CN101992101B - Precious metal catalyst - Google Patents
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- CN101992101B CN101992101B CN2009100578330A CN200910057833A CN101992101B CN 101992101 B CN101992101 B CN 101992101B CN 2009100578330 A CN2009100578330 A CN 2009100578330A CN 200910057833 A CN200910057833 A CN 200910057833A CN 101992101 B CN101992101 B CN 101992101B
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Abstract
ate is high in the prior art. The invention adopts a catalyst comprising laminated compound carrier, active component and auxiliaries, and the catalyst concretely comprises the following components: (a) at least one of platinum and palladium is selected as active component; (b) at least one of alkali metal, alkali soil metal, IB, IIB, VB, VIIB, VIII, IIIA, IVA or lanthanide series compound is selected as auxiliary; (c) a laminated compound carrier which is composed of an inner core comprising an inert carrier and a multihole coating material shell combined on the inner core is taken as a carrier; wherein the weight ratio of the shell and inner core of the laminated compound carrier is(0.002-1):1.The problems are well solved, and the invention can be applied to industrial production for removing hydrogen by CO mixed gas selective oxidation.
Description
Technical field
The present invention relates to a kind of noble metal catalyst, particularly remove the noble metal catalyst of hydrogen about the selective oxidation of CO coupling producing oxalic ester unstrpped gas.
Background technology
Oxalate is important Organic Chemicals, is used for fine chemistry industry in a large number and produces various dyestuffs, medicine, important solvent, extractant and various intermediate.Get into 21 century, oxalate receives international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the oxalate ordinary-pressure hydrolysis can get oxalic acid, and normal pressure ammonia is separated and can be got high-quality slow chemical fertilizer oxalyl ammonia.Oxalate can also be used as solvent, produces medicine and dyestuff intermediate etc., for example carries out various condensation reactions with fatty acid ester, hexamethylene acetophenone, amido alcohol and many heterocyclic compounds.It can also synthesize at the chest acyl alkali that pharmaceutically is used as hormone.In addition, the oxalate low-voltage hydrogenation can prepare crucial industrial chemicals ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import ethylene glycol every year, and import volume was nearly 4,800,000 tons in 2007.
The production route of tradition oxalate utilizes oxalic acid to prepare with alcohol generation esterification, and the production technology cost is high, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.And adopt the carbon monoxide coupling technology to produce the focus that oxalate has become domestic and international research.
As everyone knows; Carbon monoxide can be from the various gaseous mixtures that contain carbon monoxide separation and Extraction, the unstripped gas that can be used for separating carbon monoxide in the industry comprises: the tail gas of synthesis gas, water-gas, semiwater gas and steel plant, calcium carbide factory and yellow phosphorus factory that natural gas and oil transform etc.It is pressure swing adsorption method that existing CO separates the main method of purifying; China has many companies to develop transformation adsorbing separation carbon monoxide new technology; Especially the high-efficiency adsorbent of developing; Carbon monoxide there are high adsorption capacity and selectivity, can solve a difficult problem of from the high unstripped gas of nitrogen or methane content, isolating high-purity carbon monooxide, can design and build up large-scale carbon monoxide separator.However, by this technology isolated carbon monoxide from synthesis gas, under the prerequisite of taking into account the carbon monoxide yield, generally the content of its hydrogen still reaches more than 1%.And research shows that the existence of hydrogen can cause the active reduction of follow-up CO coupling reaction catalyst, can't carry out until reaction, and therefore, it is great that the exploitation carbon monoxide selects to remove the hydrogen technical meaning.
Catalyst for selective oxidation about hydrogen generally is on noble metal catalyst, to carry out; This type catalyst is a lot; But the selective oxidation dehydrogenation under existing about CO rarely has report, has for example introduced the selective catalyst combustion PtSnLi/Al that hydrogen in the styrene is produced in ethylbenzene dehydrogenation among patent US4812597 and the US4914249
2O
3Catalyst adopts Pt as major catalyst, and Sn is as co-catalyst, and Li or other alkali metal or alkaline-earth metal adopt α-Al as dressing agent
2O
3As carrier, its shortcoming is that the precious metals pt consumption is higher in the catalyst.And for example to have reported a kind of be the hydrogen selective catalyst combustion reaction catalyst of carrier with the lithium aluminate for patent US6858769 and CN1705510A, and this catalyst is active component with Pt.
