CN104689823A - Process for preparing copper-based catalyst by using formed foil as carrier - Google Patents
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- CN104689823A CN104689823A CN201510076127.6A CN201510076127A CN104689823A CN 104689823 A CN104689823 A CN 104689823A CN 201510076127 A CN201510076127 A CN 201510076127A CN 104689823 A CN104689823 A CN 104689823A
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- copper
- waste acid
- based catalysts
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- cheng foil
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Abstract
The invention discloses a process for preparing a copper-based catalyst by using a formed foil as a carrier. The process comprises the following steps: S1, preparing nitrate, wherein components of nitrate are prepared according to the components of the copper-based catalyst which is finally produced through burning, and the copper-based catalyst comprises the following substances in parts by mass: 2-20 parts of CuO, 2-20 parts of ZnO, 0.1-5 parts of ZrO, 45-95 parts of Al2O3, 0-5 parts of CeO2, and 0-5 parts of La2O3; S2, preparing a solution from nitrate; S3, dipping the formed foil into the solution obtained in the step S2; S4, drying the formed foil which is aired at room temperature after being dipped; S5, burning the dried semi-finished product; and S6, cooling to reach the room temperature. According to the process for preparing the copper-based catalyst by using the formed foil as the carrier, the surface area of the catalyst can be increased, and the hydrogen production efficiency and the conversion rate are increased.
Description
Technical field
The invention belongs to catalyst preparation technical field, relate to a kind of catalyst preparation process, particularly relate to a kind of Waste Acid From Hua Cheng Foil prepares copper-based catalysts technique as carrier.
Background technology
In recent years, along with the development of Proton Exchange Membrane Fuel Cells, particularly it is applied to automobile and distributed power generation, in the urgent need to the mobile hydrogen making system of small-sized efficient, efficient, dispersion to supply feed hydrogen.So there is hydrogen generating system miscellaneous, also there is hydrogen production process miscellaneous simultaneously.
The use liquid air speed that existing steam reformation of methanol to produce hydrogen copper-based catalysts is mainly shaping beaded catalyst maximum is less than 2.0h
-1, adopt Waste Acid From Hua Cheng Foil to improve catalyst specific surface as carrier, improve the liquid air speed of catalyst.Metallic aluminium belongs to the light metal of white, has light specific gravity, the characteristic of easily processing, and has good thermal conductivity and stronger corrosion resistance.Aluminium foil expands specific area through the process of chemical attack or electrochemical corrosion.Aluminium foil after corrosion is carried out anodic oxidation, makes it the γ-Al generating one deck compact structure in its surface
2o
3film, becomes Waste Acid From Hua Cheng Foil.
A kind of hydrogen production from methanol-steam reforming equipment that such as Chinese patent CN202519022U discloses, described equipment comprises liquid container, heat exchanger, vaporizer, reformer chamber, separation chamber.Described equipment comprises one or more heating unit, for hydrogen producer needs temperature controlled parts to carry out temperature control; The residual air that heating unit is exported by separation chamber is or/and obtained hydrogen heating.Transfer pipe between reformer chamber and separation chamber is through a preheating temperature control mechanism, and this preheating temperature control mechanism is in order to the gas of heating from reformer chamber output; Described preheating temperature control mechanism, as the buffering between reformer chamber and separation chamber, makes the temperature of the gas exported from reformer chamber identical with the temperature of separation chamber or close.
The and for example hydrogen production process that provides of China Patent Publication No. CN101033059, this hydrogen production process does not need outside heat supply due to it, and easy realization scene heats, so receive vast concern.Adopt off-gas to carry out heating system in the method, the result of generation is that each position of system is heated uneven, the most directly, is also that what to affect most is the catalytic activity of catalyst.
All hydrogen from methyl alcohol catalyst are in the market active temperatures that copper catalyst or noble metal catalyst and other catalyst all have self, or at 200-300 DEG C, or at 350-450, or more than 400, catalytic activity will be produced low, the result of catalyst efficiency during catalyst therefore in the even system of temperature distributing disproportionation in application market.Namely the catalyst on market is applied and is just had limitation in the system of non-samming.
