CN109794250A - A kind of hydrogen synthetic catalyst and preparation method thereof - Google Patents
A kind of hydrogen synthetic catalyst and preparation method thereof Download PDFInfo
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- CN109794250A CN109794250A CN201811647577.6A CN201811647577A CN109794250A CN 109794250 A CN109794250 A CN 109794250A CN 201811647577 A CN201811647577 A CN 201811647577A CN 109794250 A CN109794250 A CN 109794250A
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- synthetic catalyst
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- hydrogen synthetic
- ultrasonic vibration
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Abstract
The present invention relates to Technology for Production Hydrogen from Methanol fields, more particularly to a kind of hydrogen synthetic catalyst and preparation method thereof, include the following steps: that (1) takes copper nitrate and basic zinc carbonate to be added into deionized water, under ultrasonic vibration, it is gradually added into sodium carbonate liquor, adjusts pH value, terminate concussion, ageing, filtering, is precipitated；(2) precipitating is washed, lanthana is added and carries out ball milling dispersion, then washed, dried, roasted to get the hydrogen synthetic catalyst is arrived.The present invention utilizes the combination of a step reverse-precipitation and ultrasonic vibration technique, during ultrasonic vibration, the bigger copper carbonate precipitating of partial size more small specific surface product can be generated, and it is easy to be attached on basic zinc carbonate, relative to common a step precipitation method or two precipitation method, catalyst obtained has higher specific surface area and Cu dispersion degree；In addition, the present invention is also mixed into lanthana in precipitating, the stability and hydrogen-producing speed of catalyst can be promoted.
Description
Technical field
The present invention relates to Technology for Production Hydrogen from Methanol fields, and in particular to a kind of hydrogen synthetic catalyst and preparation method thereof.
Background technique
Hydrogen is as ideal chemical fuel, energy carrier and energy storage tool, rich reserves on earth, combustion heat value
Height, and do not generate any pollution after burning, is conducive to environmental protection, therefore is counted as 21 century ideal clean new energy.
In all too many levels of hydrogen manufacturing key technology it may first have to solve the Discussion On Development of effective catalyst.No matter from technology
Maturity or from existing infrastructure using from the point of view of degree, with fossil fuel (including methanol, natural gas, vapour
Oil, diesel oil etc.) hydrogen manufacturing is the important channel for solving small-scale distributing hydrogen source at this stage.Liquid fuel carbinol is due to hydrogen manufacturing
The features such as conversion condition (temperature, pressure, volume, quality) is relatively mild, sulfur-bearing, low toxicity, hydrogen production process are not realized relatively easily
As the first choice in these hydrogen-rich fuels.
Currently, the report that copper-based catalysts are applied to methanol steam reforming reaction is more, number of patent application is
201810320327.5 patent of invention discloses the catalyst of CuO/ZnO/ScO a kind of, which has methanol conversion high
The characteristics of, but have no and illustrate for the stability and hydrogen yield of catalyst.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of methanol conversions
High, stable and high hydrogen yield hydrogen synthetic catalyst and preparation method thereof.
The purpose of the invention is achieved by the following technical solution:
A kind of preparation method of hydrogen synthetic catalyst, includes the following steps:
(1) basic zinc carbonate of the copper nitrate and 36-40 parts by weight that take 3-6 parts by weight is added to 100 parts by weight deionizations
In water, under ultrasonic vibration, it is gradually added into sodium carbonate liquor, adjusting pH value is 7.5-8.5, terminates concussion, is aged, and filtering obtains
To precipitating；
(2) precipitating is washed, 0.5-1 parts by weight lanthana is added and carries out ball milling dispersion, then washed, done
It is dry, roasting to get arrive the hydrogen synthetic catalyst.
The present invention utilizes the combination of a step reverse-precipitation and ultrasonic vibration technique, during ultrasonic vibration, can be generated
The bigger copper carbonate precipitating of partial size more small specific surface product, and be easy to be attached on basic zinc carbonate, relative to a common step
The precipitation method or two precipitation method, catalyst obtained have higher specific surface area and Cu dispersion degree；In addition, the present invention is also heavy
It is mixed into lanthana in shallow lake, the stability and hydrogen-producing speed of catalyst can be promoted.
Wherein, the ultrasonic frequency of the ultrasonic vibration is 20-40kHz, ultrasonic power 20-30W.Ultrasonic wave generates
Cavitation effect can promote the uniform generation of the evenly dispersed of basic zinc carbonate and precipitating, but supersonic frequency or power mistake
Height, cavitation effect excessively can acutely make precipitating be not easy to be attached on basic zinc carbonate instead, reduce the dispersion degree of Cu, thus super
The ultrasonic frequency that acoustic shock is swung is 20-40kHz, ultrasonic power 20-30W.
