CN109734051A - With the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formaldehyde dehydrogenation - Google Patents
With the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formaldehyde dehydrogenation Download PDFInfo
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- CN109734051A CN109734051A CN201910024979.9A CN201910024979A CN109734051A CN 109734051 A CN109734051 A CN 109734051A CN 201910024979 A CN201910024979 A CN 201910024979A CN 109734051 A CN109734051 A CN 109734051A
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Abstract
The invention discloses a kind of methods with the catalysis formaldehyde dehydrogenation of AgPd/ porous C exCuyOz nanocatalyst, belong to technical field of chemistry and chemical engineering.This method is: the AgPd/ porous C exCuyOz nanocatalyst prepared is placed in reactor, reactor is placed in water-bath and rises to certain temperature, then formaldehyde and sodium hydroxide mixed liquor are added in reactor and are reacted, the hydrogen of generation is collected using drainage.Unlike existing catalyst: according to the present invention, the high activity for formaldehyde dehydrogenation hydrogen, highly selective, high stability nanocatalyst can be made in the molar ratio for adjusting mole when support precursor cerous nitrate, copper nitrate and the 2-methylimidazole of metal Ag, Pd in catalyst.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 330h‑1, 4h is recycled, the TOF value of reaction is still greater than 323h‑1。
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, and in particular to be catalyzed with AgPd/ porous C exCuyOz nanocatalyst
The method of formaldehyde dehydrogenation.
Background technique
Formaldehyde (HCHO) is important chemical hydride newfound in recent years, it has chemical property temperature, under room temperature
For liquid, existing energy source device can be utilized well, be considered as most promising fuel cell Hydrogen Energy supply material it
One.But Formaldehyde decomposition reaction has two paths: a kind of directly decompose generates hydrogen and carbon monoxide, wherein carbon monoxide pole
It causes the poisoning of hydrogen fuel cell catalyst；It is another that hydrogen and carbon dioxide are generated by hydrolysis pathway, it is ideal hydrogen
Approach can be discharged.The regulation key in formaldehyde dehydrogenation reaction path is to design the efficient dehydrogenation of Rational structure.
Currently, the patent about formaldehyde dehydrogenation is rarely reported, as long as a small amount of document is respectively from homogeneous catalyst
With the research for having carried out catalyst in terms of heterogeneous catalysis two.But effect is undesirable.From existing document report it is found that palladium is
The important activity component of formaldehyde dehydrogenation, how the structure of efficient design vector and regulation activity component is that design is efficient
The key of dehydrogenation.
Summary of the invention
AgPd/ porous C exCuyOz nano-catalytic is used in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of
The method that agent is catalyzed formaldehyde dehydrogenation, realizes first to the AgPd/ porous C exCuyOz nanocatalyst under the conditions of relatively mild
The complete dehydrogenation of aldehyde.
The present invention is achieved by the following technical programs.
A kind of method with the catalysis formaldehyde dehydrogenation of AgPd/ porous C exCuyOz nanocatalyst of the present invention, comprises the concrete steps that:
The AgPd/ porous C exCuyOz nanocatalyst prepared is placed in reactor, reactor is placed in water-bath and rises to -5~
20 DEG C, be then 1 by molar ratio: the formaldehyde and sodium hydroxide mixed liquor of (0.6~1.2), which are added in reactor, to react, and obtains
To hydrogen product；The catalyst and mixed liquor mass ratio is 1: (70~140).
The AgPd/ porous C exCuyOz nanocatalyst includes Ag, Pd and porous C exCuyOz, wherein the source Ag
In silver nitrate, Pd derives from potassium chloropalladate, and porous C exCuyOz forms Ce-Cu- by cerous nitrate, copper nitrate and 2-methylimidazole
MOF roasting is made, and the molar ratio of silver nitrate and potassium chloropalladate is 1: (0.3~0.6)；Silver nitrate and cerous nitrate, copper nitrate, 2- first
The molar ratio of base imidazoles is 1: (3~7): (2~5): (18~24).
The AgPd/ porous C exCuyOz nanocatalyst is through the following steps that prepared:
(1) cerous nitrate, copper nitrate and 2-methylimidazole are dissolved in methanol solution and form uniform solution, at 15~33 DEG C
18~27h of lower stirring, centrifugation obtain Ce-Cu-MOF；
(2) Ce-Cu-MOF is transferred to tube furnace, roasting obtains porous C exCuyOz；
(3) the porous C exCuyOz that roasting obtains is placed in silver nitrate and potassium chloropalladate solution, ammonia is used at -2~3 DEG C
Borane solution reductase 12~4h, centrifugal drying obtain AgPd/ porous C exCuyOz nanocatalyst.
As a kind of optimization, in the preparation step (2) of the AgPd/ porous C exCuyOz nanocatalyst: tube furnace
Maturing temperature is 480~530 DEG C, 2~5h of calcining time, calcination atmosphere O2/N2, wherein O2Volume accounting be 5%~
11%.