In view of this, nowadays in the urgent need to designing a kind of new hydrogen from methyl alcohol catalyst, to overcome the above-mentioned defect of existing catalyst.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of Waste Acid From Hua Cheng Foil to prepare the technique of copper-based catalysts as carrier, can improve the surface area of catalyst, improves hydrogen production efficiency and conversion ratio.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
Waste Acid From Hua Cheng Foil prepares a technique for copper-based catalysts as carrier, and described technique comprises the steps:
Step S1, preparation nitrate, the one-tenth assignment system of the copper-based catalysts that the composition of nitrate finally generates through calcination according to it, described copper-based catalysts comprises material and mass fraction is: the CuO of 10 parts, the ZnO of 10 parts, the ZrO of 1 part, the Al of 78 parts
2o
3, the CeO of 0.5 part
2, the La of 0.5 part
2o
3;
Step S2, above-mentioned nitrate is configured to solution;
Step S3, Waste Acid From Hua Cheng Foil is immersed in the obtained solution of step S2;
The Waste Acid From Hua Cheng Foil at room temperature dried after step S4, dry dipping; Baking temperature is set as 120 DEG C, and drying time is 2 hours;
Step S5, calcination is carried out to dried semi-finished product; Calcination temperature is 500 DEG C, and calcination time is 5 hours;
Step S6, be cooled to room temperature;
The Waste Acid From Hua Cheng Foil that the solution impregnation that step S7, continuation step S2 obtain obtains through step S6; The drying of step S4, the calcination of step S5, the cooling of step S6 is then utilized to obtain the copper-based catalysts of Waste Acid From Hua Cheng Foil as carrier.
Waste Acid From Hua Cheng Foil prepares a technique for copper-based catalysts as carrier, and described technique comprises the steps:
Step S1, preparation nitrate, the one-tenth assignment system of the copper-based catalysts that the composition of nitrate finally generates through calcination according to it, described copper-based catalysts comprises material and mass fraction is: the CuO of 2-20 part, the ZnO of 2-20 part, the Al of the ZrO of 0.1-5 part, 45-95 part
2o
3, the CeO of 0-5 part
2, the La of 0-5 part
2o
3;
Step S2, above-mentioned nitrate is configured to solution;
Step S3, Waste Acid From Hua Cheng Foil is immersed in the obtained solution of step S2;
Waste Acid From Hua Cheng Foil at room temperature dry after step S4, dry dipping;
Step S5, calcination is carried out to dried semi-finished product;
Step S6, be cooled to room temperature.
As a preferred embodiment of the present invention, described technique comprises further: the Waste Acid From Hua Cheng Foil that the solution impregnation that step S7, continuation step S2 obtain obtains through step S6; The drying of step S4, the calcination of step S5, the cooling of step S6 is then utilized to obtain the copper-based catalysts of Waste Acid From Hua Cheng Foil as carrier.
As a preferred embodiment of the present invention, described technique comprises further: the Waste Acid From Hua Cheng Foil that the solution impregnation that step S8, continuation step S2 obtain obtains through step S7; The drying of step S4, the calcination of step S5, the cooling of step S6 is then utilized to obtain the copper-based catalysts of Waste Acid From Hua Cheng Foil as carrier.
As a preferred embodiment of the present invention, described copper-based catalysts also comprises rare earth metal, described rare earth metal comprise in lanthanum, cerium, neodymium, europium, praseodymium one or more.
As a preferred embodiment of the present invention, described copper-based catalysts also comprises transition metal, transition metal comprise in zirconium, yttrium, molybdenum, niobium, manganese, cobalt one or more.
As a preferred embodiment of the present invention, in step S4, baking temperature is set as 100 DEG C-160 DEG C, and drying time is 1 to 10 hour.
As a preferred embodiment of the present invention, in step S5, calcination temperature is 400 DEG C-600 DEG C, and calcination time is 1 to 10 hour.
Beneficial effect of the present invention is: the Waste Acid From Hua Cheng Foil that the present invention proposes prepares the technique of copper-based catalysts as carrier, can improve the surface area of catalyst, improves hydrogen production efficiency and conversion ratio.
The present invention adopts Waste Acid From Hua Cheng Foil to improve catalyst specific surface as carrier, improves the liquid air speed of catalyst; Alleviate the proportion of catalyst; Add the heat conduction of powerful catalyst, make the temperature of catalyst more even, improve the service life of catalyst.