The catalyst of above-mentioned patent preparation all is that eggshell type distributes, and promptly active component concentrates on the surperficial thin-shell type on carrier top layer.Eggshell type distribution catalyst can significantly reduce noble metal dosage, improves the utilization rate of noble metal.Simultaneously, the catalyst that eggshell type distributes in many reactions also showed than the better activity of equally distributed catalyst, selectivity and life-span.In addition,, for this typical exothermic reaction of hydrogen selective catalyst combustion, more help the transfer of reaction heat, with stability that keeps catalyst and the service life that prolongs catalyst because active component concentrates on the carrier top layer.But when the catalyst of this invention is used for hydrogen selective catalyst combustion; The selectivity of burning hydrogen is high not enough, causes oxygen partial combustion CO, causes significant loss; Special under the situation of resource, energy growing tension, reduce consumption of raw materials and just seem more important.
Summary of the invention
Technical problem to be solved by this invention is that noble metal catalyst selective oxidation in the presence of carbon monoxide of prior art is high except that there being the CO loss late in the hydrogen process, and the technical problem that the hydrogen removal efficiency is low provides a kind of new noble metal catalyst.It is low that this noble metal catalyst has the CO loss late, the advantage that the hydrogen removal efficiency is high.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of noble metal catalyst, comprise lamellar composite carrier, active component and auxiliary agent, and by weight percentage, catalyst comprises following component:
A) being selected from least a for active component in platinum metal ruthenium, rhodium, palladium, osmium, iridium, the platinum, is 0.003～1% of catalyst weight in the simple substance consumption;
B) being selected from least a for auxiliary agent in alkali metal, alkaline-earth metal, IB, IIB, VB, VIIB, VIII, IIIA, IVA or the lanthanide compound, is 0.005～15% of catalyst weight in the simple substance consumption;
C) 84～99.5% lamellar composite carrier;
Wherein lamellar composite carrier is by comprising that is selected from a α-Al
2O
3, θ-Al
2O
3, at least a inert carrier in metal, SiC, cordierite, zirconia, titanium oxide, quartz, spinelle, mullite or the mullite kernel and be combined in the α-Al that is selected from the kernel
2O
3, γ-Al
2O
3, δ-Al
2O
3, η-Al
2O
3, θ-Al
2O
3, at least a porous coating material shell in silica, zeolite, non-zeolite molecular sieve, titanium oxide or the zirconia forms; Wherein the weight ratio of shell and kernel is 0.002～1: 1; The weight ratio preferable range is 0.005～0.6: 1, and weight ratio more preferably scope is 0.01～0.5: 1.
In the technique scheme, check in the lamellar composite carrier catalyst precursor adsorption capacity a little less than, preferred version is selected from α-Al
2O
3, at least a in SiC, spinelle, mullite or the cordierite.The kernel of lamellar composite carrier can be made different shapes as required, and like cylindric, spherical, sheet, tubular, cellular or Raschig ring etc., but spherical inner core is reasonable selection, and its diameter is preferably 1～6 millimeter, so that commercial Application.The porous coating material shell of lamellar composite carrier is heat-resisting porous oxide material, and preferably the sorptive material of porous is stronger to the catalyst precursor adsorption capacity, and has high specific area, and preferred version is selected from α-Al
2O
3, θ-Al
2O
3, δ-Al
2O
3, γ-Al
2O
3Or at least a in the molecular sieve.Active component is platinum in platinum metal or palladium preferably, is 0.02～0.8% of catalyst weight in its consumption preferable range of simple substance.Active component more preferably scheme is selected from the palladium in the platinum metal, in its consumption of simple substance more preferably scope be 0.02～0.6% of catalyst weight.The auxiliary agent preferred version is selected from least a in K, Mg, Ba, V, Mn, Cu, Ni, Zn, Fe, Sn, La or the Ce compound in alkali metal, alkaline-earth metal, IB, IIB, VB, VIIB, VIII, IIIA, IVA or the lanthanide series, is 0.01～10% of catalyst weight in its consumption of simple substance.Auxiliary agent more preferably scheme is selected from least a in K, Fe, Ce or the Sn compound, in its consumption of simple substance more preferably scope be 0.05～8% of catalyst weight.Activity of such catalysts component and auxiliary element composition are distributed in the shell of carrier porous coating material.
The preparation process of noble metal catalyst is following:
At first, the preparation of coating (shell) component ultrafine particle.It is more even that ultrafine particle helps the coating coating on the one hand, can increase the specific area of coating simultaneously, helps the dispersion of active component.Methods such as the coating ingredients ultrafine particle can be pulverized through air-flow, ball milling are controlled at its particle diameter below 120 microns.
