CN114931973A - SAPO-34 supported cobalt boride catalyst, and preparation method and application thereof - Google Patents
SAPO-34 supported cobalt boride catalyst, and preparation method and application thereof Download PDFInfo
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- CN114931973A CN114931973A CN202210580908.9A CN202210580908A CN114931973A CN 114931973 A CN114931973 A CN 114931973A CN 202210580908 A CN202210580908 A CN 202210580908A CN 114931973 A CN114931973 A CN 114931973A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- WRSVIZQEENMKOC-UHFFFAOYSA-N [B].[Co].[Co].[Co] Chemical compound [B].[Co].[Co].[Co] WRSVIZQEENMKOC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002808 molecular sieve Substances 0.000 claims abstract description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000005303 weighing Methods 0.000 claims description 20
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 16
- 239000012279 sodium borohydride Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 241001411320 Eriogonum inflatum Species 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/02—Boron; Borides
- C01B35/04—Metal borides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses an SAPO-34 supported cobalt boride catalyst, a preparation method and an application thereof, wherein cobalt chloride hexahydrate and a reducing agent are used as main raw materials to react to prepare cobalt boride, and the cobalt boride is dispersed on an SAPO-34 molecular sieve to prepare the catalyst. For modifying NaBH 4 The rate of the hydrolysis hydrogen production process. The catalyst of the invention has simple preparation method, low cost, safety and no pollution.
Description
Technical Field
The invention belongs to the field of hydrogen preparation, and particularly relates to an SAPO-34 supported cobalt boride catalyst, and a preparation method and application thereof.
Background
With the increasing consumption of non-renewable resources such as fossil fuels (e.g., petroleum and natural gas) and environmental pollution caused by overuse of fossil fuels, attention is paid to the development of sustainable and renewable alternative energy carriers such as nuclear energy, solar energy and hydrogen energy. Due to increased energy demand and increased environmental pollution, hydrogen energy has been considered as one of the most promising alternatives to fossil fuels in the past decade as a clean energy carrier. Among the alternative energy carriers, hydrogen has gained much attention in the last years from the point of view of the so-called hydrogen energy economy, mainly due to its cleanliness, environmental friendliness and high calorific value of combustion.
However, in practical applications, storage and transportation of hydrogen gas remains a major problem. Since the beginning of the 21 st century, various hydrogen storage and transportation strategies have been studied. One strategy is to explore chemical hydrogen storage materials, such as NaBH 4 、KBH 4 And NH 3 BH 3 . These materials have a large hydrogen storage capacity and release pure hydrogen by hydrolysis in the presence of a catalyst at room temperature. Among the various chemical hydrides, NaBH 4 Is considered the most promising hydrogen storage material because it can produce clean H at room temperature at a very high rate 2 And non-toxic hydrolysis by-products. The principle of the method is as follows:
NaBH 4 +(2+x)H 2 O=NaBO 2 ·xH 2 O+4H 2 ΔH=-248.9KJ/mol
although borohydride has a high hydrogen storage density, the hydrolysis/pyrolysis hydrogen production reaction shows slow kinetic performance. The wide application of borohydride hydrogen production systems relies on the development of highly efficient and practical hydrogen production catalysts. Sodium borohydride does not add any catalyst at normal temperature, and the reaction rate is very slow, so sodium borohydride hydrolyzes and can be used as a good hydrogen storage material only by adding a catalyst.
The invention content is as follows:
the invention aims to solve the problems mentioned above and provides a SAPO-34 supported cobalt boride catalyst and a preparation method thereof, which are used for improving NaBH 4 The hydrogen desorption rate of.
The invention also aims to provide the SAPO-34 supported cobalt boride catalyst material for improving NaBH 4 The hydrogen release rate, the preparation process of the catalyst does not need complex design and process, other chemical reagents do not need to be added, the cost is low, and the catalyst is safe and environment-friendly.
