CN106466638A - The ruthenium catalyst of efficient cryogenic anti-poison guard catalyst formic acid hydrogen manufacturing and its preparation method and application - Google Patents
The ruthenium catalyst of efficient cryogenic anti-poison guard catalyst formic acid hydrogen manufacturing and its preparation method and application Download PDFInfo
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- CN106466638A CN106466638A CN201510504502.2A CN201510504502A CN106466638A CN 106466638 A CN106466638 A CN 106466638A CN 201510504502 A CN201510504502 A CN 201510504502A CN 106466638 A CN106466638 A CN 106466638A
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Abstract
The invention discloses a kind of ruthenium catalyst of the anti-poison guard catalyst formic acid hydrogen manufacturing of efficient cryogenic and its preparation method and application.Described catalyst is selected from has lower formula I, the metal complex of structure shown in (II)：Wherein R includes H, Me or OMe.The catalyst of the present invention can resolve into hydrogen and carbon dioxide by efficient catalytic formic acid under the conditions of low temperature, normal pressure, aqueous phase, and do not contain any CO etc. in the admixture of gas being obtained for fuel cell toxic component, process is simple, gained hydrogen purity is high and is easy to and CO2Separate, electromotor, fuel cell etc. can be directly fed, described catalyst all has anti-toxic effects well to most of common catalyst poison simultaneously, after continuous for a long time use, need not separate and just can continue to be re-used for Catalyzed by Formic Acid decomposition reaction, and still keep higher stability and activity, application cost can be greatly reduced.
Description
Technical field
The present invention relates to a kind of homogeneous catalyst, the ruthenium catalyst of the anti-poison guard catalyst formic acid hydrogen manufacturing of particularly a kind of efficient cryogenic,
Its preparation method and application, belong to energy catalysis material, hydrogen manufacturing technology field.
Background technology
Hydrogen, as the material of a kind of high chemism and extensive use, occupies critical role in national product and scientific research field,
Hydrogen has also attracted increasing concern as the high-efficiency cleaning energy.But the application of hydrogen faces Three Difficult Issues：Hydrogen manufacturing,
Hydrogen storage, extensively economic application form.
Formic acid is a kind of potential hydrogen carrier, and hydrogen mass content reaches 4.4%, and formic acid is the by-product that carboxylic acid is prepared in light oil oxidation
Thing, low price；Formic acid is liquid, and relative hydrogen density more great Yi storage, transportation safety are convenient；Formic acid passes through suitable
Catalytic reaction, catabolite only has H2And CO2, without other impurities gas.
The liquid mobile hydrogen making being currently based on chemical process has become one of the hot issue in current fuel cell field, formic acid because
The advantages of its high hydrogen content and become the study hotspot of mobile hydrogen making, current problem encountered is how in a mild condition
Continuous catalysis formic acid decomposes acquisition hydrogen.
JP2005-289742, CN101541668B, CN103240108A disclose to be decomposed by formic acid and produce H2And CO2's
Method, but reaction condition is all more harsh, is infeasible for practical applications such as fuel cell, portability hydrogen storage equipments.
Have in recent years in some researchs and achieve efficient formic acid hydrogen production reaction at low temperature using some homogeneous catalysts, but
Reaction medium is organic faciess, and in practical application, during the making of such as fuel cell uses, fire is dangerous.
Every technology generally existing hydrogen conversion before summary is low, contain toxic gas, reaction temperature is higher, desirable pressure
The defect such as larger.
Bi et al. (J.Am.Chem.Soc., 2012,134,8926-8933) discloses and is existed with zirconium oxide supported nano-gold granule, cluster
The method that under temperate condition, catalytic decomposition formic acid generates hydrogen.Chinese Academy of Sciences Changchun should change Xing Wei et al., using nanometer palladium carbon,
Technique of Nano Pd silver catalyst is it is also possible to efficiently decompose formic acid hydrogen manufacturing.But a lot of materials are held by the catalyst of precious metal simple substance
Easily it is poisoned, for example, minimal amount of formaldehyde, most of protein-based material and mercapto radical species all can lead to catalyst poisoning.
Therefore using such noble metal heterogeneous catalysis it is necessary to before formic acid decomposition reaction, by a small amount of harmful toxic matter in formic acid
Remove, but so can greatly increase the cost of hydrogen making.
