CN109622009A - With Pd@CeO2-CNxThe method of core-shell catalyst catalysis formaldehyde dehydrogenation - Google Patents
With Pd@CeO2-CNxThe method of core-shell catalyst catalysis formaldehyde dehydrogenation Download PDFInfo
- Publication number
- CN109622009A CN109622009A CN201811488314.5A CN201811488314A CN109622009A CN 109622009 A CN109622009 A CN 109622009A CN 201811488314 A CN201811488314 A CN 201811488314A CN 109622009 A CN109622009 A CN 109622009A
- Authority
- CN
- China
- Prior art keywords
- cnx
- core
- ceo
- shell catalyst
- mof
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000011258 core-shell material Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 12
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 11
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 44
- 238000005119 centrifugation Methods 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 30
- 238000001035 drying Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Pd@CeO is used the invention discloses a kind of2The method of-CNx core-shell catalyst catalysis formaldehyde dehydrogenation.The catalyst prepared is placed in reactor by the present invention, and reactor is placed in water-bath, and then formaldehyde and sodium hydroxide mixed liquor are added in reactor and react, and the hydrogen of generation is collected using drainage.The Pd@CeO2The synthesis of-CNx core-shell catalyst is as follows: a) cerous nitrate and 2-methylimidazole being dissolved in methanol solution and form uniform solution, is centrifuged after stirring under room temperature and obtains (Ce) MOF；B) Na is dispersed by (Ce) MOF2PdCl4It in solution, is restored after being sufficiently stirred using sodium borohydride solution, obtains Pd@(Ce) MOF；C) Pd@(Ce) MOF is transferred to tube-type atmosphere furnace, Pd@CeO is made after roasting under gaseous mixture2- CNx core-shell catalyst.The high activity for formaldehyde dehydrogenation hydrogen, highly selective and high stability Pd@CeO can be made by adjusting the molar ratio of metal Pd in catalyst, Ce, CNx in the present invention2- CNx core-shell catalyst.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, and in particular to a kind of to use Pd@CeO2The catalysis of-CNx core-shell catalyst
The method of formaldehyde dehydrogenation.
Background technique
The energy is one of the major impetus of human development and social progress.The increasingly exhausted and its combustion of traditional fossil energy
Serious environmental problem is caused largely to limit the high speed development of society after burning.Therefore, seeking efficient clean can be again
The raw energy is imperative for future social development, very urgent.
Hydrogen Energy has many advantages, such as that from a wealth of sources, calorific value is high, product is pollution-free, it is considered to be the ideal energy of the following human development
One of source.Since hydrogen has very low volume energy density and mass energy density and more difficult liquefaction, largely limit
Therefore its large-scale application as the energy seeks safe and efficient ground hydrogen storage technology and is expected to push its as cleaning energy
The large-scale application in source.Formaldehyde mass energy density with higher, and being in a liquid state at room temperature, can safely store and
Transport.Importantly, formaldehyde is hydrogen and carbon dioxide by the product that hydrolysis/dehydrogenation reaction generates, to the nothing of fuel cell
Detrimental effect, be particularly suitable as hydrogen fuel cell for hydrogen carrier.
For formaldehyde as hydrogen fuel cell for one of hydrogen carrier, the key of current research is the hydrolysis/dehydrogenation catalysis of synthesizing efficient
Agent, constructing, there is the palladium-based catalyst of composite construction to be expected to the undesirable problem of the existing catalyst effect of very good solution.
Summary of the invention
Pd@CeO is used in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of2- CNx core-shell catalyst is urged
Change the method for formaldehyde dehydrogenation, the Pd@CeO2- CNx is hud typed to realize the complete dehydrogenation of formaldehyde, the catalyst under the conditions of relatively mild
With good catalytic activity, selectivity and stability.
The technical solution adopted by the present invention to solve the technical problems is as follows.
