CN101703919A - Load type manganese and copper series deoxidizer and preparation method and application thereof - Google Patents
Load type manganese and copper series deoxidizer and preparation method and application thereof Download PDFInfo
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- CN101703919A CN101703919A CN200910237867A CN200910237867A CN101703919A CN 101703919 A CN101703919 A CN 101703919A CN 200910237867 A CN200910237867 A CN 200910237867A CN 200910237867 A CN200910237867 A CN 200910237867A CN 101703919 A CN101703919 A CN 101703919A
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Abstract
The invention discloses a preparation method and application of a load type manganese and copper series deoxidizer. The load type manganese and copper series deoxidizer comprises a carrier and an active compound oxide, wherein the carrier is alumina and X-type or Y-type molecular sieves; the active compound oxide comprises a copper oxide, a manganese oxide and a metal assistant oxide; the spherical alumina carrier can be directly soaked with a mixed solution of an active component to obtain the strip-shaped deoxidizer; and the powder of the X-type or Y-type molecular sieve needs to carry out ion exchange firstly and then is kneaded with the mixed solution of the active component and a binding agent, extruded into strips and roasted to obtain the formed strip-shaped deoxidizer. The formed strip-shaped deoxidizer needs to be reduced and activated at certain temperature when in use, can not only remove the tiny oxygen contained in inert atmosphere, but also continuously remove the tiny oxygen contained in higher-concentration to high-purity carbonic oxide, and has high mechanical strength, difficult pulverization in the using process and difficult temperature runaway of pretreatment reduction.
Description
Technical field
The present invention relates to a kind of deoxidier, particularly a kind of carried copper manganese deoxidier and preparation method thereof and application.
Background technology
In fields such as material, electronics, chemical industry, the existence of micro amount of oxygen is harmful to often.In order to eliminate these oxygen, people have invented a series of such as copper system, silver system, palladium system, nickel system, manganese system and molybdenum deoxidier.The transformation absorption purifying carbon oxide technology that nineteen nineties is grown up around cupric carbon monoxide selective adsorbent by Beijing Peking University Pioneer Technology Co., Ltd. promptly is subjected to the harm of micro amount of oxygen deeply, because the core that micro amount of oxygen makes transformation absorption---and the performance of carbon monoxide selective adsorbent becomes unstable.But above-mentioned deoxidier is the deoxidizing agent of molybdenum oxide except the disclosed molybdenum of Chinese patent CN1302686A, and other all can not play a role under the higher concentration carbon monoxide atmosphere effectively, and the molybdenum deoxidier is expensive, is 1/2～1/3 of precious metal palladium deoxidier.
The lower valency oxide of known copper and manganese all has deoxidizing capacity, and wherein copper is that the deoxidation degree of depth reaches 10ppm, but can only use in inert atmosphere, so its deoxidizing capacity will reach capacity behind the certain hour.Manganese is that the deoxidation degree of depth can reach 0.1ppm, but very unstable, is that a large amount of heat releases were lost efficacy in case expose air.As far back as World War I period, the two high valence state composite oxides just are used for breathing mask to remove the CO of super safe limit in the air, promptly famous Hopcalite catalyst.These composite oxides are reduced into lower valency use the purpose that can reach eliminating minute oxygen in the high concentration CO.But the deoxidier that obtains like this is the same with manganese deoxidier unstable, also has in addition such as forming machine intensity difference in enormous quantities, preliminary treatment to reduce in easy temperature runaway, the use the easily problem of efflorescence.These all make Cu-Mn complex oxide be restricted in industrial application as deoxidier.
Summary of the invention
The purpose of this invention is to provide a kind of carried copper manganese system complex oxide deoxidier and preparation method thereof and application.
Carried copper manganese system complex oxide deoxidier provided by the invention comprises carrier and active composite oxides;
Described carrier is selected from least a in aluminium oxide, X type molecular sieve and the Y zeolite;
Described active composite oxides are made up of Cu oxide, Mn oxide and metal promoter oxide, and its general structure is suc as formula shown in the I:
MnO
2·(CuO)x·(AOa)y
(formula I)
Among the formula I, x=0.3～1.0, x specifically can be 0.4-0.9,0.42-0.85,0.45-0.85,0.48-0.85,0.4-0.85,0.5-0.9,0.5-0.8,0.42-0.48 or 0.55-0.75, preferred x=0.4-0.9; Y=0.02～0.15, y specifically can be 0.04-0.15,0.08-0.15,0.10-0.15,0.12-0.15,0.08-0.12 or 0.08-0.10, preferred y=0.04-0.10; A=1.0～3.0, a specifically can be 1.2-3,1.5-3,1.5-2.8,1-2.8,1.5-2.8 or 1.0-1.5, preferred a=1.2-2.8; The molecular formula of described metal promoter oxide is AOa, and A is selected from least a in metallic elements of ferrum, cobalt and the molybdenum.