Secondly, the preparation of coating ingredients slurries.At least a, distilled water in coating ingredients such as aluminium oxide or the molecular sieve are stirred according to a certain percentage, mix, make slurries.Aluminium oxide can be used α-Al
2O
3, θ-Al
2O
3, δ-Al
2O
3, γ-Al
2O
3Also need add a kind of organic adhesive in the slurries to increase the intensity of coating material on kernel.Polyvinyl alcohol, CMC, hydroxypropyl cellulose, methyl or ethyl or carboxyethyl cellulose, ring essence etc. recklessly for example, but be not limited to these.The addition of organic adhesive is controlled at 0.3～5% of slurries gross mass.Also contain inorganic binder in the slurries, like inorganic clay, aluminium colloidal sol, Ludox, calcium silicates, potassic feldspar etc., addition is controlled at 0.1～20% of slurries gross mass.In addition; Also need add surfactant in the slurries; Kind to surfactant does not have particular restriction, can be anionic surfactant, cationic surface active agent, amphoteric surfactant and non-ionic surface active agent, like tween, sapn, softex kw, tetraethylammonium bromide etc.; To reduce the surface tension of slurries, addition is controlled at 0.01～1.0% of slurries gross mass.
Once more, the control of coating slurries particle diameter.For the firmness of enhancement coating, need to reduce particle size in the slurries, obtain the slurries that particle size is little, distribution is narrow.This can carry out through ball-milling method, but is not limited to this method.The ball milling time was controlled at 20 minutes～6 hours, preferably was controlled at 1～3 hour, thereby the slurries particle diameter is controlled at below 10 microns.
Then, slurries form coating through the surface that sprays, methods such as glue is coated with, spin, dipping, dip-coating cover kernel, preferred spraying process.The thickness of coating can change as required, but should be controlled between 30～250 microns, preferably is controlled at 50～200 microns.When the coated material of the kernel of lamellar composite carrier apply good after, 40～200 ℃ of dryings 1～24 hour, then 700～1200 ℃ of roastings 1～8 hour so that coating and carrier kernel effectively combine, thereby obtain lamellar composite carrier.
At last, supported catalyst active component on lamellar composite carrier.Catalyst activity component such as platinum group metal and co-catalyst can be dispersed on the lamellar composite carrier with any method that is suitable for obtaining surface impregnation.When preparation catalyst of the present invention, can use any decomposable platinum family compound, like halide, nitrate, oxide etc.; For example chlorine palladium acid sodium, tetrachloro-palladium acid sodium, potassium chloropalladate, chlorine four ammonia palladiums, palladium oxide, the acid of chlorine palladium, ammonium chloropalladate, the inferior palladium acid of chlorine.Platinum group metal active component and auxiliary agent can combine with carrier with random order.Can on the lamellar composite carrier surface, flood platinum-group component earlier; Then again at one or more auxiliary agents of surface impregnation or dressing agent; Also can on carrier surface, flood one or more auxiliary agents or dressing agent earlier; Then, flood platinum-group component and auxiliary agent or dressing agent certainly simultaneously and also can again in the surface impregnation platinum-group component.
Co-catalyst does not have special limitation to its source, and is comparatively suitable with nitrate, oxalates, ammonium salt or chloride.Co-catalyst can load on earlier on the lamellar composite carrier surface, also can after the palladium load, carry out surface impregnation again.Method comparatively commonly used is first load cocatalyst, after dry and roasting, adopts the surface impregnation technology to flood to contain palladium and alkali metal, alkaline earth metal compound solution.At last; The catalyst precursor that will contain active component is earlier 100～150 ℃ of dryings 1～24 hour, then 200～700 ℃ of roastings 1～24 hour, under hydrogen or other reducing atmosphere; In 300～800 ℃ of reduction 4 hours, promptly make required noble metal catalyst.
The hydrogen removal efficiency and the CO loss late of indication of the present invention obtain through following account form:
Quality * 100% of hydrogen removal efficiency=(quality of the quality of raw hydrogen-product hydrogen)/raw hydrogen
Quality * 100% of CO loss late=(quality of quality-product C O of raw material CO)/raw material CO
As everyone knows, carbon monoxide and hydrogen are the stronger gas of reproducibility, and under the condition of the two and oxygen coexistence, normal conditions are when hydrogen is removed in selective oxidation, and the CO loss that equally also can react is bigger.Even only occur that CO reacts and the nonreactive situation of hydrogen.Therefore, how developing the catalyst that high selection removes hydrogen in the CO gas is challenging problem.And we are surprised to find in big quantity research, adopt noble metal catalyst of the present invention in the presence of carbon monoxide, to select to remove in the hydrogen reaction process, and CO loses hardly, and hydrogen can take off to 1ppm, even are 0.And further dynamics research is found, adopts noble metal catalyst of the present invention to carry out the high selection of CO gas and removes in the hydrogen reaction process, and far faster than the adsorption rate of CO, CO and oxygen generate CO to the adsorption rate in hydrogen and activated centre
2The reaction activity of step is far above the activation energy of hydrogen and oxygen reaction generation water reactions step, and this transforms hydrogen for realizing maximization, and the while is avoided the oxidational losses of CO to greatest extent, provides the most important theories basis to support with theoretical from the kinetics angle.