Accompanying drawing explanation
Fig. 1 is Waste Acid From Hua Cheng Foil of the present invention prepares the technique of copper-based catalysts flow chart as carrier.
Detailed description of the invention
The preferred embodiments of the present invention are described in detail below in conjunction with accompanying drawing.
Embodiment one
Refer to Fig. 1, present invention is disclosed a kind of Waste Acid From Hua Cheng Foil prepares copper-based catalysts technique as carrier, described technique comprises the steps:
[step S1] prepares nitrate, and the one-tenth assignment system of the copper-based catalysts that the composition of nitrate finally generates through calcination according to it, described copper-based catalysts comprises material and mass fraction is: the CuO of 10 parts, the ZnO of 10 parts, the ZrO of 1 part, the Al of 78 parts
2o
3, the CeO of 0.5 part
2, the La of 0.5 part
2o
3;
Above-mentioned nitrate is configured to solution by [step S2];
Waste Acid From Hua Cheng Foil is immersed in the obtained solution of step S2 by [step S3];
The Waste Acid From Hua Cheng Foil at room temperature dried after [step S4] drying dipping; Baking temperature is set as 120 DEG C, and drying time is 2 hours;
[step S5] carries out calcination to dried semi-finished product; Calcination temperature is 500 DEG C, and calcination time is 5 hours;
[step S6] is cooled to room temperature;
The Waste Acid From Hua Cheng Foil that the solution impregnation that [step S7] continuation step S2 obtains obtains through step S6; The drying of step S4, the calcination of step S5, the cooling of step S6 is then utilized to obtain the copper-based catalysts of Waste Acid From Hua Cheng Foil as carrier.
Embodiment two
Refer to Fig. 1, in the present embodiment, the technique that Waste Acid From Hua Cheng Foil prepares copper-based catalysts as carrier comprises the steps:
[step S1] prepares nitrate, and the one-tenth assignment system of the copper-based catalysts that the composition of nitrate finally generates through calcination according to it, described copper-based catalysts comprises material and mass fraction is: the CuO of 2-20, the Al of the ZrO of the ZnO of 2-20,0.1-5,45-95
2o
3, the CeO of 0-5
2, the La of 0-5
2o
3;
In addition, described copper-based catalysts can also comprise rare earth metal, transition metal, described rare earth metal comprise in lanthanum, cerium, neodymium, europium, praseodymium one or more; Transition metal comprise in zirconium, yttrium, molybdenum, niobium, manganese, cobalt one or more.
Above-mentioned nitrate is configured to solution by [step S2];
Waste Acid From Hua Cheng Foil is immersed in the obtained solution of step S2 by [step S3];
The Waste Acid From Hua Cheng Foil at room temperature dried after [step S4] drying dipping; Baking temperature is set as 120 DEG C, and drying time is 2 hours;
[step S5] carries out calcination to dried semi-finished product; Calcination temperature is 500 DEG C, and calcination time is 5 hours;
[step S6] is cooled to room temperature.
Preferably, described technique can also comprise:
The Waste Acid From Hua Cheng Foil that the solution impregnation that [step S7] can also continue to obtain with step S2 obtains through step S6; The drying of step S4, the calcination of step S5, the cooling of step S6 is then utilized to obtain the copper-based catalysts of Waste Acid From Hua Cheng Foil as carrier.
The Waste Acid From Hua Cheng Foil that the solution impregnation that [step S8] continuation step S2 obtains obtains through step S7; The drying of step S4, the calcination of step S5, the cooling of step S6 is then utilized to obtain the copper-based catalysts of Waste Acid From Hua Cheng Foil as carrier.Certainly, can also have again or more time carry out step S2 to S6 step.
In sum, the Waste Acid From Hua Cheng Foil that the present invention proposes prepares the technique of copper-based catalysts as carrier, can improve the surface area of catalyst, improves hydrogen production efficiency and conversion ratio.
Here description of the invention and application is illustrative, not wants by scope restriction of the present invention in the above-described embodiments.Distortion and the change of embodiment disclosed are here possible, are known for the replacement of embodiment those those of ordinary skill in the art and the various parts of equivalence.Those skilled in the art are noted that when not departing from spirit of the present invention or substantive characteristics, the present invention can in other forms, structure, layout, ratio, and to realize with other assembly, material and parts.When not departing from the scope of the invention and spirit, can other distortion be carried out here to disclosed embodiment and change.