In this deoxidier, the preferred 13X molecular sieve of described X type molecular sieve, the preferred NaY molecular sieve of described Y zeolite; The aluminium oxide of various specific areas all is applicable to this method, is 150～250m as specific area
2The aluminium oxide of/g. above-mentioned described carried copper manganese system complex oxide deoxidier can only be made up of described carrier and described active composite oxides; Wherein, described carrier accounts for 60～80%, preferred 70～75% of described carried copper manganese system complex oxide deoxidier gross mass; Described active composite oxides account for 20～40%, preferred 25～30% of described carried copper manganese system complex oxide deoxidier gross mass; In the described active composite oxides, described metal promoter oxide accounts for 3～10% of described active composite oxides gross mass, and preferred 5～8%.
The method of the carried copper manganese system complex oxide deoxidier when the above-mentioned carrier of preparation provided by the invention is described aluminium oxide comprises the steps:
The solution of the solution of the solution of Cu oxide precursor, Mn oxide precursor, metal promoter oxide precursor mixed with described carrier flood, dipping is dried after finishing successively, roasting, after the reduction, obtaining described carrier is the described carried copper manganese system complex oxide deoxidier of aluminium oxide in reducing atmosphere.
In this method, described Cu oxide precursor is copper nitrate and/or Schweinfurt green, and the precursor of described Mn oxide is manganese nitrate and/or manganese acetate; Described metal promoter oxide precursor is selected from least a in ferric nitrate, cobalt nitrate and the ammonium molybdate; The ratio of the cumulative volume of the solution of the solution of the solution of described Cu oxide precursor, Mn oxide precursor and metal promoter oxide precursor and described carrier dry weight is 0.8～1.2mL: 1g, specifically can be 0.8-1.0mL: 1g, 0.8-1.1mL: 1g or 0.9-1.1mL: 1g.
Described dip time is 12～24 hours, preferred 16 hours; Dipping temperature is 25～80 ℃, preferred 60 ℃; Described bake out temperature is 100～120 ℃, preferred 120 ℃; Drying time is 10～24 hours, preferred 12 hours; Described sintering temperature is 500～600 ℃, preferred 550 ℃; Roasting time is 5～12 hours, preferred 10 hours; Described reducing atmosphere is the gaseous mixture of nitrogen and hydrogen or carbon monoxide, and the volume ratio of hydrogen or carbon monoxide and nitrogen is 2～50: 100; The air speed of described reducing gases is 100～1000h
-1, preferred 500h
-1Described reduction temperature is 150～220 ℃, and preferred 200 ℃, the described recovery time is 12～24 hours, preferred 24 hours.
The described carrier of preparation provided by the invention is the method for the described carried copper manganese system complex oxide deoxidier of X type molecular sieve and/or Y zeolite, comprises the steps:
1) described X type molecular sieve and/or described Y zeolite are carried out ion-exchange;
2) solution of Cu oxide precursor, the solution of Mn oxide precursor and the solution mixing of metal promoter oxide precursor are obtained maceration extract, mix in the described X type molecular sieve that described step 1) ion-exchange is finished and/or described Y zeolite and adhesive and the described maceration extract and pinch dipping, extrusion, oven dry, roasting then, after the reduction, obtaining described carrier is the described carried copper manganese system complex oxide deoxidier of X type molecular sieve and/or Y zeolite in reducing atmosphere.
In the step 1) of this method, the used ion exchange liquid of described ion-exchange step is copper nitrate or manganese nitrate aqueous solution; The number of times of described ion-exchange is at least once, preferred 1 time, 2 times or 3 times; This step is carried out according to conventional method, and the amount ratio of the temperature of ion-exchange, the concentration of ion exchange liquid and molecular sieve and ion exchange liquid is all implemented according to conventional method, and the concentration of preferred ion exchange liquid is 1mol/L.Described step 2) in, described Cu oxide precursor is copper nitrate and/or Schweinfurt green, and the precursor of described Mn oxide is manganese nitrate and/or manganese acetate; Described metal promoter oxide precursor is selected from least a in ferric nitrate, cobalt nitrate and the ammonium molybdate; Described adhesive is attapulgite or boehmite.