A method for preparing SAPO-34 supported cobalt boride catalyst takes cobalt chloride hexahydrate and sodium borohydride as main raw materials, boron element is subjected to reduction reaction through strong reducibility of the sodium borohydride in a Cl ion environment to prepare cobalt boride, the reaction raw materials and a molecular sieve are mixed and stirred before reaction, the cobalt boride generated in such a way can be uniformly dispersed on the molecular sieve, the effect is more effective than that of a physical way in which ball milling is carried out to mix the cobalt boride and the molecular sieve, the whole reaction is carried out in a nitrogen environment, and the method comprises the following specific steps:
1) firstly, weighing SAPO-34 molecular sieve and CoCl by using an electronic balance 2 ·6H 2 O, putting the weighed reagent into a reaction container, adding a certain amount of water for dissolving, firstly stirring in a heat collection type constant temperature heating magnetic stirrer for 5min at the water bath temperature of 40 ℃ to ensure that the SAPO-34 molecular sieve and the CoCl are mixed 2 ·6H 2 The O is completely dissolved.
2) After stirring, moving the reaction container into an ultrasonic cleaning machine, keeping the water bath temperature at 40 ℃, starting ultrasonic vibration, and vibrating in the ultrasonic cleaning machine for 30min to ensure that the SAPO-34 molecular sieve and the CoCl are mixed 2 ·6H 2 CoCl in mixed solution of O 2 ·6H 2 And O is uniformly dispersed into the pores of the SAPO-34 molecular sieve.
3) After the ultrasonic vibration is finished, the reaction container is moved back to the heat collection type constant temperature heating magnetic stirrer to ensure thatThe water bath temperature is 40 ℃, nitrogen is introduced into the reaction vessel for protection, and NaBH is weighed 4 Dissolving with NaOH in water, transferring into constant pressure dropping funnel, opening piston to make NaBH 4 Slowly dropping the mixed solution of the SAPO-34 molecular sieve and the CoCl into the reaction vessel 2 6H2O to obtain product.
4) After the reaction is finished, the nitrogen protection is closed, and a large amount of black precipitates can appear in the reaction container through observation, so that the black precipitates obtained after the reaction is finished are continuously stirred for 1 hour in a heat collection type constant temperature heating magnetic stirrer at the temperature of 40 ℃, and the generated cobalt boride is uniformly dispersed in the molecular sieve. And after stirring, performing suction filtration on the black precipitate in the reaction container by using a circulating water type multipurpose vacuum pump, washing the black precipitate for multiple times, finally putting the precipitate obtained by separation into an air-blowing drying oven for drying for 17 hours, removing water in the catalyst, and calcining for 7 hours at the temperature of 500 ℃.
The SAPO-34 supported cobalt boride catalyst prepared by the method has the advantages of simple components, low cost, strong reusability, safety and no pollution, and can effectively improve NaBH 4 The hydrogen production efficiency is further improved, and the method is safe and pollution-free.
Drawings
FIG. 1 is a graph of hydrogen gas produced by the hydrolysis of sodium borohydride catalyzed by calcined catalysts of examples 1-6 over time.
FIG. 2 is a graph showing the amount of hydrogen produced by hydrolysis of sodium borohydride in comparative example 1 as a function of time.
FIG. 3 is a graph showing the amount of hydrogen produced by hydrolysis of sodium borohydride with SAPO-34 molecular sieve in comparative example 2 as a function of time.
FIG. 4 is an SEM secondary electron scan image of the 5 wt.% CoB/SAPO-34 catalyst of example 2.
FIG. 5 is an XRD spectrum of uncalcined cobalt boride and the catalyst prepared in this example.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the following embodiments and accompanying drawings, but the present invention is not limited thereto.
A preparation method of a cobalt boride supported SAPO-34(CoB/SAPO-34) catalyst comprises the following specific steps:
1) firstly, weighing SAPO-34 molecular sieve and CoCl by using an electronic balance 2 ·6H 2 O, putting the weighed reagent into a reaction container, adding a certain amount of water for dissolving, firstly stirring in a heat collection type constant temperature heating magnetic stirrer for 5min at the water bath temperature of 40 ℃ to ensure that the SAPO-34 molecular sieve and the CoCl are mixed 2 ·6H 2 The O was completely dissolved.