Content of the invention
Present invention is primarily targeted at providing a kind of ruthenium catalyst and its preparation side of efficient cryogenic anti-poison guard catalyst formic acid hydrogen manufacturing
Method and application, thus overcome deficiency of the prior art.
For realizing aforementioned invention purpose, the technical solution used in the present invention includes：
A kind of low temperature anti-poisoning formic acid hydrogen manufacturing ruthenium catalyst, it is selected from has lower formula I, the metal network of structure shown in (II)
Compound：
Wherein, R includes H, Me or OMe.
Present invention also offers a kind of method preparing described ruthenium catalyst, it can include：
1) ruthenium ion and pentamethylcyclopentadiene are mixed in polar organic solvent and fully after back flow reaction, post-treated obtain
Obtain the first intermediate product；
2) by won the first place for step (1) intermediate product, mixed being incorporated under room temperature dark condition in water is fully reacted with Ag ion,
Post-treated obtain the second intermediate product；
3) by least one or at least in won the second place for step (2) intermediate product and 2,2 '-bipyridyl, 2,2 '-connection pyrimidine
Kind derivant mix in water and fully react at room temperature, more post-treated obtain target product.
Present invention also offers the purposes of described ruthenium catalyst.
For example, provide a kind of formic acid hydrogen production process among an embodiment, it includes：Made using described ruthenium catalyst
Formic acid decomposes under conditions of temperature is -20 DEG C～100 DEG C, thus obtaining hydrogen.
Among one more preferred embodiment, described formic acid hydrogen production process includes：Described ruthenium catalyst is soluble in the aqueous phase
In system, and make formic acid by described ruthenium catalyst catalytic decomposition in described aqueous phase system, thus obtaining hydrogen.
Among a highly preferred embodiment, described formic acid hydrogen production process includes：Described ruthenium catalyst is soluble in the aqueous phase
In system, and directly formic acid is continuously added to described aqueous phase system, thus continuously obtaining hydrogen.
Further, among described formic acid hydrogen production process, formic acid decomposes generation under the catalytic action of described ruthenium catalyst
Material only contain volume ratio be 1:1 hydrogen and carbon dioxide.
Among one more preferred embodiment, described formic acid hydrogen production process includes：The bar being -20 DEG C～100 DEG C in temperature
Under part, using water as the solvent of described ruthenium catalyst, make formic acid by catalytic decomposition, thus obtaining hydrogen.
Among a highly preferred embodiment, described formic acid hydrogen production process includes：In not higher than 50 DEG C of condition of temperature
Under, using water as the solvent of described ruthenium catalyst, make formic acid by catalytic decomposition, thus obtaining hydrogen.
Among an embodiment particularly preferably, described formic acid hydrogen production process includes：Under normal temperature condition, using water as
The solvent of described ruthenium catalyst, makes formic acid by catalytic decomposition, thus obtaining hydrogen.
Among a highly preferred embodiment, described formic acid hydrogen production process includes：Under conditions of temperature is 33 DEG C,
Using water as the solvent of described ruthenium catalyst, make formic acid by catalytic decomposition, thus obtaining hydrogen.
Further, described ruthenium catalyst is catalyzed the TOF of formic acid decomposition up to 420h-1.
Compared with prior art, advantages of the present invention includes：
(1) ruthenium catalyst providing energy efficient catalytic formic acid under the conditions of low temperature, normal pressure, aqueous phase resolves into volume ratio and is
1:1 hydrogen and carbon dioxide, TOF is up to 420h-1, and do not contain any CO etc. in the admixture of gas being obtained for combustion
Material battery toxic component, process is simple, gained hydrogen purity is high and is easy to and CO2Separate, can directly feed electromotor,
Fuel cell etc.；
(2) ruthenium catalyst providing all has anti-toxic effects well to most of common catalyst poison；
(3) ruthenium catalyst providing, after continuous for a long time use, need not separate and just can continue to be re-used for Catalyzed by Formic Acid decomposition instead
Should, and still keep higher stability and activity, application cost can be greatly reduced.
Brief description
Fig. 1 is the anti-poisoning test chart of the obtained ruthenium catalyst of the embodiment of the present invention 1.
Specific embodiment
As it was previously stated, in view of many defects of prior art, inventor through long-term in-depth study and a large amount of put into practice, obtain
To propose technical scheme, illustrate as follows.
