CN109908908A - A kind of base metal preparing hydrogen by reforming methanol catalyst and preparation method thereof - Google Patents
A kind of base metal preparing hydrogen by reforming methanol catalyst and preparation method thereof Download PDFInfo
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- CN109908908A CN109908908A CN201910119679.9A CN201910119679A CN109908908A CN 109908908 A CN109908908 A CN 109908908A CN 201910119679 A CN201910119679 A CN 201910119679A CN 109908908 A CN109908908 A CN 109908908A
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Abstract
The invention discloses a kind of base metal preparing hydrogen by reforming methanol catalyst and preparation method thereof, are uniform solid solution, are made by reversed coprecipitation, including carrier ZnO/Al2O3And the active component Cu and auxiliary agent Sc of load thereon2O3, wherein the amount of Sc is 1.0~5.0wt%.Base metal preparing hydrogen by reforming methanol catalyst of the invention is uniform solid solution and active metal partial size is small, the problem of being uniformly dispersed, being able to solve existing catalyst high temperature easy-sintering.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of base metal preparing hydrogen by reforming methanol catalyst and its system
Preparation Method.
Background technique
Particulate matter (PM) and nitrogen oxides (NO in vehicle exhaustx) the main reason for being city haze.PM be usually by
Caused by the imperfect combustion of fuel, and NOxBe due in engine combustion room local temperature it is higher caused by free radical
Reaction causes.Therefore, engine exhaust emission is reduced to Guan Chong by improving efficiency of combustion as far as possible and reducing ignition temperature
It wants.
In recent years, hydrogen becomes important one of mixed fuel firing technology with diesel oil mixing blending and burning technology.It is logical to air inlet
A small amount of hydrogen is added in road and forms hydrogen-rich gas, in injection engine, it will help the igniting of fuel in engine chamber
And burning.Fuel efficiency is not only increased, but also can be reduced the pollutant in tail gas, including reduces PM, while inhibiting NOx's
Formed etc..
In the chemical storage method of numerous hydrogen, methanol is considered as one of most suitable on-board hydrogen source.Using methanol recapitalization
Hydrogen producing technology prepare hydrogen have the advantages that it is very more: it is cheap and readily available firstly, methanol is general chemical raw material, and be easy to make
For fluid storage；Methanol is a kind of primary alcohol, hydrogen-carbon ratio with higher, but does not have carbon-carbon bond, therefore can be relatively low
Temperature (200~300 DEG C) under be easily converted into hydrogen-rich gas, while its energy consumption is relatively low.In addition, methanol can be by biology
The renewable resources such as matter ferment to obtain, and biomass is typically free of sulphur, therefore discharge less in reforming process or be hardly discharged
Sulfur dioxide.Traditional methanol recapitalization copper-based catalysts are easy to happen reunion, sintering when temperature is more than 300 DEG C, cause to be catalyzed
Agent inactivation.All the time for copper-based catalysts this defects all not compared with effective solution means, and noble metal catalyst or
Zn-Cr catalyst requires in cost or applicable elements higher compared to copper-based catalysts, therefore can not promote the use of.It is copper-based
Catalyst is low in cost, and Applicable temperature is low, and hydrogen selectivity is high, therefore, if can solve easy in inactivation under copper-based catalysts high temperature
Problem then can effectively extend the service life of catalyst.This is not only for diesel oil auxiliary combustion vehicle-mounted methanol hydrogen-feeding system
Exploitation has application value, and also has extensive theory significance and practical application value for other hydrogen from methyl alcohol occasions.
CN108404925A discloses a kind of preparing hydrogen by reforming methanol catalyst, involved in catalyst solve tradition
The defect of copper-based catalysts high temperature easy in inactivation, but the low temperature active of the catalyst is not very prominent, and effect is still not ideal enough.
Summary of the invention
It is an object of the invention to overcome prior art defect, providing one kind has preferable low temperature active, while anti-height again
The base metal preparing hydrogen by reforming methanol catalyst of temperature sintering.
Another object of the present invention is to provide the preparation methods of above-mentioned base metal preparing hydrogen by reforming methanol catalyst.