As a kind of optimization, in the preparation step (3) of the AgPd/ porous C exCuyOz nanocatalyst: ammonia borine
Concentration is 0.13~0.26mol/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, copper 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-Cu-MOF, by Ce-Cu-MOF
It is transferred to tube furnace, roasting obtains porous C exCuyOz under certain roasting condition and atmosphere, roasting is obtained porous
CexCuyOz is placed in the silver nitrate and potassium chloropalladate solution of definite composition, restores one section using ammonia Borane solution in a mild condition
Time, centrifugal drying obtain the AgPd/ porous C exCuyOz nanocatalyst with high dispersancy nano particle.
2, the AgPd/ porous C exCuyOz nanocatalyst PARA FORMALDEHYDE PRILLS(91,95) dehydrogenation reaction it is with higher activity, selectivity and
Stability.Formaldehyde dehydrogenation under temperate condition can be realized using the catalyst, and conversion rate of dehydrogenation and selectivity are 100%, reaction
TOF value be greater than 330h-1, 4h is recycled, the TOF value of reaction is still greater than 323h-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
3mmol cerous nitrate, 5mmol copper nitrate and 18mmol2- methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 27h at 15 DEG C, and centrifugation obtains Ce-Cu-MOF, Ce-Cu-MOF is transferred to tube furnace, roasts at 480 DEG C
Time 5h, calcination atmosphere 5%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in containing 1mmol
In silver nitrate and 0.3mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.13mol/L in -2 DEG C of reduction 4h, obtains and urge
Agent is denoted as AgPd0.3/ porous C e3Cu5Oz 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 3.5g that molar ratio is 1: 0.6 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 340h-1, 4h is recycled, instead
The TOF value answered is still greater than 334h-1。
Embodiment 2
Prepare catalyst process
7mmol cerous nitrate, 2mmol copper nitrate and 24mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 18h at 33 DEG C, and centrifugation obtains Ce-Cu-MOF, Ce-Cu-MOF is transferred to tube furnace, roasts at 530 DEG C
Time 2h, calcination atmosphere 11%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in and is contained
In 1mmol silver nitrate and 0.6mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.26mol/L in 3 DEG C of reductase 12 h, that is, make
Catalyst is obtained, AgPd is denoted as0.6/ porous C e7Cu2Oz 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 7g that molar ratio is 1: 1.2 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 580h-1, 4h, reaction is recycled
TOF value be still greater than 575h-1。
Embodiment 3
Prepare catalyst process
3mmol cerous nitrate, 4mmol copper nitrate and 19mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs for 24 hours at 28 DEG C, and centrifugation obtains Ce-Cu-MOF, and Ce-Cu-MOF is transferred to tube furnace, roasts at 520 DEG C
Time 4h, calcination atmosphere 9%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in containing 1mmol
In silver nitrate and 0.4mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.23mol/L in 3 DEG C of reduction 4h, catalysis is obtained
Agent is denoted as AgPd0.4/ porous C e3Cu4Oz 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 18 DEG C, formaldehyde and sodium hydroxide mixed liquor 6.5g that molar ratio is 1: 1.1 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 523h-1, 4h is recycled, instead
The TOF value answered is still greater than 518h-1。
Embodiment 4
Prepare catalyst process
5mmol cerous nitrate, 4mmol copper nitrate and 21mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 22h at 27 DEG C, and centrifugation obtains Ce-Cu-MOF, Ce-Cu-MOF is transferred to tube furnace, roasts at 495 DEG C
Time 4.2h, calcination atmosphere 7%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in and is contained
In 1mmol silver nitrate and 0.5mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.14mol/L in 2 DEG C of reduction 3.6h, i.e.,
Catalyst is made, is denoted as AgPd0.5/ porous C e5Cu4Oz 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 13 DEG C, formaldehyde and sodium hydroxide mixed liquor 4.5g 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 424h-1, 4h is recycled, instead
The TOF value answered is still greater than 419h-1。
Embodiment 5
Prepare catalyst process
6mmol cerous nitrate, 5mmol copper nitrate and 22mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs for 24 hours at 31 DEG C, and centrifugation obtains Ce-Cu-MOF, and Ce-Cu-MOF is transferred to tube furnace, roasts at 515 DEG C
Time 2.5h, calcination atmosphere 6%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in and is contained
In 1mmol silver nitrate and 0.4mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.23mol/L in -1 DEG C of reduction 3.5h, i.e.,
Catalyst is made, is denoted as AgPd0.4/ porous C e6Cu5Oz 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 4g that molar ratio is 1: 0.7 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 447h-1, 4h is recycled, reaction
