CN101711990A - Metal oxide-loaded molecular sieve catalyst and preparation method thereof - Google Patents
Metal oxide-loaded molecular sieve catalyst and preparation method thereof Download PDFInfo
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Abstract
A metal oxide-loaded molecular sieve catalyst comprises pure cryptomelane type manganese dioxide and transition metal. A method for preparing the molecular sieve catalyst comprises the following steps: 1, preparing solution of potassium permanganate; 2, preparing solution of manganese acetate; 3, adding the solution obtained by the step one into a three-neck flask, and heating, condensing and refluxing the solution; 4, adding the solution obtained by the step two into the three-neck flask of the step three, condensing and refluxing the solution, filtering and drying the obtained black pasty sediment, and roasting the sediment to obtain an octahedral manganese oxide molecular sieve catalyst (OMS-2) solid; 5, adding cerium ammonium nitrate, cobalt nitrate hexahydrate, copper nitrate trihydrate, ferric nitrate nonahydrate or yttrium nitrate into deionized water to form solution; and 6, mixing the solid taken from the step four and the solution in the step five, soaking cerium on the octahedral manganese oxide molecular sieve catalyst (OMS-2) solid, and drying and roasting the obtained solid to obtain the metal oxide-loaded molecular sieve catalyst. The metal oxide-loaded molecular sieve catalyst has the characteristics of high purification efficiency, low price and good thermal stability.
Description
Technical field
The present invention relates to the molecular sieve catalyst preparing technical field, particularly a kind of metal oxide-loaded molecular sieve catalyst and preparation method thereof.
Background technology
Along with the raising of industrial expansion and living standards of the people, automobile pollution sharply rises.Automobile consumption bulk petroleum resource has been aggravated the crisis of oil shortage, and a large amount of pernicious gases that contain in the vehicle exhaust cause severe contamination to environment simultaneously.For solving energy crisis and environmental pollution two large problems, select low emission, the New-type fuel that aboundresources is easy to get substitutes gasoline has become a kind of trend.On February 10th, 2004, experience is in the past summed up by eight ministries and commissions, unite once more and issue " about print and distribute＜vehicle-use alcohol gasoline enlarges the pilot scheme and＜vehicle-use alcohol gasoline expansion pilot work detailed rules for the implementation notice ".In the trial of current expansion pilot, Heilungkiang, Jilin, Liaoning, Henan, An Huiwu economize and are put into wherein, and ethanol petrol will be promoted in sealing across the entire province in these provinces, forbid selling regular gasoline.In addition, 9 districts and cities in Hubei Province, 7 districts and cities in Shandong Province, 5 districts and cities in Jiangsu Province, 6 districts and cities in Hebei province become local experimental city.Spirit as per advice, to the end of the year 2005, above-mentioned each province, districts under city administration scope realize that substantially vehicle-use alcohol gasoline substitutes other gasoline (army special procures, country and extraordinary deposit except oil).Yet because the adding of ethanol, changed the physical and chemical indexes of gasoline, compare with regular gasoline vehicular emission thing, ethanol petrol automotive emission pollutant also contains a small amount of unburned ethanol and does not have aldehydes of complete oxidation etc., and the discharging of these pollutants and motor vehicle operation conditions have very big relation.For ethanol, acetaldehyde, under engine same operation condition, its discharge capacity is along with the content of ethanol in the fuel combination increases and increases.
At present, the active component of catalytic converter mainly is noble metals such as Pt, Pd and Rh, and as rare earth or alkali earth metals such as Ce, the Ba of co-catalyst component and La, being used to improve activity of such catalysts and stability, still is that the vent gas catalytic cleaner of active component is low to the catalytic purification efficient of ethanol and acetaldehyde with the noble metal.Therefore, replace noble metal to come catalytic purification ethanol acetaldehyde with base metal and rare earth element is the domestic and international research focus always.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of metal oxide-loaded molecular sieve catalyst and preparation method thereof, be to solve existing vent gas catalytic cleaner, clean-up effect unfavorable technical problem not good to the oxidation effectiveness of the ethanol acetaldehyde of ethanol petrol vehicle exhaust remnants, has purification efficiency height, cheap, the characteristics of Heat stability is good.
