metal nitride, metal hydroxides, carbonitride, metal oxynitrides, metal boride or metal boron-carbide.The metal cation that in aforementioned inorganic substances, uses can be transition metal, alkali metal, alkaline-earth metal, rare earth metal etc.Other elements that form the part of major element comprise aluminium, boron and silicon.
The instance of the inorganic oxide that is fit to comprises silica (SiO
2), aluminium oxide (Al
2O
3), titanium dioxide (TiO
2), zirconia (ZrO
2), ceria (CeO
2), magnesia (MgO), barium monoxide (BaO), yittrium oxide (Y
2O
3), vanadium oxide (V
2O
5), gallium oxide (Ga
2O
3), zinc oxide (ZnO), aluminosilicate (Al
2SiO
5), iron oxide (for example FeO, β-Fe
2O
3, γ-Fe
2O
3, β-Fe
2O
3, Fe
3O
4Deng), calcium oxide (CaO) and manganese dioxide (MnO
2And Mn
3O
4).The instance of the inorganic carbide that is fit to comprises carborundum (SiC), titanium carbide (TiC), ramet (TaC), tungsten carbide (WC), hafnium carbide (HfC) etc.The instance of the nitride that is fit to comprises silicon nitride (Si
3N
4), titanium nitride (TiN) etc.The instance of the boride that is fit to comprises lanthanum boride (LaB
6), chromium boride (CrB and CrB
2), molybdenum boride (MoB
2, Mo
2B
5And MoB), tungsten boride (W
2B
5) etc.In one embodiment, inorganic matrix is an aluminium oxide.Used aluminium oxide can be crystallization or unbodied.In one embodiment, the porous metals inorganic carrier comprises Woelm Alumina, and catalytic metal comprises silver-colored nanocrystal.
In one embodiment, the metal inorganic carrier has the average pore size greater than about 0.5 nanometer.In one embodiment, the metal inorganic carrier can have the average pore size of about 1 nanometer to about 15 nanometers.In another embodiment, the metal inorganic carrier can have the average pore size of about 2 nanometers to about 12 nanometers.In going back another embodiment, the metal inorganic carrier can have the average pore size of about 3 nanometers to about 15 nanometers.In one embodiment, the metal inorganic carrier can have the average pore size of about 1 nanometer to about 5 nanometers.Average pore size BET method capable of using is measured with the nitrogen adsorption measurement.The BET principle is the theory of physical absorption gas molecule on the surface of solids, and as the technological basis of the important analysis of measuring the material specific area.BET is the shorthand of the Stephen Brunauer that advances a theory, Paul Hugh Emmett and Edward Teller invention name.
In certain embodiments, the aperture has narrow Unimodal Distribution.In one embodiment, the hole have less than about 1.5, less than about 1.3 or less than about 1.1 pore-size distribution polydispersity index.In one embodiment, pore-size distribution can be bimodal or multimodal.
In another embodiment, the porous metals inorganic carrier comprises one or more stabilizing agents that can be added to the metal inorganic carrier.For example, in different embodiments, comprise that mainly the metal inorganic carrier of aluminium oxide has more a spot of yittrium oxide, zirconia or the ceria that is added to it.In one embodiment, the amount of yittrium oxide, zirconia or ceria is to about 10% weight based on alumina weight about 0.1%.In another embodiment, the amount of yittrium oxide, zirconia or ceria is based on alumina weight about 1% to about 9%.In going back another embodiment, the amount of yittrium oxide, zirconia or ceria is based on alumina weight about 2% to about 6%.
In one embodiment, the hole can be controlled and repetitive mode distribution formation pattern (pattern).In another embodiment, the hole is arranged as rule and nonrandom.Like this paper definition, phrase " hole is arranged as rule " is that finger-hole can be orderly, and can have property average period.Can select to control and select average span (pore spacing) according to the surfactant that between gelation time, uses.In one embodiment, the hole is unidirectional, and periodic intervals is opened, and has property average period.A kind of porous metals inorganic carrier has the hole, and said hole has the interval greater than about 200 nanometers.In one embodiment, be spaced apart about 300 nanometers to about 400 nanometers.In another embodiment, be spaced apart about 500 nanometers to about 2000 nanometers.In going back another embodiment, be spaced apart about 600 nanometers to about 1500 nanometers.The available small angle X ray scattering of average span (periodically) is measured.In another embodiment, span is at random.
The porous metals inorganic carrier can have greater than about 50 meters
2The surface area of/gram.In one embodiment, the porous metals inorganic carrier has about 50 meters
2/ gram is to about 2000 meters
2The surface area of/gram.In another embodiment, the porous metals inorganic carrier has about 100 meters
2/ gram is to about 1000 meters
2The surface area of/gram.In one embodiment, the porous metals inorganic carrier has about 300 meters
2/ gram is to about 600 meters
2The surface area of/gram.
The porous metal oxide inorganic carrier can be made up of particle.Particle can be face coat on agglomerate, agglomerate, the carrier etc.The porous metal oxide inorganic carrier can have the highest about 4 millimeters particle mean size.In one embodiment, inorganic porous substance can have about 5 microns to about 3 millimeters particle mean size.In another embodiment, inorganic porous substance can have about 500 microns to about 2.5 millimeters particle mean size.In another embodiment also, inorganic porous substance can have about 1 millimeter to about 2 millimeters particle mean size.In one embodiment, porous matrix has about 40 microns particle mean size.In one embodiment, porous matrix has about 10 microns particle mean size.
First catalyst composition can exist based on the amount of the highest about 90% weight of antigravity system gross weight.In one embodiment, first catalyst composition can exist based on the amount of about 1% weight of antigravity system gross weight to about 90% weight.In another embodiment, first catalyst composition of bed form can exist based on the amount of about 20% weight of antigravity system gross weight to about 80% weight.In going back another embodiment, first catalyst composition can exist based on the amount of about 50% weight of antigravity system gross weight to about 70% weight.In different embodiments, through measuring ratio at the amount of substance that is used on second that produces on first.This will depend on several variablees, and these variablees are used the concrete exhaust of antigravity system capable of using wherein has specificity.Engine or type of turbine, delivery temperature, flow velocity, NO
xConcentration etc. all become the factor of the ratio that determines first catalyst composition and second catalyst composition.For concrete application, can for example in giving fixed system, reach the highest NO
xThe mode of conversion ratio is optimized this ratio.
In one embodiment, first catalyst composition comprises at least a catalytic metal that helps.Helping catalytic metal is the metal that promotes catalyst action.In one embodiment, help catalytic metal can be selected from gallium, indium, gold, vanadium, zinc, tin, bismuth, cobalt, molybdenum, zirconium, hafnium and tungsten.In one embodiment, help catalytic metal to exist based on the amount of about 0.1% weight of antigravity system gross weight to about 20% weight.In another embodiment, first catalyst composition can exist based on the amount of about 0.5% weight of antigravity system gross weight to about 15% weight.In going back another embodiment, first catalyst composition can exist based on the amount of about 1% weight of antigravity system gross weight to about 12% weight.
In one embodiment, first catalyst composition can as shown in fig. 1ly be assemblied in the antigravity system.With reference to figure 1, the NO that determines first catalyst composition is provided
xThe antigravity system 100 of reducing power.First catalyst composition 112 places the quartz ampoule 110 with 1 inch external diameter.First catalyst composition 112 places in the quartz ampoule between two quartzy tampons 114 and 116.Now, quartz ampoule 110 can be used for gas extraction system, to help to make NO
xDischarging is minimized.
In one embodiment, said antigravity system can also comprise second catalyst composition.In one embodiment, first catalytic specie of second catalyst composition can comprise zeolite.The function of first catalytic specie comprises with the ammonia of the first catalyzed combination deposits yields or type ammonia product as NO
xReducing agent further reduces other NO in the exhaust
xIn one embodiment, zeolite does not contain additional metals, that is, aluminium in the zeolite and silicon metal ion not with any other metal ion exchanged, for example iron or copper ion.Zeolite can be natural existence or synthetic.The instance of the zeolite that is fit to is zeolite Y, zeolite beta, ferrierite, modenite, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, ZSM-57, zeolite A, X zeolite or the combination that comprises at least two kinds of aforementioned zeolites.In one embodiment, first catalytic specie is made up of ferrierite basically.Exemplary zeolite is the ferrierite with silicon-aluminum ratio of about 10 to about 30.In another embodiment, ferrierite has silicon-aluminum ratio of about 12 to about 25.In going back another embodiment, ferrierite has silicon-aluminum ratio of about 15 to about 20.In one embodiment, zeolite comprises additional metals, that is, and and aluminium in the zeolite and silicon metal ion and any other metal ion exchanged, for example iron or copper ion.The instance of the zeolite of this type of ion-exchange comprises iron zeolite and copper zeolite.
The instance that can be used for the commercially available zeolite of second catalyst composition is sold with following trade name: CBV100, CBV300, CBV400, CBV500, CBV600, CBV712, CBV720, CBV760, CBV780, CBV901, CP814E, CP814C, CP811C-300, CP914, CP914C, CBV2314, CBV3024E, CBV5524G, CBV8014, CBV28014, CBV10A, CBV21A, CBV90A etc. or comprise the combination of at least two kinds of aforementioned commercially available zeolites.