Noble metal catalyst of the present invention is to be the basis with the theory of thin shell, and the effective active layer through the control catalyst concentrates in the shell of catalyst granules noble metal, presents the eggshell state structure of high dispersive, and kernel is an inert material, this class formation 2H that is highly advantageous to
2+ O
2→ 2H
2The O chemical reaction carries out, and units activity component effective rate of utilization is high, and catalyst has higher dehydrogenation activity, can bring into play the catalytic action of reactive metal palladium expeditiously.Simultaneously, catalyst effective active layer is thin, makes raw material and product have shorter the evolving path, and reactant and the product time of staying in catalyst granules shortens, thereby the side reaction minimizing, has reduced the loss of raw material, has obtained better technical effect.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
The specific embodiment
[embodiment 1]
Glycerite, the 0.5 gram sorbester p17 of 30 gram alumina sols (aluminium oxide that contains 25% mass ratio), 60 grams 2% are processed slurries.Adding 0.5 gram Ludox, 40 gram particles directly are the γ-Al below 80 microns in this mixed liquor then
2O
3Powder (specific area 200 meters squared per gram).Stir about adds 0.8 gram Ce after ten minutes
2O
3, 2.5 the gram barium monoxide and 0.6 the gram iron oxide, the slurries that obtain at room temperature ball milling made that particle size was controlled at below 10 microns in 4 hours.These slurries are sprayed to the MgAl of 4 millimeters of particle diameters
2O
4On the bead, in 80 ℃ of dryings 2 hours, then be warming up to 100 ℃ dry 2 hours once more, in 1100 ℃ of roastings 6 hours, obtain lamellar composite carrier at last.ESEM shows about 90 microns of its coating (shell) thickness, and coating (shell) specific area is 165 meters squared per gram, and the shell of lamellar composite carrier and the weight ratio of kernel are 0.045: 1.
Ammonium chloropalladate is dissolved in the water, and using the HCl regulator solution to make its pH value is about 3.5, then this solution is heated to 80 ℃; Be immersed on the lamellar composite carrier of having processed, then in 120 ℃ of dryings 4 hours, then 450 ℃ of roastings 4 hours; Reductase 12 hour in 300 ℃ of hydrogen atmospheres feeds water vapours at 650 ℃ then, in tail gas, does not have chlorion; Then in nitrogen atmosphere, be cooled to room temperature, obtain catalyst A.Elementary analysis shows with regard to whole catalyst and contains Pd 0.015% according to the mass fraction meter, and Ge 0.15%, and Ba 0.23%, and Fe 0.1%.
[embodiment 2]
With FeCl
2And cerium chloride is dissolved in the water according to mol ratio at 1: 0.5, with above-mentioned solution impregnation at θ-Al
2O
3On (solid-to-liquid ratio 1: 2) powder, in 120 ℃ of dryings 4 hours, 400 ℃ of roastings 4 hours.Polyacrylamide solution, the 0.4 gram betaine of 40 gram alumina sols (containing 15% aluminium oxide), 60 grams 3% are processed slurries.The particle diameter that in this mixed liquor, adds 0.3 gram Ludox, the pre-soaked Fe of 40 gram processes, Ce then is the θ-Al below 80 microns
2O
3Powder.Stir about adds 2.0 gram 25%MgCl after ten minutes
2The aqueous solution, the slurries that obtain at room temperature ball milling made that particle size was controlled at below 10 microns in 4 hours.Slurries spray to the α-Al of 4 millimeters of particle diameters
2O
3On the bead, in 100 ℃ of dryings 4 hours, then be warming up to 130 ℃ dry 4 hours once more, in 900 ℃ of roastings 10 hours, obtain lamellar composite carrier at last.ESEM shows about 100 microns of its coating (shell) thickness, and coating (shell) specific area is 150 meters squared per gram, and the shell of lamellar composite carrier and the weight ratio of kernel are 0.045: 1.
Potassium nitrate and ammonium chloropalladate are dissolved in the water respectively, and using the HCl regulator solution to make its pH value is about 3, then this solution is heated to 80 ℃; Be immersed on the lamellar composite carrier of having processed, then in 140 ℃ of dryings 4 hours, then 450 ℃ of roastings 4 hours; Reductase 12 hour in 300 ℃ of hydrogen atmospheres feeds water vapours at 650 ℃ then, in tail gas, does not have chlorion; Then in nitrogen atmosphere, be cooled to room temperature, obtain catalyst B.Elementary analysis shows with regard to whole catalyst and contains Pd 0.07% according to the mass fraction meter, K0.45%, and Fe 0.1%, Ce0.05%, Mg 0.01%.