The Pd@CeO that will be prepared2- CNx core-shell catalyst is placed in reactor, and reactor is placed in water-bath and is heated up
Be then 1:(0.5~1.6 by molar ratio to 5~30 DEG C) formaldehyde and sodium hydroxide mixed liquor be added in reactor carry out it is anti-
It answers, obtains hydrogen product；
The Pd@CeO2- CNx core-shell catalyst includes Pd, Ce, CNx, wherein Pd derives from chlorine palladium acid sodium, and Ce comes
Derived from cerous nitrate, CNx derives from 2-methylimidazole；
The catalyst and mixed liquor mass ratio is 1:(80~150)；
The Pd@CeO2- CNx core-shell catalyst is through the following steps that prepared:
Step (1) cerous nitrate and 2-methylimidazole are dissolved in methanol solution by certain mass ratio formed it is uniform mixing it is molten
Liquid, stirs certain time at normal temperature, and centrifugation obtains (Ce) MOF；
(Ce) MOF is dispersed Na by step (2)2PdCl4In solution, after being sufficiently stirred, at a certain temperature using certain dense
The sodium borohydride solution of degree restores certain time, obtains Pd@(Ce) MOF；
Pd@(Ce) MOF is transferred to tube-type atmosphere furnace by step (3), roasts certain time under the gaseous mixture of definite composition,
Obtain Pd@CeO2- C core-shell catalyst.
Further, the Pd@CeO2In the preparation step (1) of-CNx core-shell catalyst: cerous nitrate, 2- methyl miaow
The mass ratio of azoles is 1:(5~8).
Further, the Pd@CeO2In the preparation step (2) of-CNx core-shell catalyst: chlorine palladium acid sodium and step
(1) mass ratio of cerous nitrate is 1:(4~6 in), sodium borohydride solution concentration is 0.1mol/L~0.3mol/L, reduction temperature
It is -5~5 DEG C, the recovery time is 4~12h.
Further, the Pd@CeO2In the preparation step (3) of-CNx core-shell catalyst: tube-type atmosphere furnace roasting
Temperature is 240~320 DEG C, 2~4h of calcining time, and gaseous mixture atmosphere is O2/N2, wherein O2Volume group become 1%~5%.
Compared with prior art, the beneficial effects of the present invention are:
It is molten by certain mass ratio to be dissolved in methanol using dipping reduction roasting method by the present invention for cerous nitrate and 2-methylimidazole
Uniform solution is formed in liquid, certain time is stirred at room temperature, and centrifugation obtains (Ce) MOF；Na is dispersed by (Ce) MOF2PdCl4
It in solution, after being sufficiently stirred, is restored using sodium borohydride solution, obtains Pd@(Ce) MOF, a certain amount of Pd@(Ce) MOF is turned
Tube-type atmosphere furnace is moved to, roasts certain time under the gaseous mixture of definite composition, obtains Pd@CeO2The hud typed catalysis of-CNx
Agent, the catalyst activity, selectivity and stability with higher.Formaldehyde dehydrogenation reaction is carried out using the catalyst, dehydrogenation turns
Rate and selectivity are 100%, and the TOF value of reaction is greater than 280h-1, 2h is recycled, the TOF value of reaction is still greater than 270h-1。
Specific implementation method
The present invention is described in further details below by embodiment.But the example is not constituted to limit of the invention
System.
Embodiment 1
Prepare catalyst process
0.6g cerous nitrate and 3.0g 2-methylimidazole are dissolved in 200mL methanol solution and form uniform solution, in room temperature
Lower stirring certain time, centrifugation obtain (Ce) MOF；(Ce) MOF the and 0.1g Na that centrifugation is obtained2PdCl4100mL is scattered in go
In ionized water, 0.1mol/L sodium borohydride solution is added dropwise in Xiang Shangshu solution, restores 4h at 5 DEG C, centrifugal drying obtains Pd
(Ce)MOF；Obtained Pd@(Ce) MOF is transferred to tube-type atmosphere furnace, in 5%O2/N2Under atmosphere, 320 DEG C of roasting 4h are obtained
Pd@6(CeO2- 5CNx) core-shell catalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 5 DEG C, formaldehyde and sodium hydroxide mixed liquor 4g that molar ratio is 1:0.5 is added dropwise thereto, collects reaction gas, is measured after reaction
The selectivity of hydrogen is 100%, and the conversion ratio of formaldehyde is 100%, and the TOF value of reaction is 286h-1, 2h is recycled, reaction
