CN109748240A - With the method for CuAgPd/ porous C exCoyOz nanocatalyst catalysis formaldehyde dehydrogenation - Google Patents
With the method for CuAgPd/ porous C exCoyOz nanocatalyst catalysis formaldehyde dehydrogenation Download PDFInfo
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- CN109748240A CN109748240A CN201910048334.9A CN201910048334A CN109748240A CN 109748240 A CN109748240 A CN 109748240A CN 201910048334 A CN201910048334 A CN 201910048334A CN 109748240 A CN109748240 A CN 109748240A
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Abstract
The invention discloses a kind of methods with the catalysis formaldehyde dehydrogenation of CuAgPd/ porous C exCoyOz nanocatalyst, belong to technical field of chemistry and chemical engineering.The nanocatalyst prepared is placed in reactor by the present invention, and reactor is placed in water-bath and rises to certain temperature, and then formaldehyde and sodium hydroxide mixed liquor are added in reactor and react, and the hydrogen of generation is collected using drainage.Unlike existing catalyst: according to the present invention, adjusting Ni metal in catalyst, the high activity for formaldehyde dehydrogenation hydrogen, highly selective, high stability nanocatalyst can be made in the molar ratio of mole when support precursor cerous nitrate, cobalt nitrate and 2-methylimidazole of Ag, Pd.Formaldehyde dehydrogenation reaction is carried out using the catalyst, conversion rate of dehydrogenation and selectivity are 100%, and the TOF value of reaction is greater than 490h‑1, 4h is recycled, the TOF value of reaction is still greater than 484h‑1。
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, and in particular to be urged with CuAgPd/ porous C exCoyOz nanocatalyst
Change the method for formaldehyde dehydrogenation.
Background technique
Hydrogen is known as the cleaning green energy resource of 21 century because its energy density is high, product advantages of environment protection.In view of
The deficiencies of density of hydrogen is low, difficult liquefaction, developing efficient hydrogen storage technology is the key that realize hydrogen energy source large-scale application.
M.Trincado et al. (Nature Communications 2017,8:14990) is prepared for matching for Ru for the first time
Object is closed as homogeneous catalyst, is catalyzed formaldehyde high-efficiency dehydrogenation, the report of the paper opens the storage using formaldehyde as hydrogen storage carrier
Hydrogen technical research.But homogeneous catalyst after the completion of reaction cannot separate catalyst from reaction system, cannot recycle makes
With being unfavorable for applying on a large scale.In consideration of it, developing efficient heterogeneous dehydrogenation for promoting formaldehyde dehydrogenating technology to exist
Application in hydrogen fuel cell is of great significance.
Chun Wang et al. (Appl.Organometal.Chem.2017,31:3889) reports Pd/CeO2Catalysis
The synthesis of agent and its application as dehydrogenation in formaldehyde certain embodiments.The catalyst shows excellent catalyst performance
Energy.That rare precious metals, resource reserve are limited in view of Pd, how to be reduced using cheap metal the cost of catalyst synthesis for
Promoting formic acid, the large-scale application in hydrogen fuel cell is most important as hydrogen storage material.Chun Wang et al.
(Catal.Commun.2018,113:10-14) further devises AgPd/BC catalyst, and it is anti-to be applied to formaldehyde dehydrogenation
Ying Zhong is that resource reserve is limited and be rare precious metals in view of Ag, Pd, how to reduce the usage amount of noble metal and improve catalyst
Catalytic performance be current research hot spot.
Summary of the invention
It is urged in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of with exCoyOz nanometers of CuAgPd/ porous C
The method that agent is catalyzed formaldehyde dehydrogenation, it is real under the conditions of relatively mild to the CuAgPd/ porous C exCoyOz nanocatalyst
The existing complete dehydrogenation of formaldehyde.
The technical solution adopted by the present invention to solve the technical problems is as follows.
The CuAgPd/ porous C exCoyOz nanocatalyst prepared is placed in reactor, reactor is placed in water-bath
In rise to -10~20 DEG C, then by molar ratio be 1:(0.8~1.5) formaldehyde and sodium hydroxide mixed liquor be added reactor in
It is reacted, obtains hydrogen product；The catalyst and mixed liquor mass ratio is 1:(130~180).