Zeolite granular can be the extrudate form, and generally has the highest about 2 millimeters particle mean size.In one embodiment, zeolite granular have about 0.001 millimeter to about 1.1 millimeters particle mean size.In another embodiment, zeolite granular have about 0.1 millimeter to about 0.9 millimeter particle mean size.In another embodiment also, zeolite granular have about 0.2 millimeter to about 0.8 millimeter particle mean size.In an exemplary, zeolite granular has about 0.001 millimeter particle mean size.
Zeolite granular can have the highest about 600 meters
2The surface area of/gram.In one embodiment, zeolite granular can have about 50 meters
2/ gram is to about 600 meters
2The surface area of/gram.In another embodiment, zeolite granular can have about 80 meters
2/ gram is to about 500 meters
2The surface area of/gram.In going back another embodiment, zeolite granular can have about 100 meters
2/ gram is to about 400 meters
2The surface area of/gram.Except other factors comprised the metal of unit cell dimension, aperture, catalytic specie type and exchange, high-specific surface area generally produced more effective conversion.
In another embodiment, second catalyst composition comprises first catalytic specie that places on first matrix.The suitable material that can be used as first matrix comprises above about the described inorganic substances of metal inorganic carrier.First catalytic specie can comprise the element that is selected from tungsten, titanium and vanadium.
First catalytic specie can the highest about 50% mole amount be present in second catalyst composition based on the amount of antigravity system.In one embodiment, first catalytic specie is to be present in second catalyst composition to about 50% mole amount for about 0.025% mole based on the amount of antigravity system.In another embodiment, first catalytic specie is to be present in second catalyst composition to about 40% mole amount for about 0.5% mole based on the amount of antigravity system.In another embodiment also, first catalytic specie is to be present in second catalyst composition to about 30% mole amount for about 1.0% mole based on the amount of antigravity system.In one embodiment, the amount of first catalytic specie is about 1.5% mole based on the amount of antigravity system in second catalyst composition.In another embodiment, the amount of first catalytic specie is about 5% mole based on the amount of antigravity system in second catalyst composition.
Second catalyst composition can use based on the amount of the highest about 80% weight of antigravity system gross weight.In one embodiment, second catalyst composition can use based on the amount of about 20% weight of antigravity system gross weight to about 70% weight.In another embodiment, second catalyst composition can use based on the amount of about 30% weight of antigravity system gross weight to about 60% weight.In going back another embodiment, second catalyst composition can use based on the amount of about 40% weight of antigravity system gross weight to about 50% weight.First catalytic specie also can following amount be present in second catalyst composition: this amount is selected from as above said about first catalyst composition, the amount of the same range as of catalytic specie in the metal inorganic carrier.
In one embodiment, the antigravity system that comprises first catalyst composition and second catalyst composition can be assemblied in the antigravity system with the double bed structure as shown in Figure 2.With reference to figure 2, the NO that determines first catalyst composition is provided
xThe antigravity system 200 of reducing power.First catalyst composition 212 places the quartz ampoule 210 with 1 inch external diameter.First catalyst composition 212 places in the quartz ampoule between two quartzy tampons 214 and 216.Second catalyst composition 222 similarly places between another group silica wool 218 and 220, leaves about 1 inch of first group of silica wool.Now, quartz ampoule 210 can be used for gas extraction system, to help to make NO
xDischarging is minimized.
In one embodiment; Said antigravity system also comprises the 3rd catalyst composition in the downstream that place second catalyst composition; The 3rd catalyst composition comprises second catalytic specie that places on second matrix, and wherein second catalytic specie is selected from platinum, palladium, ruthenium, rhodium, osmium and iridium.The suitable material that can be used as second matrix comprises above about the described inorganic substances of metal inorganic carrier.Second catalytic specie generally is used for any unwanted product of oxidation or the not reactant or the reducing agent of usefulness.
In one embodiment, the 3rd catalyst composition is diesel oxidation catalyst (DOC).The flow type device that DOC is made up of the tube (canister) that contains honey comb structure or matrix.Second matrix has the high surface of the active catalyst layer of being coated with.This layer comprises the noble metal of little abundant dispersion amount, like platinum or palladium.When DOC is passed through in exhaust, carbon monoxide, carburet hydrogen and liquid hydrocarbon particle (unburned fuel and oil) oxidation, thus reduce noxious emission.
Second catalytic specie can the highest about 50% mole amount be present in the 3rd catalyst composition.In one embodiment, second catalytic specie is present in the 3rd catalyst composition to about 50% mole amount with about 0.025% mole.In another embodiment, second catalytic specie is present in the 3rd catalyst composition to about 40% mole amount with about 0.5% mole.In another embodiment also, second catalytic specie is present in the 3rd catalyst composition to about 30% mole amount with about 1.0% mole.In one embodiment, the amount of second catalytic specie is about 1.5% mole in the 3rd catalyst composition.In another embodiment, the amount of second catalytic specie is about 5% mole in the 3rd catalyst composition.
The 3rd catalyst composition can use based on the amount of the highest about 90% weight of antigravity system gross weight.In one embodiment, the 3rd catalyst composition can use based on the amount of about 10% weight of antigravity system gross weight to about 80% weight.In another embodiment, the 3rd catalyst composition can use based on the amount of about 20% weight of antigravity system gross weight to about 70% weight.In going back another embodiment, the 3rd catalyst composition can use based on the amount of about 30% weight of antigravity system gross weight to about 60% weight.
In one embodiment, second matrix can comprise inorganic substances.In one embodiment, inorganic substances can comprise above about the listed material of metal inorganic carrier.The suitable material that can be used as second matrix comprises at least a member who is selected from aluminium oxide, titanium dioxide, zirconia, ceria, carborundum and composition thereof.
In one embodiment, the antigravity system that comprises first catalyst composition, second catalyst composition and the 3rd catalyst composition can be assemblied in the antigravity system with three bed structures as shown in Figure 3.With reference to figure 3, the NO that determines first catalyst composition is provided
xThe antigravity system 300 of reducing power.First catalyst composition 312 places the quartz ampoule 310 with 1 inch external diameter.First catalyst composition 312 places in the quartz ampoule between two quartzy tampons 314 and 316.Second catalyst composition 322 similarly places between another group silica wool 318 and 320, leaves about 1 inch of first group of silica wool.The 3rd catalyst composition 328 similarly places between another group silica wool 324 and 326, leaves about 1 inch of first group of silica wool.Now, quartz ampoule 310 can be used for gas extraction system, to help to make NO
xDischarging is minimized.
In one embodiment, said antigravity system also comprises the induction system that is configured to carry reducing agent.The NO that in the emission of catalyst composition reduction, produces from heating furnace, baking oven, locomotive and engine
xThe time, multiple hydrocarbon can effectively be used as reducing agent.In one embodiment, reducing agent is a hydrocarbon.In one embodiment, hydrocarbon has the average carbon chain length degree of about 2 carbon atoms to about 24 carbon atoms.In one embodiment, reducing agent is one or more in diesel oil, ultra-low-sulphur diesel (ULSD), ethanol, gasoline and the octane.In one embodiment, reducing agent is the hydrocarbon with about 3 carbon atoms or following average carbon chain length degree.In one embodiment, reducing agent is one or more in methane, ethene and the propylene.In one embodiment, reducing agent is through oxygenated hydrocarbon.In one embodiment, be ethanol through oxygenated hydrocarbon.
In certain embodiments, can use core ductant to reduce the firing temperature of catalyst with the hydrocarbon reducing agent.In one embodiment, core ductant is a hydrogen.In one embodiment, the amount of used core ductant can be for counting (ppm) 0 to about 4000ppm based on the total volume flow rate per approximately hundred of exhaust very much.In another embodiment, the amount of used core ductant can for based on the about 10ppm of the total volume flow rate of exhaust to about 3000ppm.In another embodiment also, the amount of used core ductant can be for based on the about 20ppm of the total volume flow rate of exhaust about 2000ppm extremely.In one embodiment, the amount of used core ductant can for based on the about 0ppm of the total volume flow rate of exhaust to about 1000ppm.
In an exemplary, available diesel oil is as reducing agent.With the higher hydrocarbon with per molecule about 5 to about 9 carbon atoms during as reducing agent, the reducible NO of catalyst composition
xThe all temps scope of striding that said antigravity system is favourable works.The temperature range that is fit to can comprise greater than about 325 ℃ temperature.Other temperature ranges can comprise the highest about 425 ℃ those.
In another embodiment, the present invention provides a kind of antigravity system.Said antigravity system comprises first catalyst composition that comprises the homogeneous solid mixture, and said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier.The hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers.Catalytic metal comprises nanocrystal.Said antigravity system also comprises at least a catalytic metal that helps.Said antigravity system also comprises second catalyst composition.Second catalyst composition comprises (i) zeolite, or (ii) places first catalytic specie on first matrix.First catalytic specie comprises the element that is selected from tungsten, titanium and vanadium.