Described X type molecular sieve that the mixed solution of described Cu oxide precursor, described Mn oxide precursor and described auxiliary agent oxide precursor, described step 1) ion-exchange finish and/or described Y zeolite are 0.8～1.2mL: 1g: 0.1～0.14g with the volume mass ratio of described adhesive, specifically can be 0.8-1.1mL: 1g: 0.1-0.14g, 0.9-1.1mL: 1g: 0.1-0.13g or 0.8-1.15mL: 1g: 0.1-0.135g, preferred 1mL: 1g: the temperature of 0.12g. baking step is 100～120 ℃, preferred 120 ℃; The time of baking step is 10～24 hours, preferred 12 hours; The temperature of calcination steps is 500～600 ℃, preferred 550 ℃; The time of calcination steps is 5-12 hour, preferred 10 hours; Described reducing atmosphere is the gaseous mixture of nitrogen and hydrogen or carbon monoxide, and the volume ratio of hydrogen or carbon monoxide and nitrogen is 2～50: 100; The air speed of described reducing gases is 100～1000h
-1, specifically can be 100-900h
-1, 100-850h
-1, 100-900h
-1, 200-950h
-1, 400-950h
-1Or 500-900h
-1, preferred 500h
-1The temperature of reduction step is 150～220 ℃, and preferred 200 ℃, the reduction step time is 12～24 hours, preferred 24 hours.
In addition, the application of carried copper manganese system complex oxide deoxidier provided by the invention in method of deoxidation also belongs to protection scope of the present invention.
Carried copper manganese system complex oxide deoxidier provided by the invention at different bearer types, provides different preparation methods, wherein, when selecting the bar shaped alumina support for use, can be directly and the mixed solution of active component dipping can obtain strip-shaped deoxidizer; And when selecting X type or Y zeolite powder for use, then need to carry out earlier ion-exchange as carrier, knead with the mixed solution and the adhesive of active component again, obtain the moulding strip-shaped deoxidizer after extrusion and the roasting.The moulding deoxidier also needs reduction activation at a certain temperature in use.Deoxidier provided by the invention changes Cu-Mn complex oxide into load mutually from body, and add other metal oxides as auxiliary agent, this deoxidier has not only kept the deoxy performance of Cu-Mn complex oxide, overcome the shortcoming in original method simultaneously, have the advantages that to be difficult for temperature runaway when being difficult for efflorescence, preliminary treatment reduction in mechanical strength height, the use, be a kind of low cost, high efficiency, be applicable to that commercial Application removes the deoxidier of micro amount of oxygen in the high concentration CO.Copper manganese deoxidier provided by the invention can be used for removing of micro amount of oxygen in general nitrogen, general hydrogen, rare gas, synthesis gas or the high concentration CO after purifying.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment 1,
With 50g 50% (mass percentage concentration) Mn (NO
3)
2Solution, 16gCu (NO
3)
23H
2O and the mixing of 3.0g cobalt nitrate are dissolved in the 50ml water, obtain the mixed solution that cumulative volume is 100mL.It is 150～250m that this mixed solution is dropwise joined the 100g specific area
2The commercially available bar shaped Al of/g
2O
3In the carrier, rocking simultaneously vibrates to make mixes.Behind 60 ℃ of dipping 16h, dry 10h at 120 ℃; 550 ℃ of roasting 10h in Muffle furnace.The feeding volume ratio is 100: 2 nitrogen and a hydrogen during use, slowly is warming up to 200 ℃, at air speed 500h
-1Condition under reductase 12 be cooled to room temperature after 4 hours, obtain carried copper manganese system complex oxide deoxidier provided by the invention, wherein the structural formula of active composite oxides is MnO
2(CuO)
0.48(CoO)
0.12
Utilize above-mentioned deoxidier that general hydrogen (volumn concentration is that 99.5% hydrogen and volumn concentration are the mist that 0.5% oxygen is formed) is carried out deoxidation, at 1atm, room temperature, 1000～10000h
-1Condition under, can be with the oxygen removal in the general hydrogen to 0.1ppm, the deoxidation capacity reaches 60mlO
2/ g.
Embodiment 2,
With former powder of the commercially available 13X of 100g (dry weight) and 1L 1mol/L Mn (NO
3)
2Solution filters, washs, dries 100 ℃ of exchange twice.With 60g 50% (mass percentage concentration) Mn (NO
3)
2Solution, 16gCu (NO
3)
23H
2O and the mixing of 5.0g ammonium molybdate are dissolved in the 100ml water, obtain the mixed solution that cumulative volume is 160mL.With the former powder of 13X of 150g manganese exchange, 20g attapulgite knead repeatedly 2h, extrusion then of mixed solution therewith.Squeeze good bar at 120 ℃ of oven dry 12h; 550 ℃ of roasting 10h in Muffle furnace.The feeding volume ratio is 100: 5 nitrogen and a hydrogen during use, slowly is warming up to 180 ℃, at air speed 500h
-1Condition under reductase 12 be cooled to room temperature after 4 hours, obtain carried copper manganese system complex oxide deoxidier provided by the invention, wherein the structural formula of active composite oxides is MnO
2(CuO)
0.42(MoO
3)
0.08
(volumn concentration is respectively 70% H to this deoxidier to synthesis gas
2, 29.5% CO, 0.5% O
2The mist of forming) carries out deoxidation, at 5atm, room temperature, 3000～5000h
-1Condition under, can be with the oxygen removal in the synthesis gas to 1ppm, and deoxygenation can need not regeneration continuously.
Embodiment 3,
With former powder of the commercially available NaY of 100g (dry weight) and 1L 1mol/L Cu (NO
3)
2Solution filters, washs, dries 25 ℃ of exchange twice.With 55g 50% (mass percentage concentration) Mn (NO
3)
2Solution, 16gCu (NO
3)
23H
2O and the mixing of 3.0g ferric nitrate are dissolved in the 80ml water, obtain the mixed solution that cumulative volume is 140mL.With the former powder of NaY of 120g copper exchange, 15g boehmite knead repeatedly 2h, extrusion then of mixed solution therewith.Squeeze good bar at 120 ℃ of oven dry 12h; 550 ℃ of roasting 12h in Muffle furnace.The feeding volume ratio is 100: 20 nitrogen and a hydrogen during use, slowly is warming up to 150 ℃, is 500h in air speed
-1Condition under reductase 12 be cooled to room temperature after 4 hours, obtain carried copper manganese system complex oxide deoxidier provided by the invention, wherein the structural formula of active composite oxides is MnO
2(CuO)
0.45(FeO
1.5)
0.1
(volumn concentration is respectively 99.5% CO and 0.5% O to this deoxidier to high concentration CO
2The mist of forming) carries out deoxidation, at 5atm, 70 ℃, 3000～9000h
-1Condition under, can be with oxygen removal to 1 wherein～10ppm, and deoxygenation can need not regeneration continuously.
After tested, the average mechanical intensity of embodiment 1～embodiment 3 resulting bar shaped deoxidiers before reduction, after the reduction is respectively 15.8Kg/cm, 10.0Kg/cm, far above before non-loading type Cu-Mn complex oxide deoxidier (wherein the content of Cu, Mn oxide and support type the is identical) reduction and 11.7Kg/cm, 4.7Kg/cm after reducing.Temperature rise ratio non-loading type in the bar shaped deoxidier reduction process that embodiment 1～embodiment 3 obtains also much lower: the former is 2 ℃ for 1g deoxidier reduction temperature rise, and the latter then reaches 10 ℃.In addition, with the reduction after catalyst exposure in air, support type deoxidier heat release gentleness provided by the invention, hand is touched no burning heat sensation; The non-loading type deoxidier is very exothermic then, paper can be ignited.
Claims (10)
1. a carried copper manganese system complex oxide deoxidier comprises carrier and active composite oxides;
Described carrier is selected from least a in aluminium oxide, X type molecular sieve and the Y zeolite;
Described active composite oxides are made up of Cu oxide, Mn oxide and metal promoter oxide, and its general structure is suc as formula shown in the I:
MnO
2·(CuO)x·(AOa)y
(formula I)
Among the formula I, x=0.3～1.0; Y=0.02～0.15, a=1.0～3.0; The molecular formula of described auxiliary agent oxide is AOa, and A is selected from least a in metallic elements of ferrum, cobalt and the molybdenum.
2. deoxidier according to claim 1 is characterized in that: described carried copper manganese system complex oxide deoxidier is made up of described carrier and described active composite oxides.
3. deoxidier according to claim 1 and 2 is characterized in that: among the described formula I, and x=0.4-0.9, y=0.04-0.10, a=1.2-2.8;
Described carrier accounts for 60～80%, preferred 70～75% of described carried copper manganese system complex oxide deoxidier gross mass; Described active composite oxides account for 20～40%, preferred 25～30% of described carried copper manganese system complex oxide deoxidier gross mass; In the described active composite oxides, described metal promoter oxide accounts for 3～10% of described active composite oxides gross mass, and preferred 5～8%.
4. the method for the carried copper manganese system complex oxide deoxidier when one kind to prepare the arbitrary described carrier of claim 1～3 be described aluminium oxide comprises the steps:
The solution of the solution of the solution of Cu oxide precursor, Mn oxide precursor, metal promoter oxide precursor mixed with described carrier flood, dipping is dried after finishing successively, roasting, after the reduction, obtaining described carrier is the described carried copper manganese system complex oxide deoxidier of aluminium oxide in reducing atmosphere.
5. method according to claim 4 is characterized in that: described Cu oxide precursor is copper nitrate and/or Schweinfurt green, and the precursor of described Mn oxide is manganese nitrate and/or manganese acetate; Described metal promoter oxide precursor is selected from least a in ferric nitrate, ferric acetate, cobalt nitrate, cobalt acetate and the ammonium molybdate;
The ratio of the cumulative volume of the solution of the solution of the solution of described Cu oxide precursor, Mn oxide precursor and metal promoter oxide precursor and described carrier dry weight is 0.8～1.2mL: 1g.
6. according to claim 4 or 5 described methods, it is characterized in that: described dip time is 12～24 hours, preferred 16 hours; Dipping temperature is 25～80 ℃, preferred 60 ℃; Described bake out temperature is 100～120 ℃, preferred 120 ℃; Drying time is 10～24 hours, preferred 12 hours; Described sintering temperature is 500～600 ℃, preferred 550 ℃; Roasting time is 5-12 hour, preferred 10 hours; Described reducing atmosphere is the gaseous mixture of nitrogen and hydrogen or carbon monoxide, and the volume ratio of hydrogen or carbon monoxide and nitrogen is 2～50: 100; The air speed of described reducing gases is 100～1000h
-1, preferred 500h
-1Described reduction temperature is 150～220 ℃, and preferred 200 ℃, the described recovery time is 12～24 hours, preferred 24 hours.
7. one kind prepares that arbitrary described carrier is the method for the described carried copper manganese system complex oxide deoxidier of X type molecular sieve and/or Y zeolite among the claim 1-3, comprises the steps:
1) described X type molecular sieve and/or described Y zeolite are carried out ion-exchange;
2) solution of Cu oxide precursor, the solution of Mn oxide precursor and the solution mixing of metal promoter oxide precursor are obtained maceration extract, mix in the described X type molecular sieve that described step 1) ion-exchange is finished and/or described Y zeolite and adhesive and the described maceration extract and pinch dipping, extrusion, oven dry, roasting then, after the reduction, obtaining described carrier is the described carried copper manganese system complex oxide deoxidier of X type molecular sieve and/or Y zeolite in reducing atmosphere.
8. method according to claim 7 is characterized in that: in the described step 1), the used ion exchange liquid of described ion-exchange step is the aqueous solution of copper nitrate or manganese nitrate; The number of times of described ion-exchange is at least once, preferred 1 time, 2 times or 3 times;
Described step 2) in, described Cu oxide precursor is copper nitrate and/or Schweinfurt green, and the precursor of described Mn oxide is manganese nitrate and/or manganese acetate; Described metal promoter oxide precursor is selected from least a in ferric nitrate, cobalt nitrate and the ammonium molybdate; Described adhesive is attapulgite or boehmite;
Described X type molecular sieve that the mixed solution of the solution of described Cu oxide precursor, described Mn oxide precursor and described metal promoter oxide precursor, described step 1) ion-exchange finish and/or described Y zeolite are 0.8～1.2mL: 1g: 0.1～0.14g with the volume mass ratio of described adhesive, preferred 1mL: 1g: 0.12g.
9. according to claim 7 or 8 described methods, it is characterized in that: described step 2), the temperature of baking step is 100～120 ℃, preferred 120 ℃; The time of baking step is 10～24 hours, preferred 12 hours; The temperature of calcination steps is 500～600 ℃, preferred 550 ℃; The time of calcination steps is 5-12 hour, preferred 10 hours; Described reducing atmosphere is the gaseous mixture of nitrogen and hydrogen or carbon monoxide, and the volume ratio of hydrogen or carbon monoxide and nitrogen is 2～50: 100; The air speed of described reducing gases is 100～1000h
-1, preferred 500h
-1The temperature of reduction step is 150～220 ℃, and preferred 200 ℃, the time of reduction step is 12～24 hours, preferred 24 hours.
10. the application of the arbitrary described carried copper manganese system complex oxide deoxidier of claim 1～3 in method of deoxidation.
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