The CuAgPd/ porous C exCoyOz nanocatalyst includes Cu, Ag, Pd and porous C exCoyOz, wherein Cu
From copper nitrate, Ag derives from silver nitrate, and Pd derives from potassium chloropalladate, and porous C exCoyOz is by cerous nitrate and cobalt nitrate and 2-
Methylimidazole forms Ce-Co-MOF roasting and is made, and the molar ratio of copper nitrate, silver nitrate and potassium chloropalladate is 1:(0.2~0.4):
(0.1~0.3)；The molar ratio of copper nitrate and cerous nitrate, cobalt nitrate, 2-methylimidazole is 1:(2~4): (4~6): (23~
32)。
The CuAgPd/ porous C exCoyOz nanocatalyst is through the following steps that prepared:
(1) cerous nitrate, cobalt nitrate and 2-methylimidazole are dissolved in methanol solution and form uniform solution, at 22~34 DEG C
18~27h of lower stirring, centrifugation obtain Ce-Co-MOF；
(2) Ce-Co-MOF is transferred to tube furnace, roasting obtains porous C exCoyOz；
(3) the porous C exCoyOz that roasting obtains is placed in copper nitrate, silver nitrate and potassium chloropalladate solution, at -5~0 DEG C
Lower to restore 1.5~4h using ammonia Borane solution, centrifugal drying obtains CuAgPd/ porous C exCoyOz nanocatalyst.
Further, in the preparation step (2) of the CuAgPd/ porous C exCoyOz nanocatalyst: tube furnace roasting
Burning temperature is 510~560 DEG C, 3.5~7h of calcining time, calcination atmosphere O2/N2, wherein O2Volume accounting be 12%~
16%.
Further, in the preparation step (3) of the CuAgPd/ porous C exCoyOz nanocatalyst: ammonia borine is dense
Degree is 0.33~0.52mol/L.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention uses immersion reduction method synthetic catalyst that is easy to operate, being easy to industrial applications, catalyst carrier
Preparation is presoma using cerous nitrate cheap and easy to get, cobalt nitrate and 2-methylimidazole, and it is molten to be dissolved in methanol by certain mol proportion
Uniform solution is formed in liquid, reacts certain time under mild reaction conditions, centrifugation obtains Ce-Co-MOF, by Ce-Co-MOF
It is transferred to tube furnace, roasting obtains porous C exCoyOz under certain roasting condition and atmosphere, roasting is obtained porous
CexCoyOz is placed in the copper nitrate, silver nitrate and potassium chloropalladate solution of definite composition, uses ammonia Borane solution in a mild condition
Reduction a period of time, centrifugal drying obtain the CuAgPd/ porous C exCoyOz nano-catalytic with high dispersancy nano particle
Agent.
2, CuAgPd/ porous C exCoyOz nanocatalyst PARA FORMALDEHYDE PRILLS(91,95) dehydrogenation reaction activity with higher, selectivity
And stability.Formaldehyde dehydrogenation under temperate condition can be realized using the catalyst, and conversion rate of dehydrogenation and selectivity are 100%, instead
The TOF value answered is greater than 490h-1, 4h is recycled, the TOF value of reaction is still greater than 484h-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
2mmol cerous nitrate, 4mmol cobalt nitrate and 23mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 27h at 22 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, roasts at 510 DEG C
Time 7h, calcination atmosphere 16%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in and is contained
In 1mmol copper nitrate, 0.2mmol silver nitrate and 0.3mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.33mol/L 0
DEG C reduction 1.5h, obtain catalyst, be denoted as CuAg0.2Pd0.3/ porous C e2Co4Oz nanocatalyst, 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 6.5g that molar ratio is 1:0.8 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 550h-1, 4h is recycled, instead
The TOF value answered is still greater than 544h-1。
Embodiment 2
Prepare catalyst process
4mmol cerous nitrate, 6mmol cobalt nitrate and 32mmol2- methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 18h at 34 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, roasts at 560 DEG C
Time 3.5h, calcination atmosphere 12%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in and is contained
In 1mmol copper nitrate, 0.4mmol silver nitrate and 0.1mmol potassium chloropalladate solution, using 0.52mol/L ammonia Borane solution-
5 DEG C of reduction 1.5h, obtain catalyst, are denoted as CuAg0.4Pd0.1/ porous C e4Co6Oz nanocatalyst, 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 9g 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 780h-1, 4h, reaction is recycled
TOF value be still greater than 773h-1。
Embodiment 3
Prepare catalyst process
3mmol cerous nitrate, 5mmol cobalt nitrate and 27mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 26h at 32 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, roasts at 535 DEG C
Time 6.5h, calcination atmosphere 15%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in and is contained
In 1mmol copper nitrate, 0.3mmol silver nitrate and 0.2mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.40mol/L 0