Technical scheme is as follows:
A kind of base metal preparing hydrogen by reforming methanol catalyst is uniform solid solution, is made by reversed coprecipitation, wrapped
Include carrier ZnO/Al2O3And the active component Cu and auxiliary agent Sc of load thereon2O3, wherein the amount of Sc is 1.0~5.0wt%.
The preparation method of above-mentioned base metal preparing hydrogen by reforming methanol catalyst, includes the following steps:
(1) copper nitrate, scandium nitrate, aluminum nitrate and zinc nitrate are added in deionized water, add polyoxyethylene surface
Activating agent is uniformly mixed, and obtains metal mixed salt solution；
(2) sodium hydroxide solution is added in above-mentioned metal mixed salt solution, it is complete to metal ion in 70-80 DEG C of stirring
Precipitating, is then allowed to stand ageing, obtains the precipitating suspension of pH >=8；
(3) by above-mentioned precipitating suspension filtering after, precipitated, then by the precipitating successively through ion water washing, drying and
Roasting, obtains the base metal preparing hydrogen by reforming methanol catalyst；
The temperature of above-mentioned drying is 100~120 DEG C, and the dry time is 10~13h；The temperature of above-mentioned roasting be 380~
420 DEG C, calcining time is 3~10h.
In a preferred embodiment of the invention, the dosage of the polyoxyethylene surfactant is not more than nitric acid
Copper, scandium nitrate, 0.3 times of aluminum nitrate and zinc nitrate gross mass.
In a preferred embodiment of the invention, the copper nitrate, scandium nitrate, aluminum nitrate and zinc nitrate are in the gold
The final concentration belonged in mixed salt solution is 0.5~2.0mol/L.
In a preferred embodiment of the invention, the concentration of the sodium hydroxide solution is 1.0~3.0mol/L.
In a preferred embodiment of the invention, the temperature of the drying is 110 DEG C, and the dry time is 12h.
In a preferred embodiment of the invention, the temperature of the roasting is 400 DEG C.
It in a preferred embodiment of the invention, further include step (4): by the base metal preparing hydrogen by reforming methanol
Catalyst agate mortar grinding, tabletting machine, then pulverize and are sized to 20~40 mesh of partial size again.
The beneficial effects of the present invention are: base metal preparing hydrogen by reforming methanol catalyst of the invention be uniform solid solution and
Active metal partial size is small, is uniformly dispersed, and can not only solve the problems, such as existing copper-based catalysts high temperature easy-sintering, also greatly improve
The low temperature active of catalyst, specific: base metal preparing hydrogen by reforming methanol catalyst of the invention is anti-through preparing hydrogen by reforming methanol
Performance test is answered, is found in H2O/CH3OH (mass ratio)=0.5~1.5, O2/CH3OH (mass ratio)=0.1~0.2, catalyst
0.2g, WHSV=10~20h-1Under conditions of, 270 DEG C of temperature > whens, show higher catalytic activity, at this point, methanol is most
High conversion is close to 100%.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern of base metal preparing hydrogen by reforming methanol catalyst obtained by the embodiment of the present invention 1,2,3,4
Spectrum.
Fig. 2 is that the preparing hydrogen by reforming methanol of base metal preparing hydrogen by reforming methanol catalyst obtained by the embodiment of the present invention 1 is living
Property test result figure.
Fig. 3 is that the preparing hydrogen by reforming methanol of base metal preparing hydrogen by reforming methanol catalyst obtained by the embodiment of the present invention 2 is living
Property test result figure.
Fig. 4 is that the preparing hydrogen by reforming methanol of base metal preparing hydrogen by reforming methanol catalyst obtained by the embodiment of the present invention 3 is living
Property test result figure.
Fig. 5 is that the preparing hydrogen by reforming methanol of base metal preparing hydrogen by reforming methanol catalyst obtained by the embodiment of the present invention 4 is living
Property test result figure.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment combination attached drawing.