[embodiment 3]
Cyclodextrin solution, 2.0 gram lanthanas, the 1.0 gram softex kws of 45 gram alumina sols (aluminium oxide that contains 25% mass ratio), 5 grams, 40% Ludox, 60 grams 4% are processed slurries.In this mixed liquor, adding 0.4 gram manganous silicate, 0.3 gram potash and 40 gram particles then directly is the δ-Al below 100 microns
2O
3Powder.Behind the stir about ten minutes, the slurries that obtain at room temperature ball milling made that particle size was controlled at below 8 microns in 3 hours.Slurries spray on the mullite spheroid of 6 millimeters of particle diameters, in 100 ℃ of dryings 4 hours, then be warming up to 160 ℃ dry 2 hours once more, in 800 ℃ of roastings 4 hours, obtain lamellar composite carrier at last.ESEM shows about 40 microns of its coating (shell) thickness, and coating (shell) specific area is 175 meters squared per gram, and the shell of lamellar composite carrier and the weight ratio of kernel are 0.013: 1.
Lithium nitrate and palladium nitrate are dissolved in the water respectively, are mixed with mixed solution, using the HCl regulator solution to make its pH value is about 3.5; Then this solution is heated to 80 ℃, is immersed on the lamellar composite carrier of having processed, then in 150 ℃ of dryings 2 hours; Then 450 ℃ of roastings 4 hours; Reductase 12 hour in 300 ℃ of hydrogen atmospheres then is cooled to room temperature in nitrogen atmosphere, obtain catalyst C.Elementary analysis shows with regard to whole catalyst and contains Pd0.13% according to the mass fraction meter, and Mn 0.18%, and Li 1%, and K 0.05%.
[embodiment 4]
CMC, the 10 gram softex kws of 40 gram alumina sols (aluminium oxide that contains 20% mass ratio), 7 grams, 35% Ludox, 70 grams 4% are processed slurries.In this mixed liquor, adding 45 gram particles then directly is the δ-Al below 30 microns
2O
3Powder.Stir about adds the ammonium metavanadate aqueous solution of 6.0 grams 0.2% after 20 minutes, the slurries that obtain at room temperature ball milling made that particle size was controlled at below 4 microns in 6 hours.Slurries spray to the ZSM-5 molecular sieve of 1.5 millimeters of particle diameters, and (silica alumina ratio is 500: 1; Specific surface is 380 meters squared per gram) on the bead, in 80 ℃ of dryings 4 hours, then be warming up to 153 ℃ dry 4 hours once more; In 900 ℃ of roastings 2 hours, obtain lamellar composite carrier at last.ESEM shows about 180 microns of its coating (shell) thickness, and coating (shell) specific area is 200 meters squared per gram, and the shell of lamellar composite carrier and the weight ratio of kernel are 0.25: 1.
Lithium nitrate and platinum nitrate are dissolved in the water respectively, are mixed with mixed solution, using the HCl regulator solution to make its pH value is about 3.5; Then this solution is heated to 80 ℃, is immersed on the lamellar composite carrier of having processed, then in 150 ℃ of dryings 2 hours; Then 450 ℃ of roastings 4 hours, reduction was 4 hours in 350 ℃ of hydrogen atmospheres, obtains catalyst D; Elementary analysis shows with regard to whole catalyst and contains Pt 0.50% according to the mass fraction meter, and Li 2.5%, and V 1.2%.
[embodiment 5]
Poly-vinyl alcohol solution, the 1.O gram ceteth of 35 gram alumina sols (aluminium oxide that contains 20% mass ratio), 4 gram lanthanum nitrates, 60 grams 4% are processed slurries.In this mixed liquor, add 0.2 gram Ludox, 40 grams then through pretreated α-Al below 100 microns
2O
3Powder.The slurries that obtain at room temperature ball milling made that particle size was controlled at below 5 microns in 4 hours.Slurries spray on the cordierite spheroid of 1 millimeter of particle diameter, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, in 1050 ℃ of roastings 5 hours, obtain lamellar composite carrier at last.ESEM shows about 200 microns of its coating (shell) thickness, and coating (shell) specific area is 118 meters squared per gram, and the shell of lamellar composite carrier and the weight ratio of kernel are 0.44: 1.
With lithium nitrate, calcium nitrate is dissolved in the water, and vacuum impregnation is on the lamellar composite carrier of having processed, then in 150 ℃ of dryings 2 hours.With SnCl
4And palladium nitrate is dissolved in the ethanolic solution, is immersed on the carrier 150 ℃ of dryings 2 hours once more; Then 450 ℃ of roastings 4 hours; Reductase 12 hour in 300 ℃ of hydrogen atmospheres feeds water vapours at 650 ℃ then, in tail gas, does not have chlorion; Then in nitrogen atmosphere, be cooled to room temperature, obtain catalyst E.Elementary analysis shows with regard to whole catalyst and contains Pd 0.05% according to the mass fraction meter, and Sn 0.08%, and Li 0.24%, and La 0.03%, Ca0.01%.