TOF value is still greater than 442h-1。
Embodiment 6
Prepare catalyst process
4mmol cerous nitrate, 3mmol copper nitrate and 21mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 23h at 24 DEG C, and centrifugation obtains Ce-Cu-MOF, Ce-Cu-MOF is transferred to tube furnace, roasts at 525 DEG C
Time 4.1h, calcination atmosphere 7%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in and is contained
In 1mmol silver nitrate and 0.6mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.26mol/L in 3 DEG C of reduction 4h, that is, make
Catalyst is obtained, AgPd is denoted as0.6/ porous C e4Cu3Oz 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 2 DEG C, formaldehyde and sodium hydroxide mixed liquor 5.5g that molar ratio is 1: 1.1 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 472h-1, 4h, reaction is recycled
TOF value be still greater than 467h-1。
Claims (3)
1. with the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formaldehyde dehydrogenation, it is characterised in that: by what is prepared
AgPd/ porous C exCuyOz nanocatalyst is placed in reactor, and reactor is placed in water-bath and rises to -5~20 DEG C, then will
Molar ratio is 1: the formaldehyde and sodium hydroxide mixed liquor of (0.6~1.2), which are added in reactor, to be reacted, and hydrogen product is obtained；
The catalyst and mixed liquor mass ratio is 1: (70~140)；
The AgPd/ porous C exCuyOz nanocatalyst includes Ag, Pd and porous C exCuyOz, wherein Ag derives from nitre
Sour silver, Pd derive from potassium chloropalladate, and porous C exCuyOz forms Ce-Cu-MOF by cerous nitrate, copper nitrate and 2-methylimidazole and roasts
It fires, the molar ratio of silver nitrate and potassium chloropalladate is 1: (0.3~0.6)；Silver nitrate and cerous nitrate, copper nitrate, 2- methyl miaow
The molar ratio of azoles is 1: (3~7): (2~5): (18~24)；
The AgPd/ porous C exCuyOz nanocatalyst is through the following steps that prepared:
(1) cerous nitrate, copper nitrate and 2-methylimidazole are dissolved in methanol solution and form uniform solution, stirred at 15~33 DEG C
18~27h is mixed, centrifugation obtains Ce-Cu-MOF；
(2) Ce-Cu-MOF is transferred to tube furnace, roasting obtains porous C exCuyOz；
(3) the porous C exCuyOz that roasting obtains is placed in silver nitrate and potassium chloropalladate solution, ammonia borine is used at -2~3 DEG C
2~4h of solution reduction, centrifugal drying obtain AgPd/ porous C exCuyOz nanocatalyst.
2. as described in claim 1 with the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formaldehyde dehydrogenation, feature
Be, in the preparation step (2) of the AgPd/ porous C exCuyOz nanocatalyst: tube furnace maturing temperature be 480~
530 DEG C, 2~5h of calcining time, calcination atmosphere O2/N2, wherein O2Volume accounting be 5%~11%.
3. as described in claim 1 with the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formaldehyde dehydrogenation, feature
Be, in the preparation step (3) of the AgPd/ porous C exCuyOz nanocatalyst: ammonia borane concentration be 0.13~
0.26mol/L。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862656A (en) * | 2010-07-02 | 2010-10-20 | 北京化工大学 | Loaded nano-copper magnetic catalyst used for catalysis of solution of formaldehyde for preparing hydrogen and preparation method thereof |
| CN104307519A (en) * | 2014-09-30 | 2015-01-28 | 厦门大学 | Gold supported strontium titanate catalyst for directly preparing hydrogen from formaldehyde aqueous solution and preparation method of gold supported strontium titanate catalyst for directly preparing hydrogen from formaldehyde aqueous solution |
| CN107473183A (en) * | 2017-08-21 | 2017-12-15 | 南昌大学 | The application of phosphating sludge catalyzing manufacturing of hydrogen in alkaline formaldehyde solution |
-
2019
- 2019-01-10 CN CN201910024979.9A patent/CN109734051A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862656A (en) * | 2010-07-02 | 2010-10-20 | 北京化工大学 | Loaded nano-copper magnetic catalyst used for catalysis of solution of formaldehyde for preparing hydrogen and preparation method thereof |
| CN104307519A (en) * | 2014-09-30 | 2015-01-28 | 厦门大学 | Gold supported strontium titanate catalyst for directly preparing hydrogen from formaldehyde aqueous solution and preparation method of gold supported strontium titanate catalyst for directly preparing hydrogen from formaldehyde aqueous solution |
| CN107473183A (en) * | 2017-08-21 | 2017-12-15 | 南昌大学 | The application of phosphating sludge catalyzing manufacturing of hydrogen in alkaline formaldehyde solution |
Non-Patent Citations (2)
| Title |
|---|
| TAO FENG ET AL.: ""CuAg nanoparticles immobilized on biomass carbon nanospheres for high-efficiency hydrogen production from formaldehyde"", 《CATALYSIS COMMUNICATIONS》 * |
| TAO FENG ET AL.: ""Pd nanoparticles supported on CeO2 as efficient catalyst for hydrogen generation from formaldehyde solution at room temperature"", 《APPLIED ORGANOMETALLIC CHEMISTRY》 * |
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