To achieve these goals, the technical solution used in the present invention is: a kind of metal oxide-loaded molecular sieve catalyst comprises following component:
Pure cryptomelane type manganese dioxide is active component, accounts for 90%～95% of catalyst gross mass, difference containing transition metal Ce, Co, Cu, Fe or Y, and the transition metal component of doping accounts for 5%～10% of catalyst gross mass, and active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
A kind of preparation method of metal oxide-loaded molecular sieve catalyst utilizes the circumfluence method preparation, specifically may further comprise the steps:
One, the liquor potassic permanganate 150mL～300mL of configuration 0.30mol/L～0.40mol/L concentration adds thermal agitation, formation solution in 40～60 ℃;
Two, the manganese acetate solution 150mL～300mL of configuration 0.45mol/L～0.55mol/L concentration adds thermal agitation, formation solution in 40～60 ℃;
Three, the solution with gained in the step 1 is added in the 1000mL there-necked flask, and in 80～110 ℃ of oil bath heating, be 10～20min heat time heating time, stirs with electric mixer, and mixing speed is 350～450r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 80～110 ℃ of stirring reactions 22～26 hours, mixing speed is 350～450r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 1～2 hour, then in baking oven in 105～110 ℃ of dryings 10～12 hours; Put into Muffle furnace again in 400～500 ℃ of roastings 4～5 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 2.50g～3.50g;
Five, 0.52g～0.54g ammonium ceric nitrate, 0.66g～0.68g cabaltous nitrate hexahydrate, 0.50g～0.52g Gerhardite, 0.97g～0.99g nine nitric hydrate iron or 0.41～0.43g yttrium nitrate are joined in 45mL～50mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that cerium is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 40～60 ℃ of control water temperatures, the speed of rotation is 100～120/min; With the solid that obtains in baking oven in 105～110 ℃ of dryings 10～12 hours, put into Muffle furnace again in 400～500 ℃ of roastings 4～5 hours, obtain 5wt%M/OMS-2 (M=Ce, Co, Cu, Fe, Y) catalyst.
Advantage of the present invention is:
(1) this catalyst series is outstanding to the ethanol oxidation of acetaldehyde ability of ethanol petrol vehicle exhaust remnants, has the good advantage of low temperature active, the low characteristics of delivery temperature when being fit to cold start-up;
(2) this catalyst series Heat stability is good is fit to vehicle exhaust delivery temperature height, the characteristics that range of temperature is big;
(3) simple, the abundant raw material, with low cost of this catalyst structure possesses application prospect.
The present invention is that essential element utilizes circumfluence method to prepare octahedron manganese oxide molecular sieve catalyzer (OMS-2) with manganese, and on the basis of octahedron manganese oxide molecular sieve catalyzer (OMS-2) prescription, added Ce, Co, Cu, Fe, transition metal such as Y, a kind of cost is low, toxicity is little, Heat stability is good thereby prepared, and ethanol acetaldehyde low temperature is removed the catalyst of function admirable.
Description of drawings
Fig. 1 is reactant ethanol conversion figure in the catalytic purification ethanol synthesis process of the present invention.
Fig. 2 is the selectivity diagram of end product carbon dioxide in the catalytic purification ethanol synthesis process of the present invention.
Fig. 3 is the selectivity diagram of intermediate product acetaldehyde in the catalytic purification ethanol synthesis process of the present invention.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
A kind of metal oxide-loaded molecular sieve catalyst comprises following component:
Pure cryptomelane type manganese dioxide is active component, accounts for 94% of catalyst gross mass, 6% of the ingredients constitute catalyst gross mass of the transition metal Ce of doping, and active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
A kind of preparation method of metal oxide-loaded molecular sieve catalyst utilizes the circumfluence method preparation, specifically may further comprise the steps:
One, the liquor potassic permanganate 280mL of configuration 0.38mol/L concentration adds thermal agitation, formation solution in 56 ℃;
Two, the manganese acetate solution 288mL of configuration 0.54mol/L concentration adds thermal agitation, formation solution in 58 ℃;
Three, the solution with gained in the step 1 slowly is added in the 1000mL there-necked flask, and in 108 ℃ of oil bath heating, be 10min heat time heating time, stirs with electric mixer, and mixing speed is 350r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 106 ℃ of stirring reactions 25 hours, mixing speed is 350r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 1.8 hours, then in baking oven in 109 ℃ of dryings 10 hours; Put into Muffle furnace again in 490 ℃ of roastings 4.6 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 3.45g;
Five, the 0.54g ammonium ceric nitrate is joined in the 49mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that cerium is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 58 ℃ of control water temperatures, the speed of rotation is 117/min; With the solid that obtains in baking oven in 109 ℃ of dryings 10 hours, put into Muffle furnace again in 490 ℃ of roastings 4.9 hours, obtain the 5wt%Ce/OMS-2 catalyst.