2) After stirring, moving the reaction container into an ultrasonic cleaning machine, keeping the water bath temperature at 40 ℃, starting ultrasonic vibration, and vibrating in the ultrasonic cleaning machine for 30min to ensure that the SAPO-34 molecular sieve and the CoCl are mixed 2 CoCl in 6H2O mixture solution 2 ·6H 2 The O is uniformly dispersed into the pores of the SAPO-34 molecular sieve.
3) After the ultrasonic vibration is finished, moving the reaction vessel back to the heat collection type constant temperature heating magnetic stirrer, keeping the water bath temperature at 40 ℃, introducing nitrogen into the reaction vessel for protection, and weighing NaBH 4 Dissolving with NaOH in water, transferring into constant pressure dropping funnel, opening piston to make NaBH 4 Slowly dropping the mixed solution of the SAPO-34 molecular sieve and the CoCl into the reaction vessel 2 6H2O to obtain product.
4) After the reaction is finished, the nitrogen protection is closed, and a large amount of black precipitates can appear in the reaction container through observation, so that the black precipitates obtained after the reaction is finished are continuously stirred for 1 hour in a heat collection type constant temperature heating magnetic stirrer at the temperature of 40 ℃, and the generated cobalt boride is uniformly dispersed in the molecular sieve. And after stirring, performing suction filtration on the black precipitate in the reaction container by using a circulating water type multipurpose vacuum pump, washing with water for multiple times, and finally drying the precipitate obtained by separation in a forced air drying oven for 17 hours to remove water in the catalyst.
The prepared catalyst can obtain a plurality of catalysts with different loading amounts. This example obtained the following several loadings of catalyst: 5 wt.% CoB/SAPO-34, 10 wt.% CoB/SAPO-34, 15 wt.% CoB/SAPO-34, 20 wt.% CoB/SAPO-34, 25 wt.% CoB/SAPO-34.
FIG. 5 is an XRD spectrum of uncalcined cobalt boride and the catalyst prepared in this example. a is the XRD of uncalcined cobalt boride, b is the XRD of calcined cobalt boride, c is the XRD of 5 wt.% CoB/SAPO-34, d is the XRD of 10 wt.% CoB/SAPO-34, e is the XRD of 15 wt.% CoB/SAPO-34, f is the XRD of 20 wt.% CoB/SAPO-34, and g is the XRD of 25 wt.% CoB/SAPO-34.
Example 1
Respectively weighing uncalcined cobalt boride catalyst by an electronic balance, and weighing 0.3g NaBH 4 Weighing NaBH 4 And the catalyst is moved into a three-neck flask with magnetons, water bath heating at 40 ℃ is kept, then 10ml of distilled water is added, a bottle stopper is covered, a magnetic stirring knob of a heat collection type constant temperature heating magnetic stirrer is rotated, the rotating speed is kept at 270r/min, meanwhile, a stopwatch is used for timing, the mass of discharged water is recorded every 20s, and the recording is carried out until the hydrolysis of the sodium borohydride is finished, namely, hydrogen is not generated, and the relation between the hydrogen discharge amount and the time is shown in figure 1.
Example 2
FIG. 4 is an SEM secondary electron scan image of the 5 wt.% CoB/SAPO-34 catalyst of example 2. 5 wt.% of CoB/SAPO-34 catalyst was weighed using an electronic balance, and 0.3g of NaBH was weighed 4 Weighing NaBH 4 And the catalyst is moved into a three-neck flask with magnetons, water bath heating at 40 ℃ is kept, then 10ml of distilled water is added, a bottle stopper is covered, a magnetic stirring knob of a heat collection type constant temperature heating magnetic stirrer is rotated, the rotating speed is kept at 270r/min, meanwhile, a stopwatch is used for timing, the mass of discharged water is recorded every 20s, and the recording is carried out until the hydrolysis of the sodium borohydride is finished, namely, hydrogen is not generated, and the relation between the hydrogen discharge amount and the time is shown in figure 1.