Claims (8)
1. Waste Acid From Hua Cheng Foil prepares a technique for copper-based catalysts as carrier, it is characterized in that, described technique comprises the steps:
Step S1, preparation nitrate, the one-tenth assignment system of the copper-based catalysts that the composition of nitrate finally generates through calcination according to it, described copper-based catalysts comprises material and mass fraction is: the CuO of 10 parts, the ZnO of 10 parts, the ZrO of 1 part, the Al of 78 parts
2o
3, the CeO of 0.5 part
2, the La of 0.5 part
2o
3;
Step S2, above-mentioned nitrate is configured to solution;
Step S3, Waste Acid From Hua Cheng Foil is immersed in the obtained solution of step S2;
The Waste Acid From Hua Cheng Foil at room temperature dried after step S4, dry dipping; Baking temperature is set as 120 DEG C, and drying time is 2 hours;
Step S5, calcination is carried out to dried semi-finished product; Calcination temperature is 500 DEG C, and calcination time is 5 hours;
Step S6, be cooled to room temperature;
The Waste Acid From Hua Cheng Foil that the solution impregnation that step S7, continuation step S2 obtain obtains through step S6; The drying of step S4, the calcination of step S5, the cooling of step S6 is then utilized to obtain the copper-based catalysts of Waste Acid From Hua Cheng Foil as carrier.
2. Waste Acid From Hua Cheng Foil prepares a technique for copper-based catalysts as carrier, it is characterized in that, described technique comprises the steps:
Step S1, preparation nitrate, the one-tenth assignment system of the copper-based catalysts that the composition of nitrate finally generates through calcination according to it, described copper-based catalysts comprises material and mass fraction is: the CuO of 2-20 part, the ZnO of 2-20 part, the Al of the ZrO of 0.1-5 part, 45-95 part
2o
3, the CeO of 0-5 part
2, the La of 0-5 part
2o
3;
Step S2, above-mentioned nitrate is configured to solution;
Step S3, Waste Acid From Hua Cheng Foil is immersed in the obtained solution of step S2;
The Waste Acid From Hua Cheng Foil dried after step S4, dry dipping;
Step S5, calcination is carried out to dried semi-finished product;
Step S6, be cooled to room temperature.
3. Waste Acid From Hua Cheng Foil according to claim 2 prepares the technique of copper-based catalysts as carrier, it is characterized in that:
Described technique comprises further: the Waste Acid From Hua Cheng Foil that the solution impregnation that step S7, continuation step S2 obtain obtains through step S6; The drying of step S4, the calcination of step S5, the cooling of step S6 is then utilized to obtain the copper-based catalysts of Waste Acid From Hua Cheng Foil as carrier.
4. Waste Acid From Hua Cheng Foil according to claim 3 prepares the technique of copper-based catalysts as carrier, it is characterized in that:
Described technique comprises further: the Waste Acid From Hua Cheng Foil that the solution impregnation that step S8, continuation step S2 obtain obtains through step S7; The drying of step S4, the calcination of step S5, the cooling of step S6 is then utilized to obtain the copper-based catalysts of Waste Acid From Hua Cheng Foil as carrier.
5. Waste Acid From Hua Cheng Foil according to claim 2 prepares the technique of copper-based catalysts as carrier, it is characterized in that:
Described copper-based catalysts also comprises rare earth metal, described rare earth metal comprise in lanthanum, cerium, neodymium, europium, praseodymium one or more.
6. Waste Acid From Hua Cheng Foil according to claim 2 prepares the technique of copper-based catalysts as carrier, it is characterized in that:
Described copper-based catalysts also comprises transition metal, transition metal comprise in zirconium, yttrium, molybdenum, niobium, manganese, cobalt one or more.
7. Waste Acid From Hua Cheng Foil according to claim 2 prepares the technique of copper-based catalysts as carrier, it is characterized in that:
In step S4, baking temperature is set as 100 DEG C-160 DEG C, and drying time is 1 to 10 hour.
8. Waste Acid From Hua Cheng Foil according to claim 2 prepares the technique of copper-based catalysts as carrier, it is characterized in that:
In step S5, calcination temperature is 400 DEG C-600 DEG C, and calcination time is 1 to 10 hour.
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2015
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Application publication date: 20150610 |