In going back another embodiment, the present invention provides a kind of method.Said method comprising the steps of: the nanocrystal that at least a catalytic metal is provided; Nanocrystal is incorporated at least a metal inorganic carrier; And formation comprises first catalyst composition of homogeneous solid mixture; Said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier; Wherein the hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers, and wherein catalytic metal comprises nanocrystal.
In one embodiment, provide the nanocrystal of at least a catalytic metal to be included in the surfactant existence nanocrystal of preparation catalytic metal down.Term used herein " surfactant " is meant surface reactive material.Surfactant is generally amphiphilic organic cpd, and they comprise hydrophobic grouping (" their afterbody ") and hydrophilic radical (" their head ") amphipathic expression.Therefore, according to structure, their water solubles or organic solvent.Use surfactant to suppress silver-colored nanocrystal growth, thereby make nanocrystal have basically the size of all even control.In one embodiment, used surfactant can comprise the carboxylic acid with about 17 carbon-carbon bonds.In one embodiment, used surfactant can be selected from one or more in oleic acid, sad, laurate and the stearic acid.One skilled in the art will understand that capable of using provide required nanocrystal at any surfactant known in the art.
In one embodiment, the nanocrystal that catalytic metal is provided carries out to about 200 ℃ temperature at about 10 ℃.In another embodiment, the nanocrystal that catalytic metal is provided carries out to about 150 ℃ temperature at about 50 ℃.In another embodiment also, the nanocrystal that catalytic metal is provided carries out to about 120 ℃ temperature at about 60 ℃.
In one embodiment, provide the nanocrystal of catalytic metal under about 0.5 millimetres of mercury to the vacuum of about 10 millimetress of mercury, to carry out.In another embodiment, provide the nanocrystal of catalytic metal under about 0.8 millimetres of mercury to the vacuum of about 8 millimetress of mercury, to carry out.In going back another embodiment, provide the nanocrystal of catalytic metal under about 1 millimetres of mercury to the vacuum of about 5 millimetress of mercury, to carry out.
In one embodiment, nanocrystal has the PSD less than about 20%.In another embodiment, nanocrystal has the PSD less than about 15%.In going back another embodiment, nanocrystal has the PSD less than about 10%.
In one embodiment, the salt that provides the step of the nanocrystal of catalytic metal to comprise to form catalytic metal and the mixture of surfactant and high boiling solvent.Heating gained mixture is so that the salt of catalytic metal is dissolved in solvent.Under vacuum, add hot mixt, so that with any moisture that exists in the vacuum removal system, for example, the water that in reactive material, exists as impurity.General about 0.5 millimeter vacuum capable of using to about 10 millimetress of mercury.The salt of catalytic metal is dissolved in solvent, forms nanocrystal subsequently.
Term used herein " nanocrystal " is meant the nano-substance with at least one dimension that is less than or equal to about 100 nanometers.Because therefore their a lot of electricity and macroscopic property show strong size-dependent, and can control through careful preparation process, nanocrystal causes huge technical concerns.The synthesis of nano crystal has some advantage under vacuum and in the presence of surfactant.The salt of catalytic metal decomposes under vacuum.Known in the art, generally exist water can influence the monodispersity of metal.Through utilizing vacuum, the water removal that in reactant mixture, exists or generate, thus make the side effect that in the presence of water, takes place be reduced to bottom line.In addition, with surfactant introduce synthetic in effectively " protection " or control the growth of metal nanocrystal.Therefore, the metallic particles of method preparation has the size of nanometer range thus, and their PSD can be less than about 20%.
In one embodiment, solvent for use can comprise the organic solvent that has more than or equal to 90 ℃ of boiling points, and the also salt of solubilized catalytic metal.In one embodiment, solvent for use can comprise the amine solvent with 8 to 40 carbon atoms.The instance of suitable solvent can comprise one or more in trioctylphosphine amine, octyl amine and the hexadecylamine.
In one embodiment, filter or centrifugal before be added to solution solvent can comprise the polar solvent that is selected from ethanol, methyl alcohol and acetone.In one embodiment, the solvent that before centrifugal, utilizes is ethanol.In one embodiment, the solvent that adds after centrifugal can comprise any non-polar solven that is selected from hexane, chloroform, oxolane and toluene.In one embodiment, the solvent that utilizes in centrifugal back is hexane.
In one embodiment, in the presence of surfactant, the temperature that the salt of catalytic metal dissolves in solvent is about 10 ℃ to about 90 ℃.In another embodiment, temperature is about 60 ℃ to about 80 ℃.In one embodiment, after the salt of catalytic metal was dissolved in the solvent, reactant mixture was maintained at about 60 ℃ to about 120 ℃ temperature.In another embodiment, temperature is about 65 ℃ to about 100 ℃.In going back another embodiment, temperature is about 85 ℃ to about 90 ℃.In one embodiment, after the salt of catalytic metal was dissolved in the solvent, the time that reactant mixture keeps was about 0.5 hour to about 5 hours.In another embodiment, the time of reactant mixture maintenance is about 1 hour to about 4 hours.In going back another embodiment, the time that reactant mixture keeps is about 2 hours to about 3 hours.The amount of the solvent that can before centrifugal, add in one embodiment, can be higher than 1 milliliter.In another embodiment, the amount of this solvent can be about 10 milliliters to about 50 milliliters.In going back another embodiment, the amount of this solvent can be about 20 milliliters to about 45 milliliters.In different embodiments, according to centrifugal speed, the centrifugal time can be about 1 minute to about 1 hour.
In the method for using antigravity system, said antigravity system places the exhaust stream of internal combustion engine.Internal combustion engine can for various move or fixation device in the parts of any equipment, for example automobile, locomotive or generator.Because different engines has different ignition qualities, exhaust stream component is different between a system and another system.These differences can comprise NO
xThe existence or the amount of the existence of level variation, sulphur and other materials of product.The variation of operating parameters of engine also can change exhaust fluidity matter.The instance of different operating parameter can comprise temperature and flow velocity.The speed that can need and under the temperature that is suitable for to the needs of fixed system and operating parameter, with catalyst with NO
xBe reduced into nitrogen and oxygen.Any way of said antigravity system in can be in every way places the exhaust passage, for example with Powdered, the piece material extruded or as the form of washcoated (washcoated) matrix.Produce this type of powder bed, extrudate or through the various technology of coated substrates known in the art, and can be applicable to required composition and catalyst mode suitably the time.In addition, each catalyst composition can be carried on the carrier separately, or is carried on the identical carrier.They can in addition overlapping or partially mixed.For example, can place the exhaust passage at above Fig. 1, the antigravity system 100,200,300 described in 2 and 3, so that NO
xDischarging is minimized.
During operation, said antigravity system can make the NO that exists in the exhaust stream
xTransform about 90% weight.In one embodiment, said antigravity system be provided at about 275 ℃ to about 425 ℃ of temperature, based on NO
xPrimary quantity is at least about 40% NO
xConversion ratio.In another embodiment, said antigravity system be provided at about 275 ℃ to about 425 ℃ of temperature, based on NO
xThe NO of primary quantity about 45% to about 90%
xConversion ratio.In another embodiment also, said antigravity system be provided at about 275 ℃ to about 425 ℃ of temperature, based on NO
xThe NO of primary quantity about 55% to about 80%
xConversion ratio.In another embodiment again, said antigravity system be provided at about 275 ℃ to about 425 ℃ of temperature, based on NO
xThe NO of primary quantity about 50% to about 70%
xConversion ratio.In one embodiment, said antigravity system be provided at about 325 ℃ to about 375 ℃ of temperature, based on NO
xThe NO of primary quantity about 40% to about 70%
xConversion ratio.
In another embodiment again, the present invention provides a kind of gas extraction system, and said gas extraction system comprises the fuel delivery system that is configured to fuel is transported to engine; Be configured to receive the exhaust circulation road of exhaust stream from engine; Be configured to reducing agent is transported to the reducing agent induction system in exhaust circulation road; With the antigravity system that places the exhaust circulation road.Said antigravity system comprises: first catalyst composition that comprises the homogeneous solid mixture; Said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier; Wherein the hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers, and wherein catalytic metal is the nanocrystal form.
With reference to figure 4, providing can reductive NO
xGas extraction system 400.Gas extraction system 400 comprises fuel delivery system 410, and fuel delivery system 410 is configured to fuel contained in the fuel tank 412 414 is transported to engine 416.Produce exhaust stream 418 by engine 416, this exhaust stream 418 is through antigravity system 420, so that treated exhaust stream 422 to be provided.Fuel delivery system 410 also can comprise the reducing agent induction system 424 that is configured to carry reducing agent.In one embodiment, reducing agent is a fuel 414.In one embodiment, can be with the reducing agent that comprises fuel 414 from fuel tank 412 through syringe or vaporizer or burner 426, be delivered directly to antigravity system 420 through decanting point 428.In one embodiment, a part of fuel 414 can be transported to antigravity system 420 through decanting point 432 by exhaust stream 418 from fuel tank 412 through syringe or vaporizer or burner 430.In one embodiment, reducing agent induction system 424 also comprises core ductant 434.In one embodiment, core ductant 434 can be produced through reformer 436 by fuel 414.Source of oxygen 438 is provided to reformer 436.In one embodiment, the core ductant 434 that produces through reformer 436 comprises the synthesis gas of hydrogen and carbon monoxide.Core ductant 434 passes through antigravity system 420 through decanting point 428.In one embodiment, diesel particulate filter DPF 440 is between engine 416 and antigravity system 420, before decanting point 428.In this embodiment, through after the DPF 440, the reducing agent that contains fuel 414 and core ductant 434 is transported to antigravity system 420 through decanting point 428 at exhaust stream 418.In one embodiment, between fuel tank 412 and antigravity system 420, burner 442 is provided.Burner 442 combustion fuels 414, improving the temperature of exhaust stream 418, this is used under the situation of temperature that exhaust stream 420 has the optimum operation condition that is lower than antigravity system 422, improves the performance of antigravity system 420.In this embodiment, the output 444 of burner can exhaust flow in 418 DPF 440 and contain fuel 414 and the decanting point 428 of the reducing agent of core ductant 434 between.
In exemplary as shown in Figure 4, fuel can comprise ULSD.In some embodiment as shown in Figure 4, reducing agent comprises fuel.In reducing agent some embodiment different with fuel, available independent reducing agent case holds reducing agent therein, and this will explain in the description of the following accompanying drawing that provides.Reducing agent is not in the embodiment of fuel therein, and reducing agent can comprise the mixture of ethanol, gasoline, ethanol and gasoline and the mixture of ethanol and diesel oil.Engine 416 can be for producing exhaust (back and forth or rotation) and can be to any form of the internal combustion engine of the various fuels sources work of air inclusion, biodiesel, diesel oil and natural gas.DPF is an optional equipment, and this equipment can be positioned at the upper reaches of antigravity system, and is as shown in Figure 4, perhaps is positioned at downstream, and this will explain in the following accompanying drawing of giving is described.The purpose of filter is from exhaust diffluence particle-removing material (cigarette and ash).(not shown in the diagram) in certain embodiments, DPF can match with the diesel oil syringe, to make dpf regeneration through the cigarette ash that burnouts.Said burner burning diesel oil fuel, improving the temperature of exhaust stream, this is used in the performance of improving catalyst under the situation of optimum operation condition that delivery temperature is lower than catalyst.Burner is positioned at just at the antigravity system diesel oil before and the upper reaches of reformer injection.Be positioned at DPF under the situation at the upper reaches of antigravity system, burner can be positioned at the upper reaches or the downstream of DPF.Reformer produces core ductant hydrogen from diesel fuel and source of oxygen (most probable is from air).Also can in reforming process, produce carbon monoxide, carbon dioxide and water.Reformer also can carry out water-gas shift reaction, to improve the productive rate of hydrogen.Syringe or vaporizer or burner are in order to reducing agent (for example diesel fuel) is transported to the device of catalyst.Reducing agent can be vaporized and carried as air-flow, perhaps atomizing or spray into exhaust (or being sprayed on the antigravity system) with syringe.Antigravity system 420 can comprise the described antigravity system structure of this paper embodiment part.In addition, gas extraction system can comprise other equipment, and like pump, valve, sensor, control loop, computer (control logic), storage tank, blender (gas or liquid), insulator arrangement, stream, separator etc., these are understood by those skilled in the art.
With reference to figure 5, providing can reductive NO
xGas extraction system 500.Gas extraction system 500 comprises fuel delivery system 410, and fuel delivery system 410 is configured to the fuel that comprises in the fuel tank 412 414 is transported to engine 416.Produce exhaust stream 418 by engine 416, this exhaust stream 418 is through antigravity system 420, so that treated exhaust stream 422 to be provided.Fuel delivery system 410 also can comprise the reducing agent induction system 424 that is configured to carry reducing agent.Reducing agent induction system 424 comprises fuel fractionation device 510 and syringe or vaporizer or burner 426.In one embodiment, the reducing agent that comprises fuel 414 is at first through fuel fractionation device 510, so that light fuel cut 512 and heavy fuel cut 514 to be provided.Light fuel cut 512 comprises the hydrocarbon that has less than the average carbon chain length degree of about 12 carbon, and heavy fuel cut 514 comprises the hydrocarbon that has greater than the average carbon chain length degree of about 12 carbon.Light fuel cut 512 through syringe or vaporizer or burner 426, is transported to antigravity system 420 through decanting point 428 from fuel tank 412.In one embodiment, a part of fuel 414 can be transported to antigravity system 420 through decanting point 432 by exhaust stream 418 from fuel tank 412 through syringe or vaporizer or burner 430.Heavy fuel cut 514 is transported to engine 416 through fuel 414.In one embodiment, reducing agent induction system 424 also comprises core ductant 434.In one embodiment, core ductant 434 can be produced through reformer 436 by fuel 414.Source of oxygen 438 is provided to reformer 436.In one embodiment, the core ductant 434 that produces through reformer 436 comprises the synthesis gas of hydrogen and carbon monoxide.Core ductant 434 passes through antigravity system 420 through decanting point 428.In one embodiment, DPF 440 is between engine 416 and antigravity system 420, before decanting point 428.In this embodiment, through after the DPF 440, the reducing agent and the core ductant 434 that contain light fuel cut 512 are transported to antigravity system 420 through decanting point 428 at exhaust stream 418.In one embodiment, between fuel tank 412 and antigravity system 420, burner 442 is provided.Burner 442 combustion fuels 414, improving the temperature of exhaust stream 418, this is used under the situation of temperature that exhaust stream 418 has the optimum operation condition that is lower than antigravity system 420, improves the performance of antigravity system 420.In this embodiment, the output 444 of burner can be flowed DPF 440 in 418 and contains between the decanting point 428 of reducing agent and core ductant 434 of light fuel cut 512 in exhaust.
With reference to figure 6, providing can reductive NO
xGas extraction system 600.Gas extraction system 600 comprises fuel delivery system 410, and fuel delivery system 410 is configured to the fuel that comprises in the fuel tank 412 414 is transported to engine 416.Produce exhaust stream 418 by engine 416, this exhaust stream 418 is through antigravity system 420, so that treated exhaust stream 422 to be provided.Fuel delivery system also can comprise the reducing agent induction system 424 that is configured to carry reducing agent.In one embodiment, reducing agent is a fuel 414.In one embodiment, the reducing agent that will comprise fuel 414 through syringe or vaporizer or burner 426, is delivered directly to antigravity system 420 through decanting point 428 from fuel tank 412.In one embodiment, a part of fuel 414 can be transported to antigravity system 420 through decanting point 432 by exhaust stream 418 from fuel tank 412 through syringe or vaporizer or burner 430.In one embodiment, reducing agent induction system 424 also comprises core ductant 434.In one embodiment, core ductant 434 can be produced through reformer 436 by fuel 414.Source of oxygen 438 is provided to reformer 436.In one embodiment, the core ductant 434 that produces through reformer 436 comprises the synthesis gas of hydrogen and carbon monoxide.Core ductant 434 passes through antigravity system 420 through decanting point 432.In one embodiment, DPF 440 is positioned at after the antigravity system 420, and exhaust stream 418 leaves as treated exhaust stream 422 through antigravity system 420 and DPF 440 subsequently.In this embodiment, comprise that the reducing agent of fuel 414 is transported to exhaust stream 418 through decanting point 428.In one embodiment, between fuel tank 412 and antigravity system 420, burner 442 is provided.Burner 442 combustion fuels 414, improving the temperature of exhaust stream 418, this is used under the situation of temperature that exhaust stream 418 has the optimum operation condition that is lower than antigravity system 420, improves the performance of antigravity system 420.In this embodiment, the output 444 of burner is connected to engine 418 in the exhaust stream 418 and comprises in the exhaust stream between the decanting point 432 of reducing agent and core ductant 434 of fuel 414.
With reference to figure 7, providing can reductive NO
xGas extraction system 700.Gas extraction system 700 comprises fuel delivery system 410, and fuel delivery system 410 is configured to the fuel that comprises in the fuel tank 412 414 is transported to engine 416.Produce exhaust stream 418 by engine 416, this exhaust stream 418 is through antigravity system 420, so that treated exhaust stream 422 to be provided.Fuel delivery system also can comprise the reducing agent induction system 424 that is configured to carry reducing agent.Reducing agent induction system 424 comprises fuel fractionation device 510 and syringe or vaporizer or burner 426.In one embodiment, the reducing agent that comprises fuel 414 is at first through fuel fractionation device 710, so that light fuel cut 712 and heavy fuel cut 714 to be provided.Light fuel cut 712 comprises the hydrocarbon that has less than the average carbon chain length degree of about 12 carbon, and heavy fuel cut 714 comprises the hydrocarbon that has greater than the average carbon chain length degree of about 12 carbon.Light fuel cut 712 through syringe or vaporizer or burner 426, is transported to antigravity system 420 through decanting point 428 from fuel tank 412.In one embodiment, a part of fuel 414 can be transported to antigravity system 420 through decanting point 432 by exhaust stream 418 from fuel tank 412 through syringe or vaporizer or burner 430.Heavy fuel cut 714 is transported to engine 416 through fuel 414.In one embodiment, reducing agent induction system 424 also comprises core ductant 434.In one embodiment, core ductant 434 can be produced through reformer 436 by fuel 414.Source of oxygen 438 is provided to reformer 436.In one embodiment, the core ductant 434 that produces through reformer 436 comprises the synthesis gas of hydrogen and carbon monoxide.Core ductant 434 passes through antigravity system 420 through decanting point 432.In one embodiment, DPF 440 is positioned at after the antigravity system 420, and exhaust stream 418 leaves as treated exhaust stream 422 through antigravity system 420 and DPF 440 subsequently.In this embodiment, the reducing agent and the core ductant 434 that contain light fuel cut 712 are transported to exhaust stream 418 through decanting point 428.In one embodiment, between fuel tank 412 and antigravity system 420, burner 442 is provided.Burner 442 combustion fuels 414, improving the temperature of exhaust stream 418, this is used under the situation of temperature that exhaust stream 418 has the optimum operation condition that is lower than antigravity system 420, improves the performance of antigravity system 420.In this embodiment, the output 444 of burner is connected to engine 416 in the exhaust stream 418 and comprises in the exhaust stream between the decanting point 432 of reducing agent and core ductant 434 of fuel 414.
With reference to figure 8, providing can reductive NO
xGas extraction system 800.Gas extraction system 800 comprises fuel delivery system 410, and fuel delivery system 410 is configured to the fuel that comprises in the fuel tank 412 414 is transported to engine 416.Produce exhaust stream 418 by engine 416, this exhaust stream 418 is through antigravity system 420, so that treated exhaust stream 422 to be provided.Fuel delivery system also can comprise the reducing agent induction system 424 that is configured to carry reducing agent.In one embodiment, reducing agent is different with fuel.In this embodiment, reducing agent case 810 is provided, to pass through syringe or vaporizer or burner 426, reducing agent 812 is transported to antigravity system 422 to decanting point 428.In one embodiment, a part of fuel 414 can be transported to antigravity system 420 through decanting point 432 by exhaust stream 418 from fuel tank 412 through syringe or vaporizer or burner 430.In one embodiment, reducing agent induction system 424 also comprises core ductant 434.In one embodiment, core ductant 434 can be produced through reformer 436 by fuel 414.Source of oxygen 438 is provided to reformer 436.In one embodiment, the core ductant 434 that produces through reformer 436 comprises the synthesis gas of hydrogen and carbon monoxide.Core ductant 434 passes through antigravity system 420 through decanting point 428.In one embodiment, DPF 440 is between engine 416 and antigravity system 420, before decanting point 428.In this embodiment, through after the DPF 440, reducing agent 812 is transported to antigravity system 420 with core ductant 434 through decanting point 428 at exhaust stream 418.In one embodiment, between fuel tank 412 and antigravity system 420, burner 442 is provided.Burner 442 combustion fuels 414, improving the temperature of exhaust stream 418, this is used under the situation of temperature that exhaust stream 418 has the optimum operation condition that is lower than antigravity system 420, improves the performance of antigravity system 420.In this embodiment, the output 444 of burner can be flowed between the decanting point 428 of DPF 440 and reducing agent 812 and core ductant 434 in 418 in exhaust.
With reference to figure 9, providing can reductive NO
xGas extraction system 900.Gas extraction system 900 comprises fuel delivery system 410, and fuel delivery system 410 is configured to the fuel that comprises in the fuel tank 412 414 is transported to engine 416.Produce exhaust stream 418 by engine 416, this exhaust stream 418 is through antigravity system 420, so that treated exhaust stream 422 to be provided.Fuel delivery system also can comprise the reducing agent induction system 424 that is configured to carry reducing agent.In one embodiment, reducing agent is different with fuel.In this embodiment, reducing agent case 910 is provided, so that reducing agent 912 is transported to exhaust stream 418 from reducing agent case 910 through syringe or vaporizer or burner 430, exhaust stream 418 takes reducing agent 912 to antigravity system 420 through decanting point 432.In one embodiment, with a part of fuel 414 from fuel tank 412 through syringe or vaporizer or burner 426, be transported to antigravity system 420 through decanting point 428.In one embodiment, reducing agent induction system 424 also comprises core ductant 434.In one embodiment, core ductant 434 can be produced through reformer 436 by fuel 414.Source of oxygen 438 is provided to reformer 436.In one embodiment, the core ductant 434 that produces through reformer 436 comprises the synthesis gas of hydrogen and carbon monoxide.Core ductant 434 passes through antigravity system 420 through decanting point 432.In one embodiment, DPF 440 is positioned at after the antigravity system 420, and exhaust stream 418 leaves as treated exhaust stream 422 through antigravity system 420 and DPF 440 subsequently.In this embodiment, comprise that the reducing agent of fuel 414 is transported to exhaust stream 418 through decanting point 428, decanting point 428 is between antigravity system 420 and DPF 440.In one embodiment, between fuel tank 412 and antigravity system 420, burner 442 is provided.Burner 442 combustion fuels 414, improving the temperature of exhaust stream 418, this is used under the situation of temperature that exhaust stream 418 has the optimum operation condition that is lower than antigravity system 420, improves the performance of antigravity system 420.In this embodiment, the output 444 of burner is connected in the exhaust stream between the decanting point 432 of engine 418 and reducing agent 912 and core ductant 434 in the exhaust stream 418.
In another embodiment again; The present invention provides a kind of antigravity system; Said antigravity system comprises first catalyst composition that comprises the homogeneous solid mixture, and said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier, and wherein the hole of solid mixture has the average pore size of about 1 nanometer to about 15 nanometers; Wherein catalytic metal comprises nanocrystal, and wherein nanocrystal has the PSD less than about 20%.Catalytic metal exists to be equal to or less than about 6% mole amount based on the homogeneous solid mixture weight.
Embodiment
Following examples illustrate method of the present invention and embodiment, therefore, should not be construed as the restriction to claim.These embodiment show the preparation of carbon monoxide-olefin polymeric described herein, and show the performance that they and other commercially available carbon monoxide-olefin polymerics compare.Unless otherwise indicated, all components all available from common chemical supplier such as Aldrich (St.Louis, Missouri), Gelest. (Morrisville, Pennsylvania), Spectrum Chemical Mfg.Corp. (Gardena, California) etc.Component is listed following giving in the table 1 with the source.
Table 1
| Component | The source |
| Ethyl acetoacetate | ?Aldrich |
| triton?X114 | ?Aldrich |
| Three aluminium secondary butylates | ?Gelest |
| The stone silver nitrate | ?Strem?chemicals |
| Isopropyl alcohol | ?EM?Scientific |
| Iron zeolite and copper zeolite | ?Umicore |
Embodiment 1: prepare silver-colored nanocrystal
In about 25 ℃ of temperature (room temperature), to the 3-neck flask that is equipped with agitator add silver acetate (4 mMs, SA), oleic acid (4 milliliters, OA, technical grade, 90%, Aldrich) with trioctylphosphine amine (15 milliliters, TOA).Under 1 millimetres of mercury vacuum, the gained mixture is heated to about 60 ℃ of temperature.Along with temperature raises, silver acetate begins to be dissolved in trioctylphosphine amine.Because the bubble of emerging in the flask is observed in the water that in reactive material, exists as impurity boiling.Water is removed with the water vapour form under vacuum.When temperature was elevated to 60 ℃, silver acetate was dissolved in trioctylphosphine amine fully, and gained solution becomes palm fibre-ash-black, showed that silver acetate decomposes, and generated silver-colored nanocrystal.Then, temperature is elevated to 90 ℃, and mixture was kept about 2 hours in this temperature, accomplishes to guarantee reaction.The gained mixture is cooled to 25 ℃, dark solution is transferred to the centrifuge tube of 50 milliliters of capacity.25 milliliters of ethanol are added to centrifuge tube, observe deposition immediately.Centrifuge tube is put into laboratory centrifuge (Centra CL2), and centrifugal about 10 minutes.Mixture in centrifuge tube centrifugal after, separate at the yellowish-brown supernatant at top with in the black precipitate of bottom.Supernatant discards through pouring out, heavily about 0.5 gram of black precipitate.After discharging ethanol fully, 20 milliliters of hexanes are added to pipe, in hexane (AgNC is in hexane) solution, silver-colored nanocrystal to be provided.5 milliliters of AgNC in hexane solution are dry with aliquot.The gained solid is weighed, to measure the concentration of AgNC in hexane.5 milliliters of AgNC hexane solutions are provided at the AgNC of dry back 32.4 grams per liters to about 53.9 grams per liters (that is, 0.3 mole to 0.5 mole).The amount of used reactant, AgNC concentration and the PSD of AgNC in hexane is contained in the following table 3.
As above mention, PSD measures through transmission electron microscopy (TEM) and graphical analysis.The high power photo is taken by the TEM that covers hundreds of independent AgNC.Particle mean size and standard deviation are through measuring each grain count with graphical analysis.Figure 10,11 and 12 shows the TEM of the AgNC that utilizes 20 nanometer-scale chis, and Figure 13 shows the TEM of the AgNC that utilizes 2 nanometer-scale chis.
Figure 14 shows the EDS of AgNC.EDS is the analytical technology that elemental analysis of samples or chemical characterization are used.EDS relies on through the interaction between electromagnetic radiation and the material, and the amalyzing substances response comes study sample with the x-ray of charged particle collision emission.It characterizes the ability major part: each element has unique atomic structure, thereby allows to discern uniquely each other X-ray (for the character of pantogen minor structure).In order to encourage ray, make beam of high energy charged particles (like electronics or proton) or X-beam focusing to the sample of being studied from sample emission characteristic X-.In inactive state, the atom in the sample comprises ground state (or unexcited state) electronics of discrete energy level, or is bound by the electronic shell of nuclear.Incident beam can excite the electronics in the internal layer, and it is evicted from from layer, produces the electron hole of the electronics that wherein comes into existence simultaneously.From the electronics of outside, higher-energy layer filling hole then, and can X-ray form be released in the higher-energy layer and than the energy difference between the low energy layers.Can measure from the X-number of rays and the energy of sample emission through the energy-dispersive spectroscopy appearance.Because the energy of X-ray is two interlayer energy differences and in order to the characteristic of the atoms of elements structure of launching them, this allows the element of working sample to form.EDS spectrum clearly illustrates the existence of silver atoms.
Be diluted in the AgNC of preparation among the embodiment 1 with hexane, and use the UV-Vis spectrum analysis.Absorbance at different wave length is contained in the following table 2.
Table 2
| Wavelength, nanometer | Absorbance, arbitrary unit | Wavelength, nanometer | Absorbance, |
| 800 | 12.01 | 430 | 14.3 |
| 750 | 12.02 | 410 | 14.9 |
| 700 | 12.02 | 390 | 14.2 |
| 650 | 12.03 | 375 | 13.6 |
| 600 | 12.05 | 350 | 12.9 |
| 550 | 12.1 | 325 | 12.4 |
| 500 | 12.25 | 300 | 12.6 |
| 475 | 12.5 | 250 | 12.9 |
| 450 | 13.2 | 200 | 13.1 |
With reference to Figure 15, Figure 15 is provided at Figure 150 0 of the wavelength (nanometer) of absorbance on the Y axle 1510-on X axle 1512.Figure shows absorption maximum at about 411 nano wave lengths, shows to have AgNC.
Embodiment 2-3: prepare silver-colored nanocrystal
Table 3
Embodiment 4-7: prepare first catalyst composition
Add three aluminium secondary butylates (50 gram) and IPA (200 milliliters) to the 3-neck flask that is equipped with agitator.Then, be added in the scheduled volume AgNC in the hexane solution to flask, hexane solution contains 43.1 gram (0.4 mole) AgNC in hexane, to form first solution.In adding hexane solution the scheduled volume of AgNC and in carbon monoxide-olefin polymeric the load capacity of gained AgNC be contained in the following table 4.After being added to flask, in another independent flask, open mechanical agitator with about 60 rev/mins of speed, add ethyl acetoacetate (2.65 gram), Triton X-114 (14 gram) and 65 milliliters of isopropyl alcohols, to form second solution.Pour second solution into first solution then.With the gained mixture in about 25 ℃ of temperature, with about 180 rev/mins of speed stir abouts 30 minutes.During stirring in 30 minutes, drip the mixture of 7.5 ml distilled waters and 85 milliliters of isopropyl alcohols with syringe pump.
After 30 minutes, will add rate adaptation, and under vigorous stirring, accomplish adding in 2.5 hours with about 200 rev/mins of warps to 0.6 ml/min.Through the water yield and the hydrolysis of adding rate controlled.In hydrolytic process, the solution in the flask becomes white gels gradually, and it is thicker that gel becomes, and this slows down mixing speed.Consider that gel viscosity increases, and the agitator control knob is adjusted to 300 rev/mins, and the actual speed that reaches is about 100rpm to 150rpm.When adding entry/IPA mixture and accomplish, hydrolysis is accomplished, and generates and have full-bodied white gels.After hydrolysis is accomplished, with mixture about 25 ℃ of temperature stir abouts 0.5 hour.After about 0.5 hour, under about 60 rev/mins of stirrings, reactant mixture is heated to 60 ℃, and kept 24 hours at 60 ℃.When being heated to 60 ℃, white gels loses its viscosity, and begins to become dark-brown.At 60 ℃ after aging 24 hours, the gained gel becomes dark-brown.Then, utilize 150 mm dia Buchner funnels and No. 50 Whatman filter paper, filter gel with the standard laboratory vacuum filtering system.General filtration needs about 12 to 24 hours.Under 125 millimetres of mercury vacuum, will be through the gel that filters 60 ℃ of vacuum drying oven dryings, and 550 ℃ of calcinings.Final silver-colored nanocrystal concentration shows well consistent with load, and error is+/-0.2% weight.This catalyst composition is called AgNCMPA (the silver-colored nanocrystal in the mesoporous aluminas)
Table 4
| Embodiment | The solution of AgNC in hexane, in the least | AgNC in carbon monoxide-olefin polymeric |
The PSD of carbon monoxide-olefin polymeric measures through TEM and graphical analysis.The high power photo is taken by the TEM that in this aluminium oxide, comprises AgNC and blapharoplast.Particle mean size and standard deviation are through measuring each grain count with graphical analysis.Figure 16,17 and 18 shows respectively the TEM about the AgNC of 100 nanometers, 20 nanometers and 50 nanometer-scales.
Figure 19 shows the EDS of the carbon monoxide-olefin polymeric that comprises AgNC.Shown in figure, the EDS demonstration exists element aluminum, oxygen and silver, and therefore the element of the homogeneous solid mixture of proof formation first catalyst composition is formed.
The stability of AgNC in hexane solution
AgNC in hexane solution is stable, that is, particle did not show through at least 6 months and decomposes or change of granularity.The stability of AgNC is attributable to surface ligand oleic acid in hexane solution, and it is as surfactant and protect AgNC not decompose.Thermodynamic stability is attributable to the thin layer of silver oxide on nanocrystal surface, and this thin layer is used to make galactic nucleus stable.This oxidation silver layer is extremely thin, so that can not be detected by X-ray diffraction (XRD) usually.The dark color of AgNC also is attributable to this oxide skin(coating).
The hydrothermal stability of first catalyst composition (AgNCMPA (the silver-colored nanocrystal in the mesoporous aluminas))
Shown in Figure 20 and 21, through measuring NO after 48 hours and 144 hours at hydrothermal aging
xConversion capability, the hydrothermal stability of research AgNCMPA (the silver-colored nanocrystal in the mesoporous aluminas) catalyst.With reference to Figure 20 and 21, Figure 200 0 and 2100 is presented at the catalyst of preparation among embodiment 5 (3% weight sol-gel) and the embodiment 6 (4% weight sol-gel) respectively under the different temperatures that shows on the X axle 2012,2112, the NO shown on Y axle 2010,2110
xConversion ratio.For the carbon monoxide-olefin polymeric according to embodiment 5 preparations, curve 2014 shows the NO with the carbon monoxide-olefin polymeric of new preparation AgNCMPA Preparation of Catalyst
xConversion ratio, curve 2016 are presented at the NO of 25 ℃ of aging about 48 hours catalyst
xConversion ratio, curve 2018 are presented at the NO of 25 ℃ of aging about 144 hours catalyst
xConversion ratio.Similarly, for the carbon monoxide-olefin polymeric according to embodiment 6 preparations, curve 2114 shows the NO with the carbon monoxide-olefin polymeric of new preparation AgNCMPA Preparation of Catalyst
xConversion ratio, curve 2116 shows the NO of the carbon monoxide-olefin polymeric that is used in 25 ℃ of aging about 48 hours Preparation of Catalyst
xConversion ratio, curve 2118 are presented at the NO of 25 ℃ of aging about 144 hours catalyst
xConversion ratio.Curve 2014,2114,2016,2116,2018 and 2118 are illustrated in NO
xShow the hydrothermal stability of AgNCMPA catalyst not a lot of the decomposition therefore in the conversion.
Embodiment 8: pilot-scale prepares first catalyst composition
Comparing embodiment 1: preparation carbon monoxide-olefin polymeric
, and these solution are mixed together preparation metal inorganic carrier through preparing first solution, second solution and the 3rd solution.In about 25 ℃ of temperature (room temperature), with first solution of three aluminium secondary butylates (500 gram, 2 moles) and isopropyl alcohol (2 liters), the 5 liter of 3 neck flask of packing into, flask is equipped with charging hopper, condenser and mechanical agitator.Second solution comprises ethyl acetoacetate (26.5 grams, 0.2 mole), TRITON X-114 (139 grams, template) and isopropyl alcohol (500 milliliters).Under agitation, second solution with a collection of first solution that joins, and is kept the gained mixture about 30 minutes at 25 ℃.The 3rd solution comprises water (75 milliliters, 4 moles), silver nitrate (5.33 grams, 0.03 mole) and isopropyl alcohol (950 milliliters), and through the speed of charging hopper with 12 ml/min, joins the mixture that comprises first solution and second solution through about 90 minutes.The gained reactant mixture was kept about 3 hours at 25 ℃, be heated to backflow then, and under refluxing, kept about 20 hours to 24 hours.
Make flask be cooled to 25 ℃ then, content filters with No. 50 Whatman filter paper.Then, solid extracted about 20 hours to about 24 hours through Suo Shi with ethanol.Then, with solid in 125 millimetres of mercury vacuum drying ovens 80 ℃ of dryings, obtain about 164 the gram products.Desciccate in tube furnace, is flowed down at nitrogen,, in about 260 minutes, be heated to 550 ℃ from 25 ℃ with about 2 ℃/minute rate of heat addition.After reaching 550 ℃ of temperature, desciccate was kept 1 hour at 550 ℃.Subsequently, product was calcined about 5 hours at 550 ℃ in air stream.Calcine, remove the template of any remnants.Matrix has about 300 millimeters
2/ gram is to about 600 millimeters
2The surface area of/gram.Carbon monoxide-olefin polymeric has 3% moles of silver load capacity.The catalyst that will in comparing embodiment 1, prepare is called AgMPA (Ag in the mesoporous aluminas).
Experimental condition
The experimental condition of aforementioned carbon monoxide-olefin polymeric is following.Weigh up preparation catalyst material (～50mg), and put into 2 milliliters of GC bottles, until being used for reactor.Catalyst is about 7 hours of 450 ℃ of nitrogen preliminary treatment with 7% water, 30ppm sulfur dioxide and 12% oxygen and surplus, with " wearing out " or " sulphur soaks " catalyst.To put into high flux sieve (HTS) reactor from the sample of above listed embodiment, to measure their conversion of nitrogen oxides abilities in simulated exhaust stream.Reactor has 32 pipes, and each pipe can receive carbon monoxide-olefin polymeric.In pipe #1, do not put catalyst.Measure the NO in the exhaust stream with pipe #1
xConcentration, and therefore NO is provided
xThe reference of conversion ratio.Pipe #32 is equipped with and makes reducing agent change into CO
2The DOC catalyst.Ratio with its calibration C and N.The catalyst combination matter sample is put into other pipes, and detect NO
xConcentration reduces.Each carbon monoxide-olefin polymeric is used 3 to 4 parallel determinations, NO
xConversion value is the mean value of parallel determination.NO
xIt is relevant with the catalytic activity of carbon monoxide-olefin polymeric that concentration reduces.
Simulated exhaust stream comprises exhaust banks compound and reducing agent.The nitrogen that consists of 7% water, 1ppm sulfur dioxide, 300ppm nitric oxide, 12% oxygen and surplus of used simulated exhaust stream.Utilize the NO of the carbon monoxide-olefin polymeric of diesel oil reducing agent
xConversion results is shown among Figure 22.For all samples, use the HTS reactor, the C that in the exhaust banks compound, uses
1: the NO ratio is 4 or 6 (C
1: NO is defined as each nitrogen oxide (NO) molecular number purpose carbon number in the reducing agent stream).Three samples of each catalyst of test in each test are at 275 ℃ of four temperature, 325 ℃, 375 ℃ and 425 ℃ of each catalyst of test.Used reducing agent is the cut 1 of ULSD.After each reduction, 1 hour burn-out steps at 500 ℃ is arranged in air.
Mensuration is through the NO of the pipe #1 that do not have catalyst and exist
xConcentration is measured the NO through other pipes with catalyst
xConcentration, and measure percentage change, as NO
xConversion percentage provides data.CO/CO also is provided
2Concentration changes into CO/CO to understand reducing agent
2Degree.Table 5 provides the average N O of the sample with 2,3,4 and 5% moles of AgNC sol-gels that in embodiment 4-7, prepare
xConversion value and average CO
2Conversion value.Sample is designated as the load percentage (2AgNCMPA, 3AgNCMPA, 4AgNCMPA and 5AgNCMPA) of AgNC in the mesoporous aluminas.Table 5 also is provided at the average N O of the sample AgMPA of preparation in the comparing embodiment 1
xConversion value and average CO
2Conversion value.
Table 5
With reference to Figure 22, block diagram 2200 is presented at the above average N O that mentions 4 temperature, 5 samples
xConversion ratio 2210 ((bottom of each block diagram) and standard deviation 2212 (top of each block diagram).With reference to Figure 23, block diagram 2300 is presented at the above average CO that mentions 4 temperature, 5 samples
2Conversion ratio 2310 ((bottom of each block diagram) and standard deviation 2312 ((top of each block diagram).The result that provides in the table 5 shows, temperature 325 with 375 ℃, catalyst shows the NO of raisings in all load capacity of silver-colored nanocrystal
xReduction.In addition, in different load capacity 1%, 3%, 4% and 5%, 3% and 4% load capacity shows the NO more preferable with comparing embodiment 1
xReducing power, and 2% and 5% load capacity provides the conversion value suitable with comparing embodiment 1.The result also shows generation CO
2, show diesel oil (ULSD) burning.
Embodiment 9: the performance of carbon monoxide-olefin polymeric
Present embodiment is with respect to carbon monoxide-olefin polymeric relatively, relatively comprises contained NO in the exhaust stream of sample of embodiment of the present invention
xConversion performance.Relatively carbon monoxide-olefin polymeric does not contain the nanocrystal of catalytic metal.
With aforesaid simulated exhaust current test catalyst.Simulated exhaust stream comprises exhaust banks compound and reducing agent.Reducing agent comprises the cut 1 of ULSD.
The NO of the AgMPA catalyst that will in comparing embodiment 1, prepare
xThe NO of carbon monoxide-olefin polymeric (3AgNCMPA) of conversion capability and preparation in embodiment 5
xConversion capability four temperature relatively.Data are provided in the following table 6.
Table 6
With reference to Figure 24, Figure 24 is provided under all temps that shows on the X axle 2412, the average N O that on Y axle 2410, shows
xFigure 24 00 of conversion ratio.Figure shows, in all four temperature, by the NO of the catalyst composition of the embodiment 5 of curve 2414 indications
xConversion capability is greater than the NO of the catalyst composition of the comparing embodiment 1 of being indicated by curve 2512
xConversion capability.With respect to the carbon monoxide-olefin polymeric that contains templating matrix and Ag, the catalyst composition that comprises AgNC and surfactant all produces relative superior results in all temperature.
The NO of the AgMPA catalyst that will in comparing embodiment 1, prepare
xConversion capability compares with the catalyst composition (4AgNCMPA) of preparation in embodiment 8.Data are provided in the following table 7.
Table 7
With reference to Figure 25, Figure 25 is provided under all temps that shows on the X axle 2512, the average N O that on Y axle 2510, shows
xFigure 25 00 of conversion ratio.Figure shows, and relatively by the carbon monoxide-olefin polymeric of the comparing embodiment 1 of curve 2512 indications, and by the NO of the catalyst of preparation in embodiment 8 of curve 2514 indications
xConversion capability is at 375 and 325 ℃ of NO that demonstration is bigger
xConversion ratio and show suitable NO at 425 and 275 ℃
xConversion ratio.This shows that the catalyst composition for preparing with pilot-scale provides the NO suitable with the catalyst composition of bench scale preparation
xTherefore conversion ratio shows the scalability of embodiment.
About term " product ", the material that relates to, component or composition just according to the disclosure at first with one or more other materials, component or composition contacts, original position formation, blend or mix before time exist.If according to the disclosure; And application of known general knowledge and various equivalent modifications are (for example; Chemist) general technical ability is carried out; Material, component or composition as product identification possibly obtain characteristic, character or characteristic through chemical reaction or conversion in contact, original position formation, blend or married operation process.It is continuous progression that chemical reactant or feedstock conversion become chemical product or final material, does not rely on the speed of generation.Therefore because this conversion process is in progress, therefore, can have raw material and final material and according to its dynamics life-span easily or be difficult to mixture with the intermediate material of the known present analytical technology detection of those of ordinary skill in the art.
Reactant that chemical name in specification or claims or chemical formula relate to and component; No matter be odd number or plural number; All can be differentiated, because they existed before another kind of material (for example, another kind of reactant or the solvent) contact that relates to chemical name or chemical type.Preliminary and/or the transient chemistry that in gained mixture, solution or reaction medium, takes place changes, transforms or reaction (if any), can be considered to intermediate material, masterbatch etc., and can have the application that is different from product or final material.Under the condition that requires according to the disclosure, other change subsequently, transform or react and can be produced by the reactant and/or the combination of components of regulation.In changing subsequently, transform these other or reacting, the reactant that combine, composition or component can be discerned or the Indicator Reaction product.
Disclosed all scopes of this paper all comprise end points interior, and these end points can make up each other.Word used herein " first ", " second " etc. are not represented any order, amount or importance, but are used to distinguish a key element and another key element.The use of word " ", " this " and " said " and similar statement should be interpreted as and comprises odd number and plural number in the context of following claim (especially) in describing the present invention, only if this paper indicates in addition or context shows it is reverse situation.
Though, combined many embodiments to describe the present invention in detail, the invention is not restricted to these disclosed embodiments.On the contrary, can revise the present invention, with add more any change, change, replace or do not describe so far but the equivalent arrangements that adapts with scope of the present invention.In addition, though, different embodiments of the present invention has been described, should be understood that each side of the present invention can include only some described embodiments.Therefore, should not be regarded as receiving aforementioned description to limit the present invention, the present invention be limited by the scope of accessory claim only.
The key element inventory
100 antigravity systems
110 quartz ampoules
112 first antigravity systems
114 silica wools
116 silica wools
200 antigravity systems
210 quartz ampoules
212 first antigravity systems
214 silica wools
216 silica wools
218 silica wools
220 silica wools
222 second catalyst compositions
300 antigravity systems
310 quartz ampoules
312 first antigravity systems
314 silica wools
316 silica wools
318 silica wools
320 silica wools
322 second catalyst compositions
324 silica wools
326 silica wools
328 the 3rd catalyst compositions
400 gas extraction system
410 fuel delivery systems
412 fuel tanks
414 fuel
416 engines
418 exhausts stream
420 antigravity systems
422 treated exhausts are flowed
424 reducing agent induction systems
426 burners/syringe/vaporizer
428 decanting points
430 burners/syringe/vaporizer
432 decanting points
434 core ductants
436 reformers
438 source of oxygen
440 diesel particulate filters
442 burners
The output of 444 burners
500 gas extraction system
510 fuel fractionation devices
512 light fuel cuts
514 heavy fuel cuts
600 gas extraction system
700 gas extraction system
710 fuel fractionation devices
712 light fuel cuts
714 heavy fuel cuts
800 gas extraction system
810 reducing agent casees
812 reducing agents
900 gas extraction system
910 reducing agent casees
912 reducing agents
1500 figure
1510 absorbency Y-axles
1512 wavelength X-axles
2000 figure
2010 NO
xConversion ratio Y-axle
2012 temperature X-axles
2014 curves
2016 curves
2018 curves
2100 figure
2110 NO
xConversion ratio Y-axle
2112 temperature X-axles
2114 curves
2116 curves
2118 curves
2300 figure
2310 average CO
2Conversion ratio Y-axle
2312 standard deviation X-axles
2400 figure
2410 average N O
xConversion ratio Y-axle
2412 temperature X-axles
2414 curves
2416 curves
2500 figure
2510 average N O
xConversion ratio Y-axle
2512 temperature X-axles
2514 curves
2516 curves
Claims (10)
1. antigravity system, said antigravity system comprises:
First catalyst composition that comprises the homogeneous solid mixture, said homogeneous solid mixture comprise at least a catalytic metal and at least a metal inorganic carrier, and the hole of wherein said solid mixture has the average pore size of about 1 nanometer to about 15 nanometers; And
Wherein said catalytic metal comprises nanocrystal.
2. the antigravity system of claim 1, said antigravity system also comprises at least a catalytic metal that helps.
3. the antigravity system of claim 1, said antigravity system also comprises second catalyst composition, and wherein second catalyst composition comprises:
(i) zeolite, or
(ii) place first catalytic specie on first matrix, first catalytic specie comprises the element that is selected from tungsten, titanium and vanadium.
4. the antigravity system of claim 3, said antigravity system also comprises the 3rd catalyst composition, and wherein the 3rd catalyst composition comprises: place second catalytic specie on second matrix, wherein second catalytic specie is selected from platinum, palladium, ruthenium, osmium and iridium.
5. the antigravity system of claim 1, said antigravity system also comprises the induction system that is configured to carry reducing agent.
6. the antigravity system of claim 5, wherein said induction system also comprises core ductant.
7. antigravity system, said antigravity system comprises:
First catalyst composition, said first catalyst composition comprises:
Homogeneous solid mixture, said homogeneous solid mixture comprise at least a catalytic metal and at least a metal inorganic carrier; The hole of wherein said solid mixture has the average pore size of about 1 nanometer to about 15 nanometers; Wherein said catalytic metal comprises nanocrystal; With
At least a catalytic metal that helps;
Second catalyst composition, said second catalyst composition comprises:
(i) zeolite, or
(ii) place first catalytic specie on first matrix, first catalytic specie comprises the element that is selected from tungsten, titanium and vanadium.
8. method, said method comprises:
The nanocrystal of at least a catalytic metal is provided;
Said nanocrystal is incorporated at least a metal inorganic carrier; With
Formation comprises first catalyst composition of homogeneous solid mixture, and said homogeneous solid mixture comprises at least a catalytic metal and at least a metal inorganic carrier; The hole of wherein said solid mixture has the average pore size of about 1 nanometer to about 15 nanometers, and wherein said catalytic metal comprises nanocrystal.
9. gas extraction system, said gas extraction system comprises:
Be configured to fuel is transported to the fuel delivery system of engine;
Be configured to receive the exhaust circulation road of exhaust stream from engine;
Be configured to reducing agent is transported to the reducing agent induction system in exhaust circulation road; With
Place the antigravity system in exhaust circulation road, wherein said antigravity system comprises:
First catalyst composition, said first catalyst composition comprises:
Homogeneous solid mixture, said homogeneous solid mixture comprise at least a catalytic metal and at least a metal inorganic carrier; The hole of wherein said solid mixture has the average pore size of about 1 nanometer to about 15 nanometers; Wherein said catalytic metal is the nanocrystal form.
10. antigravity system, said antigravity system comprises:
Homogeneous solid mixture, said homogeneous solid mixture comprise at least a catalytic metal and at least a metal inorganic carrier; The hole of wherein said solid mixture has the average pore size of about 1 nanometer to about 15 nanometers;
Wherein said catalytic metal comprises nanocrystal;
Wherein said nanocrystal has the size distribution less than about 20%; And
Wherein said catalytic metal exists to be less than or equal to about 6% mole amount based on said homogeneous solid mixture weight.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505079B (en) * | 2022-04-20 | 2022-06-24 | 山东万达环保科技有限公司 | Preparation method of low-temperature manganese-based SCR denitration catalyst and application of low-temperature manganese-based SCR denitration catalyst in flue gas denitration |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0714693A1 (en) * | 1994-11-28 | 1996-06-05 | Kabushiki Kaisha Riken | Exhaust gas cleaner and method for cleaning exhaust gas |
| US20080053073A1 (en) * | 2005-06-21 | 2008-03-06 | Mohan Kalyanaraman | Reformer assisted lean NOx catalyst aftertreatment system and method |
| CN101541402A (en) * | 2006-09-20 | 2009-09-23 | 巴斯福催化剂公司 | Catalysts to reduce NOx in an exhaust gas stream and methods of preparation |
| CN101816933A (en) * | 2009-01-30 | 2010-09-01 | 通用电气公司 | Templated catalyst composition and correlation technique |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0714693A1 (en) * | 1994-11-28 | 1996-06-05 | Kabushiki Kaisha Riken | Exhaust gas cleaner and method for cleaning exhaust gas |
| US20080053073A1 (en) * | 2005-06-21 | 2008-03-06 | Mohan Kalyanaraman | Reformer assisted lean NOx catalyst aftertreatment system and method |
| CN101541402A (en) * | 2006-09-20 | 2009-09-23 | 巴斯福催化剂公司 | Catalysts to reduce NOx in an exhaust gas stream and methods of preparation |
| CN101816933A (en) * | 2009-01-30 | 2010-09-01 | 通用电气公司 | Templated catalyst composition and correlation technique |
Non-Patent Citations (2)
| Title |
|---|
| EROL SEKER ET AL: ""Nitric oxide reduction by propene over silver/alumina and silver–gold/alumina catalysts: effect of preparation methods"", 《APPLIED CATALYSIS A: GENERAL》, vol. 183, 5 July 1999 (1999-07-05), XP004271836, DOI: doi:10.1016/S0926-860X(99)00045-9 * |
| HYUNJOON SONG ET AL: ""Hydrothermal Growth of Mesoporous SBA-15 Silica in the Presence of PVP-Stabilized Pt Nanoparticles: Synthesis, Characterization, and Catalytic Properties"", 《J. AM. CHEM. SOC.》, vol. 128, 2 September 2006 (2006-09-02) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505079B (en) * | 2022-04-20 | 2022-06-24 | 山东万达环保科技有限公司 | Preparation method of low-temperature manganese-based SCR denitration catalyst and application of low-temperature manganese-based SCR denitration catalyst in flue gas denitration |
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