TOF value is still greater than 280h-1。
Embodiment 2
Prepare catalyst process
0.4g cerous nitrate and 3.2g 2-methylimidazole are dissolved in 200mL methanol solution and form uniform solution, in room temperature
Lower stirring certain time, centrifugation obtain (Ce) MOF；(Ce) MOF the and 0.1g Na that centrifugation is obtained2PdCl4100mL is scattered in go
In ionized water, 0.3mol/L sodium borohydride solution is added dropwise in Xiang Shangshu solution, 12h is restored at -5 DEG C, centrifugal drying obtains
Pd@(Ce)MOF；Obtained Pd@(Ce) MOF is transferred to tube-type atmosphere furnace, in 1%O2/N2Under atmosphere, 240 DEG C of roasting 2h, i.e.,
4 (CeO of Pd@is made2- 8CNx) core-shell catalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 30 DEG C, formaldehyde and sodium hydroxide mixed liquor 7.5g that molar ratio is 1:1.6 is added dropwise thereto, reaction gas is collected, after reaction
The selectivity for measuring hydrogen is 100%, and the conversion ratio of formaldehyde is 100%, and the TOF value of reaction is 320h-1, 2h is recycled, instead
The TOF value answered is still greater than 310h-1。
Embodiment 3
Prepare catalyst process
0.5g cerous nitrate and 3.5g 2-methylimidazole are dissolved in 200mL methanol solution and form uniform solution, in room temperature
Lower stirring certain time, centrifugation obtain (Ce) MOF；(Ce) MOF the and 0.1g Na that centrifugation is obtained2PdCl4100mL is scattered in go
In ionized water, 0.1mol/L sodium borohydride solution is added dropwise in Xiang Shangshu solution, 8h is restored at -2 DEG C, centrifugal drying obtains
Pd@(Ce)MOF；Obtained Pd@(Ce) MOF is transferred to tube-type atmosphere furnace, in 3%O2/N2Under atmosphere, 280 DEG C of roasting 3h, i.e.,
5 (CeO of Pd@is made2- 7CNx) core-shell catalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 25 DEG C, formaldehyde and sodium hydroxide mixed liquor 5g that molar ratio is 1:0.8 is added dropwise thereto, collects reaction gas, is surveyed after reaction
The selectivity for obtaining hydrogen is 100%, and the conversion ratio of formaldehyde is 100%, and the TOF value of reaction is 480h-1, 2h, reaction is recycled
TOF value be still greater than 470h-1。
Embodiment 4
Prepare catalyst process
0.5g cerous nitrate and 2.5g 2-methylimidazole are dissolved in 200mL methanol solution and form uniform solution, in room temperature
Lower stirring certain time, centrifugation obtain (Ce) MOF；(Ce) MOF the and 0.1g Na that centrifugation is obtained2PdCl4100mL is scattered in go
In ionized water, 0.15mol/L sodium borohydride solution is added dropwise in Xiang Shangshu solution, 9h is restored at -1 DEG C, centrifugal drying obtains
Pd@(Ce)MOF；Obtained Pd@(Ce) MOF is transferred to tube-type atmosphere furnace, in 2%O2/N2Under atmosphere, 260 DEG C of roasting 2.5h,
Obtain 5 (CeO of Pd@2- 5CNx) core-shell catalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 15 DEG C, formaldehyde and sodium hydroxide mixed liquor 6g that molar ratio is 1:0.7 is added dropwise thereto, collects reaction gas, is surveyed after reaction
The selectivity for obtaining hydrogen is 100%, and the conversion ratio of formaldehyde is 100%, and the TOF value of reaction is 360h-1, 2h, reaction is recycled
TOF value be still greater than 350h-1。
Embodiment 5
Prepare catalyst process
0.6g cerous nitrate and 4.2g 2-methylimidazole are dissolved in 200mL methanol solution and form uniform solution, in room temperature
Lower stirring certain time, centrifugation obtain (Ce) MOF；(Ce) MOF the and 0.1g Na that centrifugation is obtained2PdCl4100mL is scattered in go
In ionized water, 0.25mol/L sodium borohydride solution is added dropwise in Xiang Shangshu solution, 6h is restored at 2 DEG C, centrifugal drying obtains
Pd@(Ce)MOF；Obtained Pd@(Ce) MOF is transferred to tube-type atmosphere furnace, in 4%O2/N2Under atmosphere, 310 DEG C of roasting 2h, i.e.,
6 (CeO of Pd@is made2- 7CNx) core-shell catalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 10 DEG C, formaldehyde and sodium hydroxide mixed liquor 7g that molar ratio is 1:1.5 is added dropwise thereto, collects reaction gas, is surveyed after reaction