Embodiment 1
Reversed coprecipitation prepares catalyst: CuO/ZnO (is abbreviated as CZ)
(1) 8.6g copper nitrate and 13.0g zinc nitrate are added to deionized water: ethyl alcohol=1: the mixing of 1 (volume ratio) is molten
In liquid, polyoxyethylene surfactant 0.2g is added, is uniformly mixed, metal mixed salt solution is obtained；
It (2) is that 1.0~3.0mol/L sodium hydroxide solution instills metal mixed salt solution by 100mL concentration, in 75 DEG C of machines
Tool is stirred to metal ion and is precipitated completely, keeps old terms to be aged 2h after precipitating, is obtained pH >=8 and is precipitated suspension；
(3) it is washed with deionized, dries, roasts by the filtering of obtained precipitating suspension, again, obtain the catalyst；
Above-mentioned drying temperature is 110 DEG C, drying time 12h；The temperature of above-mentioned roasting is 400 DEG C, and calcining time is 3~10h；
(4) above-mentioned catalyst is taken, with agate mortar grinding, tabletting machine is used again, then pulverizes and sieved again to get to urging
Agent finished product.
Embodiment 2
Reversed coprecipitation prepares catalyst: CuO/Sc2O3- ZnO (is abbreviated as CSZ)
8.6g copper nitrate, 13.0g zinc nitrate and 0.5g scandium nitrate are added to deionized water and ethyl alcohol 1: 1 (volume ratio) is mixed
It closes in solution, adds polyoxyethylene surfactant 0.2g, be uniformly mixed, obtain metal mixed salt solution；Remaining
With embodiment 1.
Embodiment 3
Reversed coprecipitation prepares catalyst: CuO-ZnO/Al2O3(being abbreviated as CZA)
8.6g copper nitrate, 13.0g zinc nitrate and 7.9g aluminum nitrate are added in deionized water, polyoxyethylene table is added
Face activating agent 0.2g, is uniformly mixed, and obtains metal mixed salt solution；Remaining is the same as embodiment 1.
Embodiment 4
Reversed coprecipitation prepares catalyst: CuO/Sc2O3-ZnO/Al2O3(being abbreviated as CSZA)
3.6g copper nitrate, 19.3g zinc nitrate, 7.9g aluminum nitrate and 1.1g scandium nitrate are added in deionized water, added
Polyoxyethylene surfactant 0.2g, is uniformly mixed, and obtains metal mixed salt solution；Remaining is the same as embodiment 1.
Embodiment 5
CZ, CSZ, CZA, CSZA catalyst prepared in the embodiment of the present invention 1 to 4 is applied to preparing hydrogen by reforming methanol activity
Test.
Specific reaction condition is as follows: the preparing hydrogen by reforming methanol reactivity worth that catalyst is carried out in fixed bed reactors is surveyed
Examination, in H2O/CH3OH (M)=0.5~1.5, O2/CH3OH (M)=0.1~0.2, WHSV=10~20h-1Under conditions of, catalysis
Agent quality is 0.2g, and for nitrogen as Balance Air, reaction temperature section is 150~330 DEG C, Mei Gewen primary every 30 DEG C of detections
Degree point acquires data after reaching balance, and test result is as shown in Fig. 2,3,4,5.
As shown in Figure 1, CuO/ZnO catalyst and CuO/ZnO/Sc prepared by embodiment 1,2,3,42O3Catalyst series
Copper particle is gradually reduced with the addition size of scandium.
As shown in Fig. 2, as the temperature rises for the CuO/ZnO catalyst for preparing of embodiment 1, conversion ratio increases, first at 300 DEG C
Alcohol conversion is only 85%, and methanol conversion is below other catalyst in entire temperature range.
As shown in figure 3, CuO-ZnO/Al prepared by embodiment 22O3As the temperature rises for catalyst, and conversion ratio increases, and 300
DEG C when methanol conversion close to 100%.
As shown in figure 4, CuO/Sc prepared by embodiment 32O3As the temperature rises for ZnO catalyst, and conversion ratio increases, and 300
DEG C when methanol conversion close to 100%.