DEG C reduction 4h, obtain catalyst, be denoted as CuAg0.3Pd0.2/ porous C e3Co5Oz nanocatalyst, 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 7.5g 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 623h-1, 4h is recycled, instead
The TOF value answered is still greater than 617h-1。
Embodiment 4
Prepare catalyst process
2mmol cerous nitrate, 5mmol cobalt nitrate and 27mmol2- methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 23h at 31 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, roasts at 525 DEG C
Time 5.5h, calcination atmosphere 13%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in and is contained
In 1mmol copper nitrate, 0.2mmol silver nitrate and 0.3mmol potassium chloropalladate solution, using 0.38mol/L ammonia Borane solution-
2 DEG C of reduction 3.5h, obtain catalyst, are denoted as CuAg0.2Pd0.3/ porous C e2Co5Oz nanocatalyst, 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 8 DEG C, formaldehyde and sodium hydroxide mixed liquor 8.5g that molar ratio is 1:0.9 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 576h-1, 4h, reaction is recycled
TOF value be still greater than 571h-1。
Embodiment 5
Prepare catalyst process
3mmol cerous nitrate, 4mmol cobalt nitrate and 23mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 23h at 25 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, roasts at 535 DEG C
Time 5.5h, calcination atmosphere 14%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in and is contained
In 1mmol copper nitrate, 0.2mmol silver nitrate and 0.2mmol potassium chloropalladate solution, using 0.49mol/L ammonia Borane solution-
2 DEG C of reductase 12 .5h, obtain catalyst, are denoted as CuAg0.2Pd0.2/ porous C e3Co4Oz nanocatalyst, 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 16 DEG C, formaldehyde and sodium hydroxide mixed liquor 8g that molar ratio is 1:0.9 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 597h-1, 4h, reaction is recycled
TOF value be still greater than 594h-1。
Embodiment 6
Prepare catalyst process
3mmol cerous nitrate, 5mmol cobalt nitrate and 32mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 19h at 22 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, roasts at 560 DEG C
Time 5h, calcination atmosphere 12%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in and is contained
In 1mmol copper nitrate, 0.3mmol silver nitrate and 0.3mmol potassium chloropalladate solution, using 0.36mol/L ammonia Borane solution-
4 DEG C of reduction 4h, obtain catalyst, are denoted as CuAg0.3Pd0.3/ porous C e3Co5Oz nanocatalyst, 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 7g that molar ratio is 1:1.3 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 526h-1, 4h is recycled, reaction
TOF value is still greater than 520h-1。
Claims (3)
1. with the method for CuAgPd/ porous C exCoyOz nanocatalyst catalysis formaldehyde dehydrogenation, it is characterised in that: by what is prepared
CuAgPd/ porous C exCoyOz nanocatalyst is placed in reactor, and reactor is placed in water-bath and rises to -10~20 DEG C, is connect
By molar ratio be 1:(0.8~1.5) formaldehyde and sodium hydroxide mixed liquor be added reactor in react, obtain product hydrogen
Gas；
The catalyst and mixed liquor mass ratio is 1:(130~180)；
The CuAgPd/ porous C exCoyOz nanocatalyst includes Cu, Ag, Pd and porous C exCoyOz, wherein the source Cu
In copper nitrate, Ag derives from silver nitrate, and Pd derives from potassium chloropalladate, and porous C exCoyOz is by cerous nitrate and cobalt nitrate and 2- methyl
Imidazoles forms Ce-Co-MOF roasting and is made, and the molar ratio of copper nitrate, silver nitrate and potassium chloropalladate is 1:(0.2~0.4): (0.1
~0.3)；The molar ratio of copper nitrate and cerous nitrate, cobalt nitrate, 2-methylimidazole is 1:(2~4): (4~6): (23~32)；
The CuAgPd/ porous C exCoyOz nanocatalyst is through the following steps that prepared:
(1) cerous nitrate, cobalt nitrate and 2-methylimidazole are dissolved in methanol solution and form uniform solution, stirred at 22~34 DEG C
18~27h is mixed, centrifugation obtains Ce-Co-MOF；
(2) Ce-Co-MOF is transferred to tube furnace, roasting obtains porous C exCoyOz；
(3) the porous C exCoyOz that roasting obtains is placed in copper nitrate, silver nitrate and potassium chloropalladate solution, made at -5~0 DEG C
1.5~4h is restored with ammonia Borane solution, centrifugal drying obtains CuAgPd/ porous C exCoyOz nanocatalyst.
2. special as described in claim 1 with the method for CuAgPd/ porous C exCoyOz nanocatalyst catalysis formaldehyde dehydrogenation
Sign is, in the preparation step (2) of the CuAgPd/ porous C exCoyOz nanocatalyst: tube furnace maturing temperature is 510
~560 DEG C, 3.5~7h of calcining time, calcination atmosphere O2/N2, wherein O2Volume accounting be 12%~16%.
3. special as described in claim 1 with the method for CuAgPd/ porous C exCoyOz nanocatalyst catalysis formaldehyde dehydrogenation
Sign is, in the preparation step (3) of the CuAgPd/ porous C exCoyOz nanocatalyst: ammonia borane concentration be 0.33~
0.52mol/L。
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Application publication date: 20190514 |