The selectivity for obtaining hydrogen is 100%, and the conversion ratio of formaldehyde is 100%, and the TOF value of reaction is 320h-1, 2h, reaction is recycled
TOF value be still greater than 314h-1。
Embodiment 6
Prepare catalyst process
0.4g cerous nitrate and 2.4g 2-methylimidazole are dissolved in 200mL methanol solution and form uniform solution, in room temperature
Lower stirring certain time, centrifugation obtain (Ce) MOF；(Ce) MOF the and 0.1g Na that centrifugation is obtained2PdCl4100mL is scattered in go
In ionized water, 0.3mol/L sodium borohydride solution is added dropwise in Xiang Shangshu solution, 5h is restored at 3 DEG C, centrifugal drying obtains Pd
(Ce)MOF；Obtained Pd@(Ce) MOF is transferred to tube-type atmosphere furnace, in 2%O2/N2Under atmosphere, 270 DEG C of roasting 2.3h make
Obtain 4 (CeO of Pd@2- 6CNx) core-shell catalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 20 DEG C, formaldehyde and sodium hydroxide mixed liquor 5.5g that molar ratio is 1:1.2 is added dropwise thereto, reaction gas is collected, after reaction
The selectivity for measuring hydrogen is 100%, and the conversion ratio of formaldehyde is 100%, and the TOF value of reaction is 290h-1, 2h is recycled, instead
The TOF value answered is still greater than 284h-1。
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
A specific embodiment of the invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not taking off
Under the premise of from present inventive concept, several simple deductions and replacement can also be made, all shall be regarded as belonging to the present invention by institute
Claims of submission determine the protection scope of patent.
Claims (6)
1. using Pd@CeO2The method of-CNx core-shell catalyst catalysis formaldehyde dehydrogenation, it is characterised in that the Pd@CeO that will be prepared2-
CNx core-shell catalyst is placed in reactor, and reactor is placed in water-bath and is warming up to 5~30 DEG C, is then 1 by molar ratio:
The formaldehyde and sodium hydroxide mixed liquor of (0.5~1.6), which are added in reactor, to be reacted, and hydrogen product is obtained；
The Pd@CeO2- CNx core-shell catalyst includes Pd, Ce, CNx, wherein Pd derives from chlorine palladium acid sodium, and Ce is derived from
Cerous nitrate, CNx derive from 2-methylimidazole.
2. according to claim 1 use Pd@CeO2The method that-CNx core-shell catalyst is catalyzed formaldehyde dehydrogenation, feature exist
In the catalyst and mixed liquor mass ratio be 1:(80~150).
3. using Pd@CeO according to of any of claims 1 or 22The method that-CNx core-shell catalyst is catalyzed formaldehyde dehydrogenation, feature exist
In the Pd@CeO2- CNx core-shell catalyst is through the following steps that prepared:
Cerous nitrate and 2-methylimidazole are dissolved in methanol solution by certain mass ratio and form uniform mixed solution by step (1),
Certain time is stirred at normal temperature, and centrifugation obtains (Ce) MOF；
(Ce) MOF is dispersed Na by step (2)2PdCl4In solution, after being sufficiently stirred, at a certain temperature using certain density
Sodium borohydride solution restores certain time, obtains Pd@(Ce) MOF；
Pd@(Ce) MOF is transferred to tube-type atmosphere furnace by step (3), and certain time is roasted under the gaseous mixture of definite composition, that is, is made
Obtain Pd@CeO2- C core-shell catalyst.
4. using Pd@CeO according to as claimed in claim 32The method of-CNx core-shell catalyst catalysis formaldehyde dehydrogenation, it is characterised in that
The Pd@CeO2In the preparation step (1) of-CNx core-shell catalyst: cerous nitrate, 2-methylimidazole mass ratio be 1:(5
~8).
5. using Pd@CeO according to as claimed in claim 42The method of-CNx core-shell catalyst catalysis formaldehyde dehydrogenation, it is characterised in that
The Pd@CeO2In the preparation step (2) of-CNx core-shell catalyst: the quality of cerous nitrate in chlorine palladium acid sodium and step (1)
Than for 1:(4~6), sodium borohydride solution concentration is 0.1mol/L~0.3mol/L, and reduction temperature is -5~5 DEG C, the recovery time
For 4~12h.