As shown in figure 5, CuO/Sc prepared by embodiment 42O3-ZnO/Al2O3As the temperature rises for catalyst, and conversion ratio increases
Greatly, 300 DEG C when methanol conversion close to 100%, initial conversion is slightly lower, but as temperature increases, conversion ratio is increased speed most
Fastly, almost in entire temperature range, highest methanol conversion can be obtained.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (8)
1. a kind of base metal preparing hydrogen by reforming methanol catalyst, it is characterised in that: be uniform solid solution, by being reversely co-precipitated
Method is made, including carrier ZnO/Al2O3And the active component Cu and auxiliary agent Sc of load thereon2O3, wherein the amount of Sc be 1.0~
5.0wt%.
2. the preparation method of base metal preparing hydrogen by reforming methanol catalyst described in claim 1, it is characterised in that: including as follows
Step:
(1) copper nitrate, scandium nitrate, aluminum nitrate and zinc nitrate are added in deionized water, add polyoxyethylene surface-active
Agent is uniformly mixed, and obtains metal mixed salt solution；
(2) sodium hydroxide solution is added in above-mentioned metal mixed salt solution, it is completely heavy to metal ion in 70-80 DEG C of stirring
It forms sediment, is then allowed to stand ageing, obtains the precipitating suspension of pH >=8；
(3) it by after the filtering of above-mentioned precipitating suspension, is precipitated, then by the precipitating successively through ion water washing, drying and roasting,
Obtain the base metal preparing hydrogen by reforming methanol catalyst；
The temperature of above-mentioned drying is 100~120 DEG C, and the dry time is 10~13h；The temperature of above-mentioned roasting is 380~420
DEG C, calcining time is 3~10h.
3. preparation method as claimed in claim 2, it is characterised in that: the dosage of the polyoxyethylene surfactant is little
In 0.3 times of copper nitrate, scandium nitrate, aluminum nitrate and zinc nitrate gross mass.
4. preparation method as claimed in claim 2, it is characterised in that: the copper nitrate, scandium nitrate, aluminum nitrate and zinc nitrate exist
Final concentration in the metal mixed salt solution is 0.5~2.0mol/L.
5. preparation method as claimed in claim 2, it is characterised in that: the concentration of the sodium hydroxide solution be 1.0~
3.0mol/L。
6. preparation method as claimed in claim 2, it is characterised in that: the temperature of the drying is 110 DEG C, and the dry time is
12h。
7. preparation method as claimed in claim 2, it is characterised in that: the temperature of the roasting is 400 DEG C.
8. the preparation method as described in any claim in claim 2 to 7, it is characterised in that: further include step (4): will
The base metal preparing hydrogen by reforming methanol catalyst agate mortar grinding, tabletting machine, then pulverize and are sized to partial size again
20~40 mesh.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404547A (en) * | 2019-08-06 | 2019-11-05 | 北京蓝玖新能源科技有限公司 | A kind of catalyst and its preparation method and application |
Citations (3)
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| CN102145281A (en) * | 2010-02-10 | 2011-08-10 | 中国科学院大连化学物理研究所 | Catalyst for producing hydrogen by methanol steam reforming and preparation and application |
| CN104645985A (en) * | 2015-02-12 | 2015-05-27 | 上海摩醇动力技术有限公司 | Production process for catalyst for hydrogen production through methanol steam reforming |
| CN108404925A (en) * | 2018-04-11 | 2018-08-17 | 厦门大学 | A kind of preparing hydrogen by reforming methanol catalyst and preparation method thereof |
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2019
- 2019-02-18 CN CN201910119679.9A patent/CN109908908A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102145281A (en) * | 2010-02-10 | 2011-08-10 | 中国科学院大连化学物理研究所 | Catalyst for producing hydrogen by methanol steam reforming and preparation and application |
| CN104645985A (en) * | 2015-02-12 | 2015-05-27 | 上海摩醇动力技术有限公司 | Production process for catalyst for hydrogen production through methanol steam reforming |
| CN108404925A (en) * | 2018-04-11 | 2018-08-17 | 厦门大学 | A kind of preparing hydrogen by reforming methanol catalyst and preparation method thereof |
Non-Patent Citations (1)
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Cited By (1)
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| CN110404547A (en) * | 2019-08-06 | 2019-11-05 | 北京蓝玖新能源科技有限公司 | A kind of catalyst and its preparation method and application |
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