The effect of present embodiment is seen accompanying drawing 1～3.
Referring to Fig. 1, Fig. 1 is load C e, Co, and Cu, Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal is the temperature variant result of reactant ethanol conversion in catalytic purification ethanol synthesis process.Being reflected at 60 ℃ and rise living of Ce/OMS-2 oxidation ethanol, 160 ℃ reach fully and transform, and actively keep complete oxidation to ethanol in the time reaching 6h after transforming fully, have good low temperature active and heat endurance.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 2, Fig. 2 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal end product carbon dioxide in catalytic purification ethanol synthesis process.Carbon dioxide is 100 ℃ of generations in the course of reaction of Ce/OMS-2 oxidation ethanol, selectivity reaches 100% in the time of 160 ℃, and selectivity reach 6h after 100% in the time ethanol be completely oxidized to the end product carbon dioxide, has good low temperature active, heat endurance and end product high selectivity.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 3, Fig. 3 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal intermediate product acetaldehyde in catalytic purification ethanol synthesis process.Acetaldehyde is 60 ℃ of generations in the course of reaction of Ce/OMS-2 oxidation ethanol, selectivity reaches the highest in the time of 120 ℃, selectivity is 30%～60%, the selectivity that is higher than acetaldehyde after 120 ℃ in temperature descends, after being higher than 160 ℃, no longer include acetaldehyde and generate, and after 6h do not have the generation of acetaldehyde in the time.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
A kind of octahedron manganese oxide molecular sieve catalyzer comprises following component:
Pure cryptomelane type manganese dioxide is active component, accounts for 90% of catalyst gross mass, 10% of the ingredients constitute catalyst gross mass of the transition metal Co of doping, and active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
A kind of preparation method of metal oxide-loaded molecular sieve catalyst utilizes the circumfluence method preparation, specifically may further comprise the steps:
One, the liquor potassic permanganate 150mL of configuration 0.30mol/L concentration adds thermal agitation, formation solution in 40 ℃;
Two, the manganese acetate solution 150mL of configuration 0.45mol/L concentration adds thermal agitation, formation solution in 40 ℃;
Three, the solution with gained in the step 1 slowly is added in the 1000mL there-necked flask, and in 80 ℃ of oil bath heating, be 15min heat time heating time, stirs with electric mixer, and mixing speed is 400r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 80 ℃ of stirring reactions 22 hours, mixing speed is 400r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 1 hour, then in baking oven in 105 ℃ of dryings 11 hours; Put into Muffle furnace again in 400 ℃ of roastings 4 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 2.50g;
Five, the 0.67g cabaltous nitrate hexahydrate is joined in the 45mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that cobalt is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 40 ℃ of control water temperatures, the speed of rotation is 100/min; With the solid that obtains in baking oven in 105 ℃ of dryings 11 hours, put into Muffle furnace again in 400 ℃ of roastings 4 hours, obtain the 5wt%Co/OMS-2 catalyst.