6. using Pd@CeO according to described in claim 52The method of-CNx core-shell catalyst catalysis formaldehyde dehydrogenation, it is characterised in that
The Pd@CeO2In the preparation step (3) of-CNx core-shell catalyst: tube-type atmosphere furnace maturing temperature is 240~320 DEG C,
2~4h of calcining time, gaseous mixture atmosphere are O2/N2, wherein O2Volume group become 1%~5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811488314.5A CN109622009B (en) | 2018-12-06 | 2018-12-06 | With Pd @ CeO2-CNxMethod for catalyzing formaldehyde dehydrogenation by core-shell catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811488314.5A CN109622009B (en) | 2018-12-06 | 2018-12-06 | With Pd @ CeO2-CNxMethod for catalyzing formaldehyde dehydrogenation by core-shell catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109622009A true CN109622009A (en) | 2019-04-16 |
| CN109622009B CN109622009B (en) | 2020-09-04 |
Family
ID=66071790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811488314.5A Active CN109622009B (en) | 2018-12-06 | 2018-12-06 | With Pd @ CeO2-CNxMethod for catalyzing formaldehyde dehydrogenation by core-shell catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109622009B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110523424A (en) * | 2019-08-15 | 2019-12-03 | 广西师范大学 | One kind being based on Ru/NPC-CoxO catalyst for preparing hydrogen and preparation method |
| CN112916000A (en) * | 2021-01-15 | 2021-06-08 | 兰州大学 | Photocatalytic material for reducing nitrogen to produce ammonia and preparation method and application thereof |
| CN113426483A (en) * | 2021-05-13 | 2021-09-24 | 浙江工商大学 | GQDs/Ce-2MI composite photocatalytic bactericide and preparation and application thereof |
| US20220119270A1 (en) * | 2020-10-16 | 2022-04-21 | Research & Business Foundation Sungkyunkwan University | Ceria nanoparticles and ceria nanoparticles preparation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8691716B2 (en) * | 2006-04-18 | 2014-04-08 | Breton S.P.A. | Electrocatalysts based on mono/plurimetallic carbon nitrides for fuel cells fueled with hydrogen |
| CN105244513A (en) * | 2015-09-28 | 2016-01-13 | 南京理工大学 | Graphite-phase carbon nitride-modified carbon black-loaded platinum-palladium alloy nano electrocatalyst and preparation method |
| CN106552661A (en) * | 2016-10-28 | 2017-04-05 | 中南民族大学 | A kind of nitrogen-doped carbon material load cobalt catalyst and the method for preparing aminated compoundss using its catalytic hydrogenating reduction amination |
| CN106694020A (en) * | 2016-12-28 | 2017-05-24 | 安徽工业大学 | Method for catalyzing hydrazine hydrate dehydrogenation by using supported Rh/CeO2@C3N4 nano-catalyst |
| CN106914262A (en) * | 2017-02-07 | 2017-07-04 | 江南大学 | A kind of nitrogen-doped carbon nano-noble-metal-loaded catalyst |
| CN108855069A (en) * | 2018-06-19 | 2018-11-23 | 华侨大学 | A kind of nano bar-shape Pt/CeO2The preparation method of loaded catalyst and the application in CO catalysis reaction |
-
2018
- 2018-12-06 CN CN201811488314.5A patent/CN109622009B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8691716B2 (en) * | 2006-04-18 | 2014-04-08 | Breton S.P.A. | Electrocatalysts based on mono/plurimetallic carbon nitrides for fuel cells fueled with hydrogen |
| CN105244513A (en) * | 2015-09-28 | 2016-01-13 | 南京理工大学 | Graphite-phase carbon nitride-modified carbon black-loaded platinum-palladium alloy nano electrocatalyst and preparation method |
| CN106552661A (en) * | 2016-10-28 | 2017-04-05 | 中南民族大学 | A kind of nitrogen-doped carbon material load cobalt catalyst and the method for preparing aminated compoundss using its catalytic hydrogenating reduction amination |
| CN106694020A (en) * | 2016-12-28 | 2017-05-24 | 安徽工业大学 | Method for catalyzing hydrazine hydrate dehydrogenation by using supported Rh/CeO2@C3N4 nano-catalyst |
| CN106914262A (en) * | 2017-02-07 | 2017-07-04 | 江南大学 | A kind of nitrogen-doped carbon nano-noble-metal-loaded catalyst |
| CN108855069A (en) * | 2018-06-19 | 2018-11-23 | 华侨大学 | A kind of nano bar-shape Pt/CeO2The preparation method of loaded catalyst and the application in CO catalysis reaction |