Wherein, in the step (1), it is 60-70 DEG C that the temperature of solution is kept while ultrasonic vibration.Keep suitable temperature
Degree is conducive to improve the specific surface area of catalyst, and when temperature is 50 DEG C or 80 DEG C, the specific surface area of catalyst is not achieved
46.5m2/g。
Wherein, the digestion time is 40-80min.By control digestion time, sediment recurring structure is promoted to reset,
The catalyst prepared by has higher specific surface area and catalytic activity.
Wherein, the partial size of the basic zinc carbonate is 120-180nm, and the partial size of lanthana is 200-300nm.Basic carbonate
When the partial size of zinc is lower than 120nm, it can still find that part is reunited under the ultrasound condition of 20-40kHz and 20-30W of the invention
Phenomenon, partial size are higher than 180nm, are unfavorable for being deposited in the uniform attachment on basic zinc carbonate；And pass through the partial size of control lanthana
Its dispersibility can be promoted.
Wherein, the concentration of the sodium carbonate liquor is 1.0-2.0mol/L.The concentration of sodium carbonate liquor lower than 1mol/L or
Higher than 2mol/L, it is unfavorable for the control of pH, and is easy residual sodium ion in catalyst, reduces the catalytic activity of catalyst and steady
It is qualitative.
Wherein, the temperature of the drying is 80-120 DEG C.
Wherein, the maturing temperature is 340-360 DEG C, calcining time 2-3h.When by control maturing temperature and roasting
Between the catalyst of available large specific surface area and uniform component distribution, enhance copper zinc between interaction, promoted hydrogen produce
Rate.
The hydrogen synthetic catalyst specific surface area as made from method as above is 81.3-89.6m2The dispersion degree of/g, Cu is
12.1-13.8%.
The beneficial effects of the present invention are: the present invention utilizes the combination of a step reverse-precipitation and ultrasonic vibration technique, surpasses
During acoustic shock is swung, the bigger copper carbonate precipitating of partial size more small specific surface product can be generated, and be easy to be attached to basic carbonate
On zinc, relative to common a step precipitation method or two precipitation method, catalyst obtained has higher specific surface area and Cu points
Divergence；In addition, the present invention is also mixed into lanthana in precipitating, the stability and hydrogen-producing speed of catalyst can be promoted.
Detailed description of the invention
Fig. 1 be the hydrogen synthetic catalyst of embodiment 1 for hydrogen from methyl alcohol when methanol conversion-temperature profile.
Specific embodiment
For the ease of the understanding of those skilled in the art, make below with reference to 1 couple of present invention of examples and drawings further
Illustrate, the content that embodiment refers to not is limitation of the invention.
Embodiment 1
A kind of preparation method of hydrogen synthetic catalyst, includes the following steps:
(1) basic zinc carbonate of the copper nitrate and 38g that take 4.5g is added into 100g deionized water, under ultrasonic vibration,
It is gradually added into sodium carbonate liquor, adjusting pH value is 8, terminates concussion, is aged, and filtering is precipitated；
(2) precipitating is washed, 0.7g lanthana is added and carries out ball milling dispersion, is then washed, dried, roasted,
Obtain the hydrogen synthetic catalyst.
Wherein, the ultrasonic frequency of the ultrasonic vibration is 30kHz, ultrasonic power 25W
Wherein, in the step (1), it is 65 DEG C that the temperature of solution is kept while ultrasonic vibration.
Wherein, the digestion time is 60min.
Wherein, the partial size of the basic zinc carbonate is 150nm, and the partial size of lanthana is 250nm.
Wherein, the concentration of the sodium carbonate liquor is 1.5mol/L.
Wherein, the temperature of the drying is 100 DEG C.
Wherein, the maturing temperature is 350 DEG C, calcining time 2.5h.
The hydrogen synthetic catalyst specific surface area as made from method as above is 89.6m2The dispersion degree of/g, Cu are 13.8%.
Catalyst is crushed, after taking 8-10 mesh 2.5g to be packed into reactor, (30ml/min) is risen in a nitrogen atmosphere
Reaction temperature after temperature arrives, starts charging and reacts, the methanol conversion (result is as shown in Figure 1) of test reaction, at 350 DEG C,
Alcohol conversion reaches 98.6%, and measuring the hydrogen content produced in gas is 75.8%.
Embodiment 2
A kind of preparation method of hydrogen synthetic catalyst, includes the following steps:
(1) basic zinc carbonate of the copper nitrate and 36g that take 3g is added into 100g deionized water, under ultrasonic vibration, by
Sodium carbonate liquor is gradually added, adjusting pH value is 7.5, terminates concussion, is aged, and filtering is precipitated；
(2) precipitating is washed, 0.5g lanthana is added and carries out ball milling dispersion, is then washed, dried, roasted,
Obtain the hydrogen synthetic catalyst.
Wherein, the ultrasonic frequency of the ultrasonic vibration is 20kHz, ultrasonic power 20W
Wherein, in the step (1), it is 60 DEG C that the temperature of solution is kept while ultrasonic vibration.