Example 3
Respectively weighing 10 wt.% of CoB/SAPO-34 catalyst by using an electronic balance, and weighing 0.3g of NaBH 4 Weighing NaBH 4 Transferring the catalyst into a three-neck flask with magnetons, heating in water bath at 40 deg.C, adding 10ml distilled water, covering with a bottle stopper, rotating the magnetic stirring knob of the heat-collecting constant-temperature heating magnetic stirrer, keeping the rotation speed at 270r/min, counting with a stopwatch, recording the mass of discharged water every 20s, and recording until sodium borohydride hydrolysis is finished, i.e. no hydrogen is generatedThe relationship between the amount of hydrogen released from the gas and the time is shown in FIG. 1.
Example 4
15 wt.% of CoB/SAPO-34 catalyst was weighed out separately with an electronic balance, and 0.3g of NaBH was weighed out 4 Weighing NaBH 4 And the catalyst is moved into a three-neck flask with magnetons, water bath heating at 40 ℃ is kept, then 10mL of distilled water is added, a bottle stopper is covered, a magnetic stirring knob of a heat collection type constant temperature heating magnetic stirrer is rotated, the rotating speed is kept at 270r/min, meanwhile, a stopwatch is used for timing, the mass of discharged water is recorded every 20s, and the recording is carried out until the hydrolysis of the sodium borohydride is finished, namely, hydrogen is not generated, and the relation between the hydrogen discharge amount and the time is shown in figure 1.
Example 5
Respectively weighing 20 wt.% of CoB/SAPO-34 catalyst by using an electronic balance, and weighing 0.3g of NaBH 4 Weighing NaBH 4 And the catalyst is moved into a three-neck flask with magnetons, water bath heating at 40 ℃ is kept, then 10mL of distilled water is added, a bottle stopper is covered, a magnetic stirring knob of a heat collection type constant temperature heating magnetic stirrer is rotated, the rotating speed is kept at 270r/min, meanwhile, a stopwatch is used for timing, the mass of discharged water is recorded every 20s, and the recording is carried out until the hydrolysis of the sodium borohydride is finished, namely, hydrogen is not generated, and the relation between the hydrogen discharge amount and the time is shown in figure 1.
Example 6
Respectively weighing 25 wt.% of CoB/SAPO-34 catalyst by using an electronic balance, and weighing 0.3g of NaBH 4 Weighing NaBH 4 And the catalyst is moved into a three-neck flask with magnetons, water bath heating at 40 ℃ is kept, then 10mL of distilled water is added, a bottle stopper is covered, a magnetic stirring knob of a heat collection type constant temperature heating magnetic stirrer is rotated, the rotating speed is kept at 270r/min, meanwhile, a stopwatch is used for timing, the mass of discharged water is recorded every 20s, and the recording is carried out until the hydrolysis of the sodium borohydride is finished, namely, hydrogen is not generated, and the relation between the hydrogen discharge amount and the time is shown in figure 1.
Comparative example 1:
0.3001g of NaBH is weighed with an electronic balance 4 Weighing NaBH 4 Transferring into a three-neck flask containing magneton, heating in water bath at 40 deg.C, and adding 10mL distilled waterCovering a bottle stopper, rotating a magnetic stirring knob of the heat collection type constant temperature heating magnetic stirrer, keeping the rotating speed at 270r/min, simultaneously timing by using a stopwatch, recording the quality of discharged water every 20s at the beginning, recording data once in 1min after the reaction is slowed down for a period of time, and timing for 2h in total. The relationship between the hydrogen release amount and time is shown in fig. 2.
Comparative example 2:
0.0205g of SAPO-34 molecular sieve and 0.3045g of NaBH are weighed by an electronic balance 4 Transferring a weighed SAPO-34 molecular sieve and sodium borohydride into a three-neck flask with magnetons, heating in water bath at 40 ℃, adding 10mL of distilled water, covering a bottle stopper, rotating a magnetic stirring knob of a heat collection type constant temperature heating magnetic stirrer, keeping the rotating speed at 270r/min, timing by using a stopwatch, recording the mass of discharged water every 20s at the beginning, recording data once in 1min after the reaction is slowed down for a period of time, and timing for 2h in total. The relationship between the hydrogen release amount and time is shown in FIG. 3.