Non-Patent Citations (1)
| Title |
|---|
| TAO FENG，ET AL: "Pd nanoparticles supported on CeO2 as efficient catalyst for hydrogen generation from formaldehyde solution at room temperature", 《APPL ORGANOMETAL CHEM.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110523424A (en) * | 2019-08-15 | 2019-12-03 | 广西师范大学 | One kind being based on Ru/NPC-CoxO catalyst for preparing hydrogen and preparation method |
| CN110523424B (en) * | 2019-08-15 | 2021-09-07 | 广西师范大学 | Catalyst for hydrogen production based on Ru/NPC-CoxO and preparation method thereof |
| US20220119270A1 (en) * | 2020-10-16 | 2022-04-21 | Research & Business Foundation Sungkyunkwan University | Ceria nanoparticles and ceria nanoparticles preparation method |
| CN112916000A (en) * | 2021-01-15 | 2021-06-08 | 兰州大学 | Photocatalytic material for reducing nitrogen to produce ammonia and preparation method and application thereof |
| CN113426483A (en) * | 2021-05-13 | 2021-09-24 | 浙江工商大学 | GQDs/Ce-2MI composite photocatalytic bactericide and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109622009B (en) | 2020-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109622009A (en) | With Pd@CeO2-CNxThe method of core-shell catalyst catalysis formaldehyde dehydrogenation | |
| CN106694020B (en) | With support type Rh/CeO2@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| CN105217568A (en) | A kind of loading type Ag-Pd/C 3n 4the method of nanocatalyst catalysis formate dehydrogenase | |
| CN106744677B (en) | Use RhNiCo/CeO2@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| CN106694008B (en) | With support type RhNi/CeO2@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| CN109529935A (en) | With the method for Pd@CoO-CNx core-shell catalyst catalysis formaldehyde dehydrogenation | |
| CN106672899A (en) | Method for catalyzing hydrazine hydrate dehydrogenation with RhNiFe/CeO2@C3N4 nanometer catalyst | |
| CN110075848A (en) | The catalyst and preparation that are removed for non-methane total hydrocarbons in total hydrocarbon and application | |
| CN109876841A (en) | A kind of method of 2- amino terephthalic acid (TPA) and amine compounds combined polymerization preparation graphite phase carbon nitride visible light catalyst | |
| CN106362720B (en) | A kind of dehydrogenation catalyst with core-shell structure, preparation method and application | |
| CN105197886A (en) | Method for catalyzing formic acid for dehydrogenation by use of supported Au-Pd/mpg-C3N4 nano-catalyst | |
| CN109999878A (en) | For photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof | |
| CN114887625A (en) | Fe-based metal organic framework material derived catalyst and preparation method and application thereof | |
| Luciani et al. | Syngas production through H2O/CO2 thermochemical splitting over doped ceria-zirconia materials | |
| CN113318745A (en) | Preparation method of hydrogen-rich catalyst for biomass pyrolysis | |
| CN101537374A (en) | Method for protecting reforming catalyst of molten carbonate fuel cell and applications thereof | |
| CN105688997A (en) | High-selectivity catalyst and preparation method thereof | |
| CN109665493A (en) | With the method for NiPd/ porous C exCuyOz nanocatalyst catalysis formaldehyde dehydrogenation | |
| CN106045948A (en) | Method for preparing 5-hydroxymethyl furfural by CO2-liquid water system | |
| CN102533367B (en) | System and method for catalytic combustion deoxidation of methane gas | |
| CN106586954B (en) | Use RhNiFe/CeO2@P@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| KR101842581B1 (en) | Stand-alone Heat-exchanger Type Modular Self-sustaining Reformer | |
| CN109433226A (en) | With the method for NiAgPt/ porous C exCoyOz nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| CN111167465A (en) | Nickel molybdate nano catalyst and preparation method and application thereof | |
| CN109622010A (en) | With the method for Pd@CNx mosaic catalyst formaldehyde dehydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |