CN101716533A - Integrated catalyst carriers and method thereof for preparing catalyst - Google Patents
Integrated catalyst carriers and method thereof for preparing catalyst Download PDFInfo
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- CN101716533A CN101716533A CN200910238117A CN200910238117A CN101716533A CN 101716533 A CN101716533 A CN 101716533A CN 200910238117 A CN200910238117 A CN 200910238117A CN 200910238117 A CN200910238117 A CN 200910238117A CN 101716533 A CN101716533 A CN 101716533A
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Abstract
The invention provides a novel integrated catalyst using eggshell type porous silicon dioxide nano particles as a coating and a preparation method thereof. The integrated catalyst has the characteristics that active components are distributed in a form of double shell layers, a catalysis layer and carriers have strong bonding force and uniform coating structure, and primary carriers and the active components are not easy to flow away in a catalytic reaction process. A primary structure of the catalyst is a hollow eggshell type structure, and a secondary structure is a cellular structure, thus the catalyst has the characteristics of high mechanical strength, larger specific surface area, centralized mesopore distribution, convenient processing and easy filling. Moreover, the catalyst has higher catalytic activity and higher selectivity particularly to the consecutive reaction of a product for the purpose of an intermediate product. The catalyst keeps the characteristics of an eggshell type porous silicon dioxide nano catalyst in properties, can meet the requirement of different processes through changing the shape and the size of a ceramic base material or metal, and can be used as a catalytic distillation element and a hetero catalyst.
Description
Technical field
The present invention relates to a kind of integral catalyzer and preparation method thereof, specifically a kind of is integral catalyzer of coating and preparation method thereof with eggshell type porous silicon dioxide nano particle.
Background technology
Integral catalyzer (monolithic catalysts) is the integrated catalyst by many narrow parallel channels proper alignment.The cross section of the integral catalyzer used carrier of early development is honeycomb, so be referred to as honeycombed catalyst again.
The integral catalyzer first industrial application is in 1966, and people carry out reduction-decolor with it to NOx in the nitric acid workshop tail gas; The mid-1970s, the U.S. and Japan use it for the CO, the NO that handle in the vehicle exhaust and imperfect combustion hydro carbons, and to handle all be to adopt this ceramic honeycomb or alloy cellular carrier to vehicle exhaust basically at present.Bed pressure drop is little, catalytic efficiency is high, the little advantage of enlarge-effect owing to having, integral catalyzer has been widely used in many chemical fields in recent years, SCR (SCR) as NO, the catalytic combustion of VOC and the heterogeneous reaction of some organic syntheses become in the current heterogeneous catalysis field one of the most potential research direction.
Integral catalyzer generally is made up of three parts: carrier, be coated on the porous oxide on the carrier and be scattered in active component on the oxide surface.Wherein carrier plays a part the carrying coating, and provides suitable fluid passage for catalytic reaction.Carrier commonly used has the pottery of integrated structure and the alloy of integrated structure, and wherein representative is honeycomb-like cordierite and sheet or column FeCrAl alloy.The geometrical feature of this class carrier is decided by the thickness of shape, size and the partition of passage, and these factors have determined their unit weight, porosity, total surface area and kinetic diameter.The specific area of general these two kinds of carriers is all very low, and (for example the specific area of honeycomb-like cordierite is less than 1m
2/ g), if therefore also very low as its catalytic efficiency of carrier separately.
Integral catalyzer is compared with traditional particles filled bed bioreactor as the favorable substitutes of traditional heterogeneous catalyst, has the practical value of more advantage and Geng Gao.At first, integral catalyzer has the little advantage of bed pressure drop.Integral catalyzer is made of many parallel and straight ducts, and porosity is higher, and suffered resistance was less when this Open architecture made fluid flow through beds, and pressure drop is very little.Compare with pellet type catalyst, the integral catalyzer bed pressure drop has reduced by 2～3 orders of magnitude; Secondly, concentration gradient is little, can obviously reduce the probability that the bed heat spot produces, and has good hear resistance and improves mass transfer and heat-transfer character.Each duct of integral catalyzer is relatively independent, no any effect of mass transmitting between adjacent duct, thereby do not have radially heat transfer; The footpath thermotropism conduction that sees through cell walls in addition is also very low, and very low with thermal conductivity especially, ceramic monolith is then lower in this way; The 3rd, geometrical surface is bigger, and diffusion length is short.For the gas-liquid-solid phase reaction on the monolith honeycomb reactor, when the suitable gas of maintenance, liquid two-phase speed, the flow pattern that can occur approximate piston flow in the catalyst duct, at this moment, drop by different bubbles separately, the very thin liquid film of one deck is arranged between bubble and duct inwall, and this layer liquid film increased the contact area of gas-liquid two-phase, and gas can reach the catalyst activity surface by liquid film at an easy rate.Exist liquid phase to circulate in drop inside, circulation has been accelerated gas from the transmission of bubble edge to the catalyst wall, compare with trickle bed, the piston flow in the monolith honeycomb reactor has improved the mass transfer rate of gas phase, and then impels the raising of catalyst utilization and reaction selectivity.In a word, what integral catalyzer (monolith honeycomb reactor) helped reactant enters discharge with product fast, and suitably application can also be strengthened chemical process, helps to form the novel catalyzing technology process of low energy consumption, zero-emission.
In order to improve the utilization rate of integrated structure carrier, usually in the adhere to position of its surface-coated one deck inorganic oxide, to increase its specific area as active component.Patent CN 101391233A is the integral catalyzer that coating has been prepared magnalium mesoporous composite oxides carried noble metal with magnalium mesoporous composite oxides carried noble metal; Patent CN 101234345A is first carrier with Al-base ceramic, and aluminium oxide is second carrier, CeO
2Adding an amount of blended metal oxide is that active component has been prepared a kind of flue gas denitrating integral catalyst; Patent CN 101138720A is to apply Al
2O
3The FeCrAl alloy sheet of layer is compound integrated structure carrier, with Na
2WO
4-Mn is the integral catalyzer that main active component has been prepared methane oxidation coupling system ethene.
Above patent documentation all improves the catalytic efficiency of integral catalyzer with the specific area that increases the integrated structure carrier, perhaps merely active component is coated in by adhesive to prepare the higher integral catalyzer of catalytic efficiency on the integrated structure carrier.
Summary of the invention
The object of the present invention is to provide a kind of is integral catalyzer of coating and preparation method thereof with eggshell type porous silicon dioxide nano particle.Utilizing the eggshell type porous silica is second carrier, is coated on the structurized monolithic substrate (first carrier) by adhesive colloidal sol as coat, and preparing eggshell type porous silicon dioxide nano particle is the integrated catalyst carrier of coating; Further active component in the load is that coating, active component are the integral catalyzer (its illustraton of model is seen Fig. 1) that dual shell distributes thereby prepare with eggshell type porous silicon dioxide nano particle.
A kind of integrated catalyst carrier is characterized in that: outer is eggshell type porous silicon dioxide nano particle, is coated in inner on the matrix of integrated structure by inorganic bond.Inorganic bond is 3～10wt% aluminium colloidal sol or Ludox; The matrix of integrated structure is cordierite, carborundum or the FeCrAl alloy with alveolate texture.
About eggshell type porous silicon dioxide nano particle, in the patent of the previous application of the applicant (Beijing University of Chemical Technology), detailed description is arranged.In Chinese invention patent Shen Qing Publication specification CN1511785A, introduced with the nano-calcium carbonate is template, the method for preparing eggshell type porous silicon dioxide nano particle with the sodium metasilicate for the silicon source, the eggshell type porous silicon dioxide nano grain diameter of its preparation is 50～120nm, wall thickness is 5～30nm, average pore size is 2～5nm, and specific area is 300～1000m
2/ g, pore volume is 0.4～1.3mL/g.
The preparation method of described integrated catalyst carrier is characterized in that: with spherical nano-calcium carbonate is template, prepares eggshell type porous silicon dioxide nano particle by the hydrolysis sodium metasilicate; Utilize eggshell type porous silicon dioxide nano particle and 3～10wt% aluminium colloidal sol or Ludox to prepare coating liquid, wherein the mass ratio of solid is 1～5 in eggshell type porous silicon dioxide nano particle and the colloidal sol; The integral catalyzer matrix is impregnated in eggshell type porous silicon dioxide nano particle-colloidal sol coating liquid, takes out behind 3～30min; 80～120 ℃ down dry, and the time is 3～7h, after 400～700 ℃ of air atmosphere calcining 3～10h obtain eggshell type porous silicon dioxide nano particle is the integrated catalyst carrier of coating.
Use the method that described monolithic substrate prepares integral catalyzer, it is characterized in that: 0.4～1wt% is measured metal salt solution by activity component load quantity, metal salt solution dripped into fill in the container of monolithic substrate that eggshell type porous silicon dioxide nano particle is a coating, load boils off moisture after finishing; Dried catalyst is calcined 3～7h down at 400～500 ℃, and obtaining with eggshell type porous silicon dioxide nano particle is the integral catalyzer of coating.
Described active component is one or more in gold, silver and the platinum group.
Described catalyst activates with online reducing process, and reduction process is 0.05～0.1 H2/N2 mist for feeding volume ratio in the time of 70～500 ℃, and the flow-control of mist is at 10～50ml/min, and the recovery time is 1～5h.
Below monolithic substrate among the present invention and Preparation of catalysts method are described in detail:
The application number that proposed on December 30th, 2002 according to the applicant (Beijing University of Chemical Technology) is that 02160383.9 publication number is the Chinese invention patent of CN1511785A, with the nano-calcium carbonate is template, prepares eggshell type porous silicon dioxide nano particle with the sodium metasilicate for the silicon source.
With eggshell type porous silicon dioxide nano particle is the preparation process of the integrated catalyst carrier of coating, is specially:
The preparation process of eggshell type porous silicon dioxide nano particle-colloidal sol coating liquid is specially:
(1) gets an amount of Al
2O
3Powder is made into mass concentration and is 3～10% the aqueous solution; Disperse after being diluted to 3～10wt%.
(2) add the nitric acid that a little diluted, regulate pH=4～5, heating, and keep 80 ℃, and continue 5～6h, obtain transparent aluminium colloidal sol; Perhaps be diluted to 3～10wt% with commercially available Ludox.
(3) take by weighing a certain amount of eggshell type porous silicon dioxide nano particle (with the mass ratio of solid in the colloidal sol be 1～5), mix with colloidal sol, 8000～10000 change to stir 2～6h, obtain stable eggshell type porous silicon dioxide nano particle-colloidal sol coating liquid.
What this kind integral catalyzer helped reactant in chemical reaction enters discharge with product fast, be applied in the consecutive reaction that intermediate product is the purpose product, the generation of side reaction be can effectively reduce, thereby purpose product selectivity and yield improved.For example be applied in the reaction that selective hydrogenation of acetylene prepares ethene, conversion of alkyne is 96.8～98.4%, and ethylene selectivity also can remain on 52.4～54.9%.
Description of drawings
Fig. 1 is the integral catalyzer illustraton of model of coating with eggshell type porous silicon dioxide nano particle.B is the enlarged drawing of A.
Fig. 2 is the TEM photo of eggshell type porous silicon dioxide nano particle.
Fig. 3 is is the integrated structure carrier with the cordierite, be the SEM photo (surface) of the integrated catalyst carrier of coating with eggshell type porous silicon dioxide nano particle.
Fig. 4 is is the integrated structure carrier with the cordierite, be the SEM photo (cross section) of the integrated catalyst carrier of coating with eggshell type porous silicon dioxide nano particle.
Fig. 5 is the integrated structure carrier, is the SEM photo of the load type palladium integral catalyzer of coating with eggshell type porous silicon dioxide nano particle with the FeCrAl alloy.
Fig. 6 is the integrated structure carrier, is the SEM photo of the load type double-metal integral catalyzer of coating with eggshell type porous silicon dioxide nano particle with the FeCrAl alloy.
Fig. 7 is is the integrated structure carrier with the cordierite, be the SEM photo of the load type platinum integral catalyzer of coating with eggshell type porous silicon dioxide nano particle.
Fig. 8 is to be the selective hydrogenation of acetylene performance-temperature relation figure of the precious metal palladium integral catalyzer of matrix with the cordierite.
Fig. 9 is to be the selective hydrogenation of acetylene performance-temperature relation figure of the noble metal platinum integral catalyzer of matrix with the FeCrAl alloy.
The specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment, but do not limit the scope of the invention.
Embodiment 1
(1) preparation eggshell type porous silicon dioxide nano particle, it according to the inventor (Beijing University of Chemical Technology) application number 02160383.9 Chinese patent, concrete steps are as follows: the spherical nano-calcium carbonate of measuring the 0.8mol/L of 500ml places reactor, be warming up to 80 ℃, dripping concentration is the sodium silicate solution 250ml of 0.68mol/L, keep stirring, the salt acid for adjusting pH value with 10wt% remains 9 simultaneously, ageing 4h; Washing then, drying is calcined 3h under 750 degree; Remove the calcium carbonate template with the hydrochloric acid of 20wt% after reducing to room temperature, washing obtains eggshell type porous silicon dioxide nano particle (see figure 2) to neutral.
(2) colloidal sol of the bonding usefulness of preparation in turn includes the following steps: take by weighing commercially available SB powder (a kind of Al of 8.67g
2O
3Powder), adding fills in the 150ml four-hole bottle of deionized water, is heated to 80 ℃ and stirring, drips the nitric acid that diluted, to pH=3; Keep stirring and be incubated 4h, reduce to room temperature naturally, obtain the transparent aluminium colloidal sol of 10wt%.
(3) take by weighing 5g eggshell type porous silicon dioxide nano particle, mix with the colloidal sol of 105ml step (1) preparation, disperse 4h, rotating speed 9000 commentaries on classics/min obtain eggshell type porous silicon dioxide nano particle-aluminium colloidal sol coating liquid; Get a honeycomb-like cordierite, impregnated in the coating liquid, take out behind the 15min, room temperature is dried, 100 ℃ of dry 5h, Muffle furnace calcining 3h, 500 ℃ of calcining heats, obtain eggshell type porous silica/honeycomb-like cordierite complex carrier, see Fig. 3 (surface) and Fig. 4 (cross section), specific area is 5m
2/ g.
Embodiment 2
Take by weighing 8g eggshell type porous silicon dioxide nano particle, mix with the commercially available Ludox of 10ml 30wt%, be diluted to 100ml with deionized water, disperse 6h, rotating speed 9000 commentaries on classics/min obtain eggshell type porous silicon dioxide nano particle-Ludox coating liquid; Get a sheet FeCrAl alloy, impregnated in the coating liquid, take out behind the 5min, room temperature is dried, 120 ℃ of dry 3h, and Muffle furnace calcining 5h, 500 ℃ of calcining heats obtain eggshell type porous silica/FeCrAl alloy complex carrier (see figure 5), and specific area is 25.2m
2/ g.
Embodiment 3
(1) take by weighing 10g eggshell type porous silicon dioxide nano particle, put into and fill the beaker of 70ml by the aluminium colloidal sol of embodiment 1 step (2) preparation, stir 4h, rotating speed 8000 commentaries on classics/min obtain eggshell type porous silicon dioxide nano particle-colloidal sol coating liquid, and are standby.
(2) get a honeycomb-like cordierite carrier, its quality of weighing is 25g; Be impregnated in eggshell type porous silicon dioxide nano particle-colloidal sol coating liquid, take out behind the 10min; At room temperature dry, 110 ℃ of dry 4h are after 450 ℃ of air atmosphere calcining 7h; Its quality of weighing then repeats this step 4 times, weightening finish 6.1%.Obtain integrated catalyst carrier.
(3) with immersion process for preparing carried noble metal palladium integral type catalyst, in turn include the following steps: at first compound concentration is 5.64 * 10
-3The palladium chloride solution of mol/L, stand-by; Taking by weighing 10g is the monolithic substrate of coating with eggshell type porous silicon dioxide nano particle, puts in the beaker that fills the 15ml deionized water; Measure the 66.67mL palladium chloride solution then and join in the beaker, flood; Dip time is 20h, boils off the moisture rear catalyst and calcines, and calcining heat is 450 ℃, and calcination time is 6h, can obtain unreduced palladium load quality mark and is 0.4% active component and be the integral catalyzer that dual shell distributes.
(4) online hydrogen reducing, H
2/ N
2(V/V=1/10) flow-control is at 30ml/min, and temperature is 70 ℃, and time 2h obtains active component and is the precious metal palladium integral catalyzer that dual shell distributes.
Embodiment 4
(1) Ludox of the commercially available 30wt% of 3g is got in the preparation of colloidal sol, and adding deionized water, to be diluted to gross mass be 10g; Said mixture is disperseed 2h, obtain silica quality concentration and be the stabilized colloidal silica of 9.0wt%, standby.
(2) take by weighing 6g eggshell type porous silicon dioxide nano particle, put into and fill the beaker of 10ml by the Ludox of step (1) preparation, stir 2h, rotating speed 10000 commentaries on classics/min obtain eggshell type porous silicon dioxide nano particle-colloidal sol coating liquid, and are standby.
(3) get a honeycomb-like cordierite carrier, its quality of weighing; Be impregnated in catalyst-colloidal sol coating liquid, take out behind the 5min; At room temperature dry, 120 ℃ of dry 3h are after 600 ℃ of air atmosphere calcining 7h; Obtain integrated catalyst carrier, its quality of weighing, weightening finish 7.8%.
(4) active component is the step (3) in preparation method's similar embodiment 3 of the palladium-based monolithic catalyst that dual shell distributes.Be used palladium chloride solution concentration be 22.56 * 10
-3Mol/L, consumption is 41.66ml, palladium content is 1.0wt% in the integral catalyzer that obtains at last; Reducing condition is: flow is 20ml/min, and temperature is 300 ℃, time 1.5h.
Embodiment 5
(1) preparation of adhesive colloidal sol is with the step among the embodiment 1 (2).
(2) take by weighing 5g eggshell type porous silicon dioxide nano particle, mix with 35ml colloidal sol, stir 5h, rotating speed 9000 commentaries on classics/min obtain catalyst-colloidal sol coating liquid, stand for standby use.
(3) get the FeCrAl alloy that a tablet quality is 15g, be impregnated in above-mentioned eggshell type porous silicon dioxide nano particle-colloidal sol coating liquid, take out behind the 3min, dry under the room temperature, 110 ℃ of dry 4h, 550 ℃ of calcining 10h; Obtain with the FeCrAl alloy is the monolithic substrate of matrix.
(4) take by weighing the H of 1.12g
2PtCl
66H
2The O solid is dissolved in the 50mL deionized water, adds the concentrated hydrochloric acid of 1mL 35% then.The above-mentioned monolithic substrate of 10g is immersed in the solution, leaves standstill dipping and filter behind the 12h, the platinum ion of not load is removed in washing, and in 80 ℃ of oven dry down, heating rate is 10 ℃/min.Calcine 3h at last under 500 ℃, its heating rate is 5 ℃/min, can obtain unreduced load type platinum integral catalyzer.
(5) online reduction 150min, H
2/ N
2(V/V=1/10) flow 20ml/min, 450 ℃ of reduction temperatures, time 1h obtains active component and is the noble metal platinum integral catalyzer (see figure 6) that dual shell distributes.
Embodiment 6
Get the load type palladium integral catalyzer of preparation among the 6g embodiment 3, adopt step impregnation method, further impregnated in and fill the Ni (NO that 19.82ml concentration is 0.21mol/L
3)
2In the beaker of solution+30ml water, after dipping spends the night,, calcine 3h down, obtain unreduced Ni: Pd=4: 1 dual-active component integral catalyzer (see figure 7) for 400 ℃ in 100 ℃ of evaporating water.
Get the catalyst of embodiment 3 preparation, through broken, sieve out 20～40 purpose particle 1.5g, placing internal diameter is that the stainless steel tubular type reactor of 10mm carries out activity rating.Appreciation condition: reacting gas consists of H
2: C
2H
2: C
2H
4: N
2=2: 1: 99: 18, reaction temperature was 35～60 ℃, pressure 0.1MPa, air speed 1000h
-1Behind the stable reaction 2h, sample analysis.Product enters GC-6890 type gas-chromatography by six-way valve and carries out on-line analysis, and with ethene in the PorapakQ assay products and acetylene ratio, hydrogen flame detector detects, N
2Do carrier gas.Evaluation result is seen Fig. 8.
Get the dual-component catalyst 1.8g of embodiment 6 preparation, be curled into cylindricly, placing internal diameter is that the stainless steel tubular type reactor of 10mm carries out activity rating.Appreciation condition: reacting gas consists of H
2: C
2H
2: C
2H
4: N
2=2: 1: 99: 18, reaction temperature was 35～60 ℃, pressure 0.1MPa, air speed 3000h
-1Behind the stable reaction 2h, sample analysis.Product enters GC-6890 type gas-chromatography by six-way valve and carries out on-line analysis, and with ethene in the Porapak Q assay products and acetylene ratio, hydrogen flame detector detects, N
2Do carrier gas.Evaluation result is seen Fig. 9.
By the data among Fig. 8 and Fig. 9 as seen, eggshell type porous silicon dioxide nano particle according to embodiment 3 and embodiment 6 preparations is the integral catalyzer of coating, for the reaction that selective hydrogenation of acetylene is removed a little acetylene in a large amount of ethene, have higher conversion of alkyne and ethylene selectivity.When wherein using the catalyst that is prepared by embodiment 3, conversion of alkyne is 98.4% o'clock, and ethylene selectivity can reach 52.4%; Use is during by the catalyst of embodiment 6 preparation, and conversion of alkyne is 96.8% o'clock, and ethylene selectivity can reach 54.9%.
Claims (6)
1. integrated catalyst carrier is characterized in that: outerly be eggshell type porous silicon dioxide nano particle, be coated in inner on the matrix of integrated structure by inorganic bond.
2. catalyst carrier according to claim 1 is characterized in that: described porous silicon dioxide nano grain diameter is 50～120nm, and wall thickness is at 5～30nm; Specific area is 300～1000m
2/ g; Pore volume is 0.4～1.3mL/g; Inorganic bond is 3～10wt% aluminium colloidal sol or Ludox; The matrix of integrated structure is cordierite, carborundum or the FeCrAl alloy with alveolate texture.
3. the preparation method of integrated catalyst carrier according to claim 1, it is characterized in that: with spherical nano-calcium carbonate is template, prepares eggshell type porous silicon dioxide nano particle by the hydrolysis sodium metasilicate; Utilize eggshell type porous silicon dioxide nano particle and 3～10wt% aluminium colloidal sol or Ludox to prepare coating liquid, wherein the mass ratio of solid is 1～5 in eggshell type porous silicon dioxide nano particle and the colloidal sol; The integral catalyzer matrix is impregnated in eggshell type porous silicon dioxide nano particle-colloidal sol coating liquid, takes out behind 3～30min; 80～120 ℃ down dry, and the time is 3～7h, after 400～700 ℃ of air atmosphere calcining 3～10h obtain eggshell type porous silicon dioxide nano particle is the integrated catalyst carrier of coating.
4. application rights requires 1 described monolithic substrate to prepare the method for integral catalyzer, it is characterized in that: 0.4～1wt% is measured metal salt solution by activity component load quantity, metal salt solution dripped into fill in the container of monolithic substrate that eggshell type porous silicon dioxide nano particle is a coating, load boils off moisture after finishing; Dried catalyst is calcined 3～7h down at 400～500 ℃, and obtaining with eggshell type porous silicon dioxide nano particle is the integral catalyzer of coating.
5. according to the described method for preparing integral catalyzer of claim 4, it is characterized in that: described active component is one or more in gold, silver and the platinum group.
6. according to the described method for preparing integral catalyzer of claim 4, described catalyst activates with online reducing process, and reduction process is 0.05～0.1 H for feeding volume ratio in the time of 70～500 ℃
2/ N
2Mist, the flow-control of mist are at 10～50ml/min, and the recovery time is 1～5h.
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