[embodiment 6]
Cyclodextrin solution, the 1.0 gram ceteths of 35 gram alumina sols (aluminium oxide that contains 20% mass ratio), 4 gram zinc nitrates, 60 grams 4% are processed slurries.In this mixed liquor, add 0.2 gram aluminium colloidal sol, 40 grams then through pretreated θ-Al below 100 microns
2O
3Powder.The slurries that obtain at room temperature ball milling made that particle size was controlled at below 5 microns in 4 hours.Slurries spray on the zirconia spheroid of 1 millimeter of particle diameter, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, in 1000 ℃ of roastings 3 hours, obtain lamellar composite carrier at last.ESEM shows about 180 microns of its Xu's layer (shell) thickness, and coating (shell) specific area is 110 meters squared per gram, and the shell of lamellar composite carrier and the weight ratio of kernel are 0.7: 1.
Copper nitrate is dissolved in the water, and vacuum impregnation is on the lamellar composite carrier of having processed, then in 150 ℃ of dryings 2 hours.With SnCl
4And ammonium chloroplatinite is dissolved in the ethanolic solution, is immersed on the carrier 150 ℃ of dryings 2 hours once more; Then 450 ℃ of roastings 4 hours; Reductase 12 hour in 300 ℃ of hydrogen atmospheres feeds water vapours at 650 ℃ then, in tail gas, does not have chlorion; Then in nitrogen atmosphere, be cooled to room temperature, obtain catalyst F.Elementary analysis shows with regard to whole catalyst and contains Pt 0.3% according to the mass fraction meter, and Sn 4%, and Cu 1%, and Zn 0.03%.
[embodiment 7]
Hydroxypropyl cellulose solution, the 1.0 gram ceteths of 50 gram alumina sols (aluminium oxide that contains 15% mass ratio), 3 gram nickel nitrates, 20 grams 4% are processed slurries.In this mixed liquor, add 0.2 gram aluminium colloidal sol, 40 grams then through pretreated θ-Al below 100 microns
2O
3Powder.The slurries that obtain at room temperature ball milling made that particle size was controlled at below 5 microns in 4 hours.Slurries spray on the titanium oxide spheroid of 3 millimeters of particle diameters, in 80 ℃ of dryings 2 hours, then be warming up to 160 ℃ dry 2 hours once more, in 1000 ℃ of roastings 3 hours, obtain lamellar composite carrier at last.ESEM shows about 80 microns of its Xu's bed thickness (shell) degree, and coating (shell) specific area is 120 meters squared per gram, and the shell of lamellar composite carrier and the weight ratio of kernel are 0.08: 1.
The nitric acid niobium is dissolved in the water, and vacuum impregnation is on the lamellar composite carrier of having processed, then in 150 ℃ of dryings 2 hours.The acid of chlorine rhodium is dissolved in the ethanolic solution, is immersed in once more on the carrier, 150 ℃ of dryings 2 hours; Then 450 ℃ of roastings 4 hours; Reductase 12 hour in 300 ℃ of hydrogen atmospheres feeds water vapours at 650 ℃ then, in tail gas, does not have chlorion; Then in nitrogen atmosphere, be cooled to room temperature, obtain catalyst G.Elementary analysis shows with regard to whole catalyst and contains Rh 0.008% according to the mass fraction meter, and Ni 4%, and Nb 1.5%.
[embodiment 8]
35 gram alumina sols (aluminium oxide that contains 20% mass ratio), 4 gram nitric acid molybdenums, the poly-vinyl alcohol solution of 60 grams 4%, 1.0 gram ceteths are processed slurries.In this mixed liquor, add 0.2 gram Ludox, 40 grams then through pretreated α-Al below 100 microns
2O
3Powder.The slurries that obtain at room temperature ball milling made that particle size was controlled at below 5 microns in 4 hours.Slurries spray on the SiC spheroid of 3.5 millimeters of particle diameters, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, in 800 ℃ of roastings 5 hours, obtain lamellar composite carrier at last.ESEM shows about 100 microns of its coating (shell) thickness, and coating (shell) specific area is 130 meters squared per gram, and the shell of lamellar composite carrier and the weight ratio of kernel are 0.057: 1.