The effect of present embodiment is seen accompanying drawing 1～3.(please contrast the effect that accompanying drawing describes present embodiment in detail)
Referring to Fig. 1, Fig. 1 is load C e, Co, and Cu, Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal is the temperature variant result of reactant ethanol conversion in catalytic purification ethanol synthesis process.Being reflected at 60 ℃ and rise living of Co/OMS-2 oxidation ethanol, 160 ℃ reach fully and transform, and actively keep complete oxidation to ethanol in the time reaching 6h after transforming fully, have good low temperature active and heat endurance.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 2, Fig. 2 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal end product carbon dioxide in catalytic purification ethanol synthesis process.Carbon dioxide is 100 ℃ of generations in the course of reaction of Co/OMS-2 oxidation ethanol, selectivity reaches 100% in the time of 160 ℃, and selectivity reach 6h after 100% in the time ethanol be completely oxidized to the end product carbon dioxide, has good low temperature active, heat endurance and end product high selectivity.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 3, Fig. 3 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal intermediate product acetaldehyde in catalytic purification ethanol synthesis process.Acetaldehyde is 60 ℃ of generations in the course of reaction of Co/OMS-2 oxidation ethanol, selectivity reaches the highest in the time of 120 ℃, selectivity is 30%～60%, the selectivity that is higher than acetaldehyde after 120 ℃ in temperature descends, after being higher than 160 ℃, no longer include acetaldehyde and generate, and after 6h do not have the generation of acetaldehyde in the time.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Embodiment 3
A kind of octahedron manganese oxide molecular sieve catalyzer comprises following component:
Pure cryptomelane type manganese dioxide is active component, accounts for 95% of catalyst gross mass, 5% of the ingredients constitute catalyst gross mass of the transition metal Cu of doping, and active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
A kind of preparation method of metal oxide-loaded molecular sieve catalyst utilizes the circumfluence method preparation, specifically may further comprise the steps:
One, the liquor potassic permanganate 300mL of configuration 0.40mol/L concentration adds thermal agitation, formation solution in 60 ℃;
Two, the manganese acetate solution 300mL of configuration 0.55mol/L concentration adds thermal agitation, formation solution in 60 ℃;
Three, the solution with gained in the step 1 slowly is added in the 1000mL there-necked flask, and in 110 ℃ of oil bath heating, be 20min heat time heating time, stirs with electric mixer, and mixing speed is 450r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 110 ℃ of stirring reactions 26 hours, mixing speed is 450r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 2 hours, then in baking oven in 110 ℃ of dryings 12 hours; Put into Muffle furnace again in 500 ℃ of roastings 5 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 3.50g;
Five, the 0.52g Gerhardite is joined in 45mL～50mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that copper is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 60 ℃ of control water temperatures, the speed of rotation is 120/min; With the solid that obtains in baking oven in 110 ℃ of dryings 12 hours, put into Muffle furnace again in 500 ℃ of roastings 5 hours, obtain the 5wt%Cu/OMS-2 catalyst.
The effect of present embodiment is seen accompanying drawing 1～3.(please contrast the effect that accompanying drawing describes present embodiment in detail)
Referring to Fig. 1, Fig. 1 is load C e, Co, and Cu, Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal is the temperature variant result of reactant ethanol conversion in catalytic purification ethanol synthesis process.Being reflected at 60 ℃ and rise living of Cu/OMS-2 oxidation ethanol, 160 ℃ reach fully and transform, and actively keep complete oxidation to ethanol in the time reaching 6h after transforming fully, have good low temperature active and heat endurance.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 2, Fig. 2 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal end product carbon dioxide in catalytic purification ethanol synthesis process.Carbon dioxide is 100 ℃ of generations in the course of reaction of Cu/OMS-2 oxidation ethanol, selectivity reaches 100% in the time of 160 ℃, and selectivity reach 6h after 100% in the time ethanol be completely oxidized to the end product carbon dioxide, has good low temperature active, heat endurance and end product high selectivity.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 3, Fig. 3 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal intermediate product acetaldehyde in catalytic purification ethanol synthesis process.Acetaldehyde is 60 ℃ of generations in the course of reaction of Cu/OMS-2 oxidation ethanol, selectivity reaches the highest in the time of 120 ℃, selectivity is 30%～60%, the selectivity that is higher than acetaldehyde after 120 ℃ in temperature descends, after being higher than 160 ℃, no longer include acetaldehyde and generate, and after 6h do not have the generation of acetaldehyde in the time.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Embodiment 4
A kind of octahedron manganese oxide molecular sieve catalyzer comprises following component:
Pure cryptomelane type manganese dioxide is active component, accounts for 93% of catalyst gross mass, 7% of the ingredients constitute catalyst gross mass of the transition-metal Fe of doping, and active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
A kind of preparation method of metal oxide-loaded molecular sieve catalyst utilizes the circumfluence method preparation, specifically may further comprise the steps:
One, the liquor potassic permanganate 270mL of configuration 0.35mol/L concentration adds thermal agitation, formation solution in 50 ℃;
Two, the manganese acetate solution 280mL of configuration 0.5mol/L concentration adds thermal agitation, formation solution in 55 ℃;
Three, the solution with gained in the step 1 slowly is added in the 1000mL there-necked flask, and in 96 ℃ of oil bath heating, be 16min heat time heating time, stirs with electric mixer, and mixing speed is 410r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 95 ℃ of stirring reactions 24 hours, mixing speed is 410r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 1.5 hours, then in baking oven in 104 ℃ of dryings 10 hours; Put into Muffle furnace again in 450 ℃ of roastings 4.5 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 3.45g;
Five, 0.98g nine nitric hydrate iron are joined in the 47mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that iron is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 50 ℃ of control water temperatures, the speed of rotation is 110/min; The solid that obtains was spent the night in 107 ℃ of dryings in baking oven in 10 hours, put into Muffle furnace again, obtain the 5wt%Fe/OMS-2 catalyst in 450 ℃ of roastings 4.5 hours.
The effect of present embodiment is seen accompanying drawing 1～3.(please contrast the effect that accompanying drawing describes present embodiment in detail)
Referring to Fig. 1, Fig. 1 is load C e, Co, and Cu, Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal is the temperature variant result of reactant ethanol conversion in catalytic purification ethanol synthesis process.Being reflected at 60 ℃ and rise living of Fe/OMS-2 oxidation ethanol, 160 ℃ reach fully and transform, and actively keep complete oxidation to ethanol in the time reaching 6h after transforming fully, have good low temperature active and heat endurance.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 2, Fig. 2 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal end product carbon dioxide in catalytic purification ethanol synthesis process.Carbon dioxide is 100 ℃ of generations in the course of reaction of Fe/OMS-2 oxidation ethanol, selectivity reaches 100% in the time of 160 ℃, and selectivity reach 6h after 100% in the time ethanol be completely oxidized to the end product carbon dioxide, has good low temperature active, heat endurance and end product high selectivity.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 3, Fig. 3 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal intermediate product acetaldehyde in catalytic purification ethanol synthesis process.Acetaldehyde is 60 ℃ of generations in the course of reaction of Fe/OMS-2 oxidation ethanol, selectivity reaches the highest in the time of 120 ℃, selectivity is 30%～60%, the selectivity that is higher than acetaldehyde after 120 ℃ in temperature descends, after being higher than 160 ℃, no longer include acetaldehyde and generate, and after 6h do not have the generation of acetaldehyde in the time.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (0
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Embodiment 5
A kind of metal oxide-loaded molecular sieve catalyst comprises following component:
Pure cryptomelane type manganese dioxide is active component, accounts for 91% of catalyst gross mass, 9% of the ingredients constitute catalyst gross mass of the transition metal yttrium of doping, and active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
A kind of preparation method of metal oxide-loaded molecular sieve catalyst utilizes the circumfluence method preparation, specifically may further comprise the steps:
One, the liquor potassic permanganate 200mL of configuration 0.33mol/L concentration adds thermal agitation, formation solution in 42 ℃;
Two, the manganese acetate solution 210mL of configuration 0.48mol/L concentration adds thermal agitation, formation solution in 44 ℃;
Three, the solution with gained in the step 1 slowly is added in the 1000mL there-necked flask, and in 85 ℃ of oil bath heating, be 14min heat time heating time, stirs with electric mixer, and mixing speed is 390r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 88 ℃ of stirring reactions 23 hours, mixing speed is 390r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 1.4 hours, then in baking oven in 106 ℃ of dryings 12 hours; Put into Muffle furnace again in 404 ℃ of roastings 4.2 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 2.7g;
Five, the 0.42g yttrium nitrate is joined in the 46mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that yttrium is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 43 ℃ of control water temperatures, the speed of rotation is 108/min; The solid that obtains was spent the night in 106 ℃ of dryings in baking oven in 12 hours, put into Muffle furnace again, obtain the 5wt%Y/OMS-2 catalyst in 410 ℃ of roastings 4.6 hours.
The effect of present embodiment is seen accompanying drawing 1～3.(please contrast the effect that accompanying drawing describes present embodiment in detail)
Referring to Fig. 1, Fig. 1 is load C e, Co, and Cu, Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal is the temperature variant result of reactant ethanol conversion in catalytic purification ethanol synthesis process.Being reflected at 60 ℃ and rise living of Y/OMS-2 oxidation ethanol, 160 ℃ reach fully and transform, and actively keep complete oxidation to ethanol in the time reaching 6h after transforming fully, have good low temperature active and heat endurance.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 2, Fig. 2 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal end product carbon dioxide in catalytic purification ethanol synthesis process.Carbon dioxide is 100 ℃ of generations in the course of reaction of Y/OMS-2 oxidation ethanol, selectivity reaches 100% in the time of 160 ℃, and selectivity reach 6h after 100% in the time ethanol be completely oxidized to the end product carbon dioxide, has good low temperature active, heat endurance and end product high selectivity.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 3, Fig. 3 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal intermediate product acetaldehyde in catalytic purification ethanol synthesis process.Acetaldehyde is 60 ℃ of generations in the course of reaction of Y/OMS-2 oxidation ethanol, selectivity reaches the highest in the time of 120 ℃, selectivity is 30%～60%, the selectivity that is higher than acetaldehyde after 120 ℃ in temperature descends, after being higher than 160 ℃, no longer include acetaldehyde and generate, and after 6h do not have the generation of acetaldehyde in the time.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
The catalyst that the foregoing description 1～5 is obtained carries out performance test.The catalyst performance test is carried out in the quartz glass fixed bed reactors of diameter 8mm.The granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1, gas component is carried out on-line analysis by Gasmet DX4000.Test result sees Table 1, accompanying drawing 1, accompanying drawing 2 and accompanying drawing 3.
Table 1 catalyst ethanol of the present invention/acetaldehyde catalytic activity data
| The catalyst numbering | ??T10/℃ | ??T100/℃ |
| ??5wt％Ce/OMS-2 | ??60/80 | ??160/160 |
| ??5wt％Co/OMS-2 | ??60/80 | ??160/160 |
| ??5wt％Cu/OMS-2 | ??60/80 | ??160/160 |
| ??5wt％Fe/OMS-2 | ??60/80 | ??160/160 |
| ??5wt％Y/OMS-2 | ??80/100 | ??180/180 |
Testing result analysis from table 1 draws: in the above-mentioned example of the present invention, to add different types of transition metal Co, Cu, Fe, Ce, Y are change condition, the temperature of its ethanol oxidation of acetaldehyde is 60～160 ℃, and outstanding to ethanol acetaldehyde catalytic oxidation ability, low temperature active is good.In addition, this catalyst series also has hydrothermal stability preferably, so this catalyst series possesses popularizing application prospect.
Referring to Fig. 1, Fig. 1 is load C e, Co, and Cu, Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal is the temperature variant result of reactant ethanol conversion in catalytic purification ethanol synthesis process.Oxidation of ethanol is reflected at 60 ℃ and rise lives, and 160 ℃ reach fully and transform, and actively keeps complete oxidation to ethanol in the time reaching 6h after transforming fully, has good low temperature active and heat endurance.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 2, Fig. 2 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal end product carbon dioxide in catalytic purification ethanol synthesis process.Carbon dioxide is 100 ℃ of generations in the oxidation of ethanol course of reaction, selectivity reaches 100% in the time of 160 ℃, and selectivity reach 6h after 100% in the time ethanol be completely oxidized to the end product carbon dioxide, have good low temperature active, heat endurance and end product high selectivity.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Referring to Fig. 3, Fig. 3 is load C e, Co, Cu, the temperature variant result of selectivity of Fe, the octahedron manganese oxide molecular sieve catalyzer of Y metal intermediate product acetaldehyde in catalytic purification ethanol synthesis process.Acetaldehyde is 60 ℃ of generations in the oxidation of ethanol course of reaction, selectivity reaches the highest in the time of 120 ℃, and selectivity is 30%～60%, and the selectivity that is higher than acetaldehyde after 120 ℃ in temperature descends, after being higher than 160 ℃, no longer include acetaldehyde and generate, and after 6h do not have the generation of acetaldehyde in the time.Reaction condition is: the granularity of catalyst is 40～60 orders, and useful load is 0.2000g, and the reaction gas of test consists of 300ppm ethanol (C
2H
5OH), 10Vol% oxygen (O
2), balanced gas is nitrogen (N
2), reaction velocity is 36000h
-1
Claims (10)
1. metal oxide-loaded molecular sieve catalyst, it is characterized in that, comprise following component: pure cryptomelane type manganese dioxide is active component, account for 90%～95% of catalyst gross mass, containing transition metal Ce, Co, Cu, Fe or Y, the transition metal component of mixing accounts for 5%～10% of catalyst gross mass, and active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
2. a kind of metal oxide-loaded molecular sieve catalyst according to claim 1, it is characterized in that, comprise following component: pure cryptomelane type manganese dioxide is active component, account for 94% of catalyst gross mass, 6% of the ingredients constitute catalyst gross mass of the transition metal Ce that mixes, active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
3. a kind of octahedron manganese oxide molecular sieve catalyzer according to claim 1, it is characterized in that, comprise following component: pure cryptomelane type manganese dioxide is active component, account for 90% of catalyst gross mass, 10% of the ingredients constitute catalyst gross mass of the transition metal Co that mixes, active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
4. a kind of octahedron manganese oxide molecular sieve catalyzer according to claim 1, it is characterized in that, comprise following component: pure cryptomelane type manganese dioxide is active component, account for 95% of catalyst gross mass, 5% of the ingredients constitute catalyst gross mass of the transition metal Cu that mixes, active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
5. a kind of octahedron manganese oxide molecular sieve catalyzer according to claim 1, it is characterized in that, comprise following component: pure cryptomelane type manganese dioxide is active component, accounts for 93% of catalyst gross mass, 7% of the ingredients constitute catalyst gross mass of the transition-metal Fe of doping.Active component is passed through Mn
7+And Mn
2+Reaction generates, and both mol ratios are 0.72.
6. the preparation method of a metal oxide-loaded molecular sieve catalyst utilizes the circumfluence method preparation, it is characterized in that, may further comprise the steps:
One, the liquor potassic permanganate 150mL～300mL of configuration 0.30mol/L～0.40mol/L concentration adds thermal agitation, formation solution in 40～60 ℃;
Two, the manganese acetate solution 150mL～300mL of configuration 0.45mol/L～0.55mol/L concentration adds thermal agitation, formation solution in 40～60 ℃;
Three, the solution with gained in the step 1 slowly is added in the 1000mL there-necked flask, and in 80～110 ℃ of oil bath heating, be 10～20min heat time heating time, stirs with electric mixer, and mixing speed is 350～450r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 80～110 ℃ of stirring reactions 22～26 hours, mixing speed is 350～450r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 1～2 hour, then in baking oven in 105～110 ℃ of dryings 10～12 hours; Put into Muffle furnace again in 400～500 ℃ of roastings 4～5 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 2.50g～3.50g;
Five, 0.52g～0.54g ammonium ceric nitrate, 0.66g～0.68g cabaltous nitrate hexahydrate, 0.50g～0.52g Gerhardite, 0.97g～0.99g nine nitric hydrate iron or 0.41～0.43g yttrium nitrate are joined in 45mL～50mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that cerium is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 40～60 ℃ of control water temperatures, the speed of rotation is 100～120/min; The solid that obtains was spent the night in 105～110 ℃ of dryings in baking oven in 10～12 hours, put into Muffle furnace again, obtain 5wt%M/OMS-2 (M=Ce, Co, Cu, Fe, Y) catalyst in 400～500 ℃ of roastings 4～5 hours.
7. the preparation method of a kind of metal oxide-loaded molecular sieve catalyst according to claim 6 utilizes the circumfluence method preparation, specifically may further comprise the steps:
One, the liquor potassic permanganate 280mL of configuration 0.38mol/L concentration adds thermal agitation, formation solution in 56 ℃;
Two, the manganese acetate solution 288mL of configuration 0.54mol/L concentration adds thermal agitation, formation solution in 58 ℃;
Three, the solution with gained in the step 1 slowly is added in the 1000mL there-necked flask, and in 108 ℃ of oil bath heating, be 10min heat time heating time, stirs with electric mixer, and mixing speed is 350r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 106 ℃ of stirring reactions 25 hours, mixing speed is 350r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 1.8 hours, then in baking oven in 109 ℃ of dryings 10 hours; Put into Muffle furnace again in 490 ℃ of roastings 4.6 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 3.45g;
Five, the 0.54g ammonium ceric nitrate is joined in the 49mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that cerium is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 58 ℃ of control water temperatures, the speed of rotation is 117/min.With the solid that obtains in baking oven in 109 ℃ of dryings 10 hours, put into Muffle furnace again in 490 ℃ of roastings 4.9 hours, obtain the 5wt%Ce/OMS-2 catalyst.
8. the preparation method of a kind of metal oxide-loaded molecular sieve catalyst according to claim 6 utilizes the circumfluence method preparation, it is characterized in that, may further comprise the steps:
One, the liquor potassic permanganate 150mL of configuration 0.30mol/L concentration adds thermal agitation, formation solution in 40 ℃;
Two, the manganese acetate solution 150mL of configuration 0.45mol/L concentration adds thermal agitation, formation solution in 40 ℃;
Three, the solution with gained in the step 1 slowly is added in the 1000mL there-necked flask, and in 80 ℃ of oil bath heating, be 15min heat time heating time, stirs with electric mixer, and mixing speed is 400r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 80 ℃ of stirring reactions 22 hours, mixing speed is 400r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 1 hour, then in baking oven in 105 ℃ of dryings 11 hours; Put into Muffle furnace again in 400 ℃ of roastings 4 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 2.50g;
Five, the 0.67g cabaltous nitrate hexahydrate is joined in the 45mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that cobalt is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 40 ℃ of control water temperatures, the speed of rotation is 100/min; The solid that obtains was spent the night in 105 ℃ of dryings in baking oven in 11 hours, put into Muffle furnace again, obtain the 5wt%Co/OMS-2 catalyst in 400 ℃ of roastings 4 hours.
9. the preparation method of a kind of metal oxide-loaded molecular sieve catalyst according to claim 6 utilizes the circumfluence method preparation, it is characterized in that, may further comprise the steps:
One, the liquor potassic permanganate 300mL of configuration 0.40mol/L concentration adds thermal agitation, formation solution in 60 ℃;
Two, the manganese acetate solution 300mL of configuration 0.55mol/L concentration adds thermal agitation, formation solution in 60 ℃;
Three, the solution with gained in the step 1 slowly is added in the 1000mL there-necked flask, and in 110 ℃ of oil bath heating, be 20min heat time heating time, stirs with electric mixer, and mixing speed is 450r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 110 ℃ of stirring reactions 26 hours, mixing speed is 450r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 2 hours, then in baking oven in 110 ℃ of dryings 12 hours; Put into Muffle furnace again in 500 ℃ of roastings 5 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 3.50g;
Five, the 0.52g Gerhardite is joined in 45mL～50mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that copper is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 60 ℃ of control water temperatures, the speed of rotation is 120/min; The solid that obtains was spent the night in 110 ℃ of dryings in baking oven in 12 hours, put into Muffle furnace again, obtain the 5wt%Cu/OMS-2 catalyst in 500 ℃ of roastings 5 hours.
10. the preparation method of a kind of metal oxide-loaded molecular sieve catalyst according to claim 6 utilizes the circumfluence method preparation, it is characterized in that, may further comprise the steps:
One, the liquor potassic permanganate 270mL of configuration 0.35mol/L concentration adds thermal agitation, formation solution in 50 ℃;
Two, the manganese acetate solution 280mL of configuration 0.5mol/L concentration adds thermal agitation, formation solution in 55 ℃;
Three, the solution with gained in the step 1 slowly is added in the 1000mL there-necked flask, and in 96 ℃ of oil bath heating, be 16min heat time heating time, stirs with electric mixer, and mixing speed is 410r/min, and uses the running water condensing reflux;
Four, the solution with gained in the step 2 slowly is added in the flask of step 3, in 95 ℃ of stirring reactions 24 hours, mixing speed is 410r/min, and use the tap water condensing reflux, obtain black pulpous state precipitation, black pulpous state precipitate with deionized water suction filtration 1.5 hours, then in baking oven in 104 ℃ of dryings 10 hours; Put into Muffle furnace again in 450 ℃ of roastings 4.5 hours, obtain octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid; The solid that obtains is measured 3.45g;
Five, 0.98g nine nitric hydrate iron are joined in the 47mL deionized water, stir and form solution;
Six, the solid and the solution in the step 5 of measuring in the step 4 is mixed, utilize Rotary Evaporators that iron is immersed on octahedron manganese oxide molecular sieve catalyzer (OMS-2) solid, 50 ℃ of control water temperatures, the speed of rotation is 110/min; With the solid that obtains in baking oven in 107 ℃ of dryings 10 hours, put into Muffle furnace again in 450 ℃ of roastings 4.5 hours, obtain the 5wt%Fe/OMS-2 catalyst.
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