Wherein, the digestion time is 40min.
Wherein, the partial size of the basic zinc carbonate is 120nm, and the partial size of lanthana is 200nm.
Wherein, the concentration of the sodium carbonate liquor is 1.0mol/L.
Wherein, the temperature of the drying is 80 DEG C.
Wherein, the maturing temperature is 340 DEG C, calcining time 2h.
The hydrogen synthetic catalyst specific surface area as made from method as above is 81.3m2The dispersion degree of/g, Cu are 12.1%.
Embodiment 3
A kind of preparation method of hydrogen synthetic catalyst, includes the following steps:
(1) basic zinc carbonate of the copper nitrate and 40g that take 6g is added into 100g deionized water, under ultrasonic vibration, by
Sodium carbonate liquor is gradually added, adjusting pH value is 8.5, terminates concussion, is aged, and filtering is precipitated；
(2) precipitating is washed, 1g lanthana is added and carries out ball milling dispersion, is then washed, dried, roasted, i.e.,
Obtain the hydrogen synthetic catalyst.
Wherein, the ultrasonic frequency of the ultrasonic vibration is 40kHz, ultrasonic power 30W
Wherein, in the step (1), it is 70 DEG C that the temperature of solution is kept while ultrasonic vibration.
Wherein, the digestion time is 80min.
Wherein, the partial size of the basic zinc carbonate is 180nm, and the partial size of lanthana is 300nm.
Wherein, the concentration of the sodium carbonate liquor is 2.0mol/L.
Wherein, the temperature of the drying is 120 DEG C.
Wherein, the maturing temperature is 360 DEG C, calcining time 3h.
The hydrogen synthetic catalyst specific surface area as made from method as above is 84.4m2The dispersion degree of/g, Cu are 12.8%.
Comparative example 1
This comparative example the difference from embodiment 1 is that: the preparation method of catalyst includes the following steps:
(1) zinc nitrate of the copper nitrate and 16g that take 4.5g is added into 100g deionized water, under ultrasonic vibration, gradually
Sodium carbonate liquor is added, adjusting pH value is 8, terminates concussion, is aged, and filtering is precipitated；
(2) precipitating is washed, 0.7g lanthana is added and carries out ball milling dispersion, is then washed, dried, roasted,
Obtain the catalyst.
The hydrogen synthetic catalyst specific surface area as made from method as above is 45.3m2The dispersion degree of/g, Cu are 7.4%.
Comparative example 2
This comparative example the difference from embodiment 1 is that: in step (1) without use ultrasonic vibration.
The hydrogen synthetic catalyst specific surface area as made from method as above is 48.1m2The dispersion degree of/g, Cu are 9.1%.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of preparation method of hydrogen synthetic catalyst, characterized by the following steps:
(1) basic zinc carbonate of the copper nitrate and 36-40 parts by weight that take 3-6 parts by weight is added into 100 parts by weight of deionized water,
Under ultrasonic vibration, it is gradually added into sodium carbonate liquor, adjusting pH value is 7.5-8.5, terminates concussion, is aged, and filtering is sunk
It forms sediment；
(2) precipitating is washed, 0.5-1 parts by weight lanthana is added and carries out ball milling dispersion, is then washed, dried, roasted
It burns to get the hydrogen synthetic catalyst is arrived.
2. a kind of preparation method of hydrogen synthetic catalyst according to claim 1, it is characterised in that: the ultrasonic vibration
Ultrasonic frequency is 20-40kHz, ultrasonic power 20-30W.
3. a kind of preparation method of hydrogen synthetic catalyst according to claim 1, it is characterised in that: in the step (1),
The temperature that solution is kept while ultrasonic vibration is 60-70 DEG C.
4. a kind of preparation method of hydrogen synthetic catalyst according to claim 1, it is characterised in that: the digestion time is
40-80min。
5. a kind of preparation method of hydrogen synthetic catalyst according to claim 1, it is characterised in that: the basic zinc carbonate
Partial size be 120-180nm, the partial size of lanthana is 200-300nm.
6. a kind of preparation method of hydrogen synthetic catalyst according to claim 1, it is characterised in that: the sodium carbonate liquor
Concentration be 1.0-2.0mol/L.
7. a kind of preparation method of hydrogen synthetic catalyst according to claim 1, it is characterised in that: the temperature of the drying
It is 80-120 DEG C.
8. a kind of preparation method of hydrogen synthetic catalyst according to claim 1, it is characterised in that: the maturing temperature is
340-360 DEG C, calcining time 2-3h.
9. a kind of hydrogen synthetic catalyst, it is characterised in that: the system of the hydrogen synthetic catalyst as described in claim 1-8 any one
Preparation Method is made.
10. hydrogen synthetic catalyst as claimed in claim 9, it is characterised in that: specific surface area 81.3-89.6m2The dispersion of/g, Cu
Degree is 12.1-13.8%.
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