Lithium nitrate is dissolved in the water, and vacuum impregnation is on the lamellar composite carrier of having processed, then in 150 ℃ of dryings 2 hours.With FeCl
2And ammonium chloropalladite is dissolved in the ethanolic solution, is immersed on the carrier 150 ℃ of dryings 2 hours once more; Then 450 ℃ of roastings 4 hours; Reductase 12 hour in 300 ℃ of hydrogen atmospheres feeds water vapours at 650 ℃ then, in tail gas, does not have chlorion; Then in nitrogen atmosphere, be cooled to room temperature, obtain catalyst H.Elementary analysis shows with regard to whole catalyst and contains Pd 0.8% according to the mass fraction meter, and Fe 12%, and Li 0.68%, and Mo 0.23%.
[embodiment 9]
Cyclodextrin solution, the 1.0 gram ceteths of 35 gram alumina sols (aluminium oxide that contains 20% mass ratio), 4 gram ferric nitrates, 60 grams 4% are processed slurries.In this mixed liquor, add 0.2 gram aluminium colloidal sol, 40 grams then through pretreated α-Al below 100 microns
2O
3Powder.The slurries that obtain at room temperature ball milling made that particle size was controlled at below 5 microns in 4 hours.Slurries spray on the zirconia spheroid of 5 millimeters of particle diameters, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, in 1000 ℃ of roastings 3 hours, obtain lamellar composite carrier at last.ESEM shows about 100 microns of its coating (shell) thickness, and coating (shell) specific area is 150 meters squared per gram, and the shell of lamellar composite carrier and the weight ratio of kernel are 0.04: 1.
Ammonium chloropalladite is dissolved in the ethanolic solution; Be immersed in once more on the carrier, 150 ℃ of dryings 2 hours are then 450 ℃ of roastings 4 hours, reductase 12 hour in 300 ℃ of hydrogen atmospheres; Feed water vapour at 650 ℃ then; In tail gas, do not have chlorion, then in nitrogen atmosphere, be cooled to room temperature, obtain catalyst I.Elementary analysis shows with regard to whole catalyst and contains Pd 0.25% according to the mass fraction meter that Fe 0.60%.
[embodiment 10]
Cyclodextrin solution, the 1.0 gram ceteths of 35 gram alumina sols (aluminium oxide that contains 20% mass ratio), 5 gram bismuth nitrates, 60 grams 4% are processed slurries.In this mixed liquor, add 0.2 gram aluminium colloidal sol, 40 grams then through pretreated α-Al below 100 microns
2O
3Powder.The slurries that obtain at room temperature ball milling made that particle size was controlled at below 5 microns in 4 hours.Slurries spray on the zirconia spheroid of 5 millimeters of particle diameters, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, in 1000 ℃ of roastings 3 hours, obtain lamellar composite carrier at last.ESEM shows about 100 microns of its coating (shell) thickness, and coating (shell) specific area is 150 meters squared per gram, and the shell of lamellar composite carrier and the weight ratio of kernel are 0.04: 1.
Palladium nitrate is dissolved in the ethanolic solution, is immersed in once more on the carrier, 150 ℃ of dryings 2 hours are then 450 ℃ of roastings 4 hours, and reductase 12 hour in 300 ℃ of hydrogen atmospheres then is cooled to room temperature in nitrogen atmosphere, obtain catalyst J.Elementary analysis shows with regard to whole catalyst and contains Pd 0.25% according to the mass fraction meter that Bi 0.55%.
[comparative example 1]
This Preparation of catalysts is shown in the embodiment 2 of 4812597 li of the U.S. Pat mentioned in the reference of front.Elementary analysis shows with regard to whole catalyst and contains Pt 0.20% according to the mass fraction meter, and Sn 0.23%, and Li 0.20%.Catalyst is marked as K.ESEM shows about 160 microns of its coating layer thickness, and the coating specific area is 53 meters squared per gram.
[comparative example 2]
The preparation of this oxidation catalyst is shown in the embodiment 3 of 6858769 li of the U.S. Pat mentioned in the reference of front.Elementary analysis shows with regard to whole catalyst and contains Pt 0.14% according to the mass fraction meter, and Sn 0.16%, and Li 0.72%.Catalyst is marked as L.ESEM shows about 150 microns of its coating layer thickness, and the coating specific area is 46 meters squared per gram.
The catalyst activity property testing:
It is to carry out in 18 millimeters the stainless steel reaction pipe that CO mist selective oxidation dehydrogenation is reflected at internal diameter, in adorn 20 milliliters of catalyst.Reaction pressure is a normal pressure, volume space velocity 3000 hours
-1, 190 ℃ of reaction temperatures, the volume ratio of hydrogen and oxygen is 1.6: 1, and CO content is 98% in the raw material, and the content of hydrogen is 2%.