The actual hydrogen release amount and the theoretical hydrogen release amount in the above examples are recorded in table 1:
TABLE 1 actual hydrogen release amount and theoretical hydrogen release amount
The fastest catalytic rate for sodium borohydride catalyzed by the 5 wt.% CoB/SAPO-34 catalyst can be seen in Table 1 and FIG. 1.
Claims (4)
- A preparation method of the SAPO-34 supported cobalt boride catalyst is characterized in that cobalt chloride hexahydrate and sodium borohydride are used as main raw materials to react to prepare cobalt boride, and the cobalt boride is dispersed on an SAPO-34 molecular sieve to prepare the catalyst.
- 2. The preparation method of the SAPO-34 supported cobalt boride catalyst as claimed in claim 1, which comprises the following steps:1) firstly, weighing SAPO-34 molecular sieve and CoCl by using an electronic balance 2 ·6H 2 O, putting the weighed reagent into a reaction vesselAdding a certain amount of water for dissolving, firstly stirring in a heat collection type constant temperature heating magnetic stirrer for 5min at the water bath temperature of 40 ℃ to ensure that the SAPO-34 molecular sieve and the CoCl are mixed 2 ·6H 2 Completely dissolving O;2) after stirring, the reaction vessel is moved into an ultrasonic cleaning machine, the water bath temperature is kept at 40 ℃, ultrasonic vibration is started, and vibration is carried out in the ultrasonic cleaning machine for 30min to ensure that the SAPO-34 molecular sieve and the CoCl are mixed 2 ·6H 2 CoCl in mixed solution of O 2 ·6H 2 O is uniformly dispersed into the pores of the SAPO-34 molecular sieve;3) after the ultrasonic vibration is finished, moving the reaction vessel back to a heat collection type constant temperature heating magnetic stirrer, keeping the water bath temperature at 40 ℃, introducing nitrogen into the reaction vessel for protection, and weighing NaBH at the same time 4 Dissolving with NaOH in water, transferring into constant pressure dropping funnel, and opening piston to make NaBH 4 Slowly dropping the mixed solution of the SAPO-34 molecular sieve and the CoCl into the reaction vessel 2 ·6H 2 Reacting in the mixed solution of O to prepare a product;4) after the reaction is finished, closing the nitrogen protection, observing that a large amount of black precipitates can appear in the reaction container, and continuously stirring the black precipitates obtained after the reaction is finished in a heat collection type constant temperature heating magnetic stirrer at 40 ℃ for 1 hour to uniformly disperse the generated cobalt boride into a molecular sieve; and after stirring, carrying out suction filtration on the black precipitate in the reaction container by using a circulating water type multi-purpose vacuum pump, washing with water for multiple times, and finally drying the precipitate obtained by separation in an air-blast drying oven for 17 hours to remove water in the catalyst.
- SAPO-34 supported cobalt boride catalyst, characterized by being obtainable by the preparation method according to claim 1 or 2.
- 4. Use of a SAPO-34 supported cobalt boride catalyst according to claim 3 for improving NaBH 4 And (4) hydrolyzing and releasing hydrogen.
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Citations (2)
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CN103691480A (en) * | 2014-01-15 | 2014-04-02 | 辽宁石油化工大学 | Preparation technology of catalyst used for preparing hydrogen by hydrolyzing sodium borohydride |
CN113976120A (en) * | 2021-11-30 | 2022-01-28 | 西安工业大学 | Preparation method of high-activity CoB catalyst |
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Patent Citations (2)
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CN103691480A (en) * | 2014-01-15 | 2014-04-02 | 辽宁石油化工大学 | Preparation technology of catalyst used for preparing hydrogen by hydrolyzing sodium borohydride |
CN113976120A (en) * | 2021-11-30 | 2022-01-28 | 西安工业大学 | Preparation method of high-activity CoB catalyst |
Non-Patent Citations (1)
Title |
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孙海杰等: "自搅拌下CoB/SiO2催化剂催化硼氢化钠水解制氢研究", 《无机盐工业》, vol. 52, no. 3, pages 101 - 106 * |
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