Activity of such catalysts and selectivity result list in the table 1.From table, can find out; The removal efficiency of the catalyst hydrogen of this method preparation all reaches 100%; And the CO loss late all is lower than 1%, and the removal efficiency of reference catalyst hydrogen all is lower than 99%, and the CO loss late all is higher than 1.5%; Shown that catalyst of the present invention is used for the selective oxidation of CO mist and removes H-H reaction, had higher hydrogen removal efficiency and lower CO loss late.
The reactivity worth of table 1 catalyst
Claims (8)
1. a noble metal catalyst comprises lamellar composite carrier, active component and auxiliary agent, and by weight percentage, catalyst comprises following component:
A) being selected from least a for active component in platinum metal ruthenium, rhodium, palladium, osmium, iridium, the platinum, is 0.003～1% of catalyst weight in the simple substance consumption;
B) being selected from least a for auxiliary agent in alkali metal, alkaline-earth metal, IB, IIB, VB, VIIB, VIII, IIIA, IVA or the lanthanide compound, is 0.005～15% of catalyst weight in the simple substance consumption;
C) 84～99.5% lamellar composite carrier;
Wherein lamellar composite carrier is by comprising that is selected from a α-Al
2O
3, θ-Al
2O
3, at least a inert carrier in metal, SiC, cordierite, zirconia, titanium oxide, quartz, spinelle, mullite or the mullite kernel and be combined in the α-Al on the kernel
2O
3The porous coating material shell is formed, and wherein the weight ratio of shell and kernel is 0.002～1: 1.
2. according to the said noble metal catalyst of claim 1, it is characterized in that the inert carrier kernel is selected from α-Al
2O
3, at least a in SiC, spinelle, mullite or the cordierite.
3. according to the said noble metal catalyst of claim 1, it is characterized in that the shell of lamellar composite carrier and the weight ratio of kernel are 0.005～0.6: 1.
4. according to the said noble metal catalyst of claim 1, it is characterized in that active component is selected from platinum or the palladium in the platinum metal, is 0.02～0.8% of catalyst weight in the simple substance consumption.
5. according to the said noble metal catalyst of claim 4, it is characterized in that active component is selected from palladium in the platinum metal, is 0.02～0.6% of catalyst weight in the simple substance consumption.
6. according to the said noble metal catalyst of claim 1, it is characterized in that auxiliary agent is selected from least a in K, Mg, Ba, V, Mn, Cu, Ni, Zn, Fe, Sn, La or the Ce compound, be 0.01～10% of catalyst weight in the simple substance consumption.
7. according to the said noble metal catalyst of claim 6, it is characterized in that auxiliary agent is selected from least a in K, Fe, Ce or the Sn compound, be 0.05～8% of catalyst weight in the simple substance consumption.
8. according to the said noble metal catalyst of claim 1, it is characterized in that activity of such catalysts component and auxiliary element composition is distributed in the shell of carrier porous coating material.
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| CN102974344A (en) * | 2012-10-30 | 2013-03-20 | 大连凯特利催化工程技术有限公司 | Dehydrogenation catalyst applicable to raw gas rich in carbon monoxide, and preparation and application thereof |
| CN104415778B (en) * | 2013-08-30 | 2016-08-10 | 中国石油化工股份有限公司 | The sulfur method that desulphurization catalyst and preparation method thereof is oily with sulfurous fuels |
| CN105396584B (en) * | 2014-08-27 | 2018-04-06 | 中国石油化工股份有限公司 | CO couplings catalyst for synthesizing oxalic ester, preparation method and its usage |
| CN106179401A (en) * | 2016-07-12 | 2016-12-07 | 陕西理工学院 | A kind of noble metal catalyst and preparation method thereof |
| CN106807398B (en) * | 2017-01-05 | 2019-03-08 | 金华铂锐催化科技有限公司 | It is a kind of under water vapour environment eliminate carbon monoxide and the catalyst of formaldehyde and preparation method thereof |
| CN109395729B (en) * | 2017-08-18 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for preparing monocyclic aromatic hydrocarbon by selective hydrogenation of polycyclic aromatic hydrocarbon |
| NL2020819B1 (en) * | 2018-04-24 | 2019-10-31 | Cochise Tech Llc | A co to co2 combustion promoter |
| CN110743567B (en) * | 2019-11-07 | 2023-03-10 | 西安凯立新材料股份有限公司 | Iridium-carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof |
| CN112892612B (en) * | 2019-12-03 | 2023-01-17 | 中国石化集团金陵石油化工有限责任公司 | Catalyst for hydrocarbon conversion reaction |
| CN112958086B (en) * | 2021-02-07 | 2023-04-07 | 西安凯立新材料股份有限公司 | Sandwich-type catalyst for propane catalytic combustion and preparation method thereof |
| CN115155651B (en) * | 2022-08-05 | 2024-02-06 | 杭州果蔬鲜科技有限公司 | Platinum-based metal catalyst and preparation method and application thereof |
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