One aspect of the present invention provides a kind of ruthenium catalyst, its can by generated in-situ catalyst, source metal and part,
Or pretreated metal complex is constituted.
Another aspect of the present invention provides the preparation method of described ruthenium catalyst.
An additional aspect of the present invention provides the Catalyzed by Formic Acid hydrogen production process based on described ruthenium catalyst.
Among some embodiments, described ruthenium catalyst is selected from has lower formula I, the metal complex of structure shown in (II)：
Wherein, R includes H, Me (methyl) or OMe (methoxyl group).
Further, the active component of described ruthenium catalyst is ruthenium, can be dissolved in water.
Further, described ruthenium catalyst can efficiently be catalyzed formic acid decomposition under the conditions of low temperature, normal pressure, aqueous phase and generate hydrogen
Any CO etc. is not contained for fuel cell toxic component in gas and carbon dioxide, and the admixture of gas being obtained.
Further, the ruthenium catalyst of the present invention can exist in atmosphere steadily in the long term, and keep good activity and stablize
Property.
Further, described ruthenium catalyst can make formic acid decompose and according to 1:1 ratio (H2：CO2=50:50 volumes %)
Discharge H2And CO2.Thus, by this catalyst, H can be obtained in lower temperature range2/CO2Mixture.
Wherein, the reaction temperature of the Catalyzed by Formic Acid hydrogen production process based on described ruthenium catalyst is preferably -20 DEG C～100 DEG C.
It is further preferred that described ruthenium catalyst is not higher than 50 DEG C of condition in temperature, such as can be long-time under normal temperature condition
Continual and steady catalysis formic acid hydrogen manufacturing, such as, after continuous catalysis hydrogen manufacturing 20 days in formic acid solution, still have good catalysis
Performance.
It is more highly preferred to, the reaction temperature of the Catalyzed by Formic Acid hydrogen production process based on described ruthenium catalyst is room temperature condition, most preferably
33 DEG C, TOF is more than 400h with this understanding-1, reach as high as 420h-1, and do not need to add other additives again.
Further, the preferred water of the solvent of described ruthenium catalyst.
Further, formic acid can be added continuously to dissolved with the aqueous phase reactions device of described ruthenium catalyst, and can be endlessly
Produce hydrogen.And terminate rear catalyst in an elementary reaction and need not separate in the reaction that just can be directly to next stage.
Further, because the anti-poisoning capability of described ruthenium catalyst is good, particularly PARA FORMALDEHYDE PRILLS(91,95), protein, aminoacid etc. are common
Toxicant has extraordinary anti-poisoning characteristic.Therefore the purity requirement to formic acid is not high, is also had using commercially pure formic acid
Good catalytic effect.
Among some embodiments, the preparation method of described ruthenium catalyst can include：
1) ruthenium ion and pentamethylcyclopentadiene are mixed in polar organic solvent and fully after back flow reaction, cooling, filter,
Washing obtains yellowish-brown intermediate product；
2) by obtained for step (1) yellowish-brown product, mixed being incorporated under room temperature dark condition in water is fully reacted with Ag ion,
Refilter, wash and obtain crocus intermediate product；
3) will be mixed in water for the derivant of obtained for step (2) crocus intermediate product and 2,2 '-bipyridyl and/or 2,2 '-connection pyrimidine
Merge and fully react at room temperature, refilter, vacuum rotary steam obtains target product.
Among some more specifically embodiment, the preparation method of described ruthenium catalyst can include：
1) ruthenium ion and pentamethylcyclopentadiene are mixed in polar organic solvent and fully after back flow reaction, cooling, filter,
Washing obtains yellowish-brown intermediate product；
2) by obtained for step (1) yellowish-brown intermediate product and Ag ion in water mixed be incorporated in fully anti-under room temperature dark condition
Should, refilter, wash and obtain crocus intermediate product；
3) will be mixed in water for the derivant of obtained for step (2) crocus intermediate product and 2,2 '-bipyridyl and/or 2,2 '-connection pyrimidine
Merge and fully react at room temperature, refilter, vacuum rotary steam obtains target product.
Wherein, described ruthenium ion can be from the ruthenium salt that can be dissolved in described polar organic solvent, such as ruthenic chloride etc..
Wherein, described polar organic solvent can industry be known, can dissolve described ruthenium salt and pentamethylcyclopentadiene
The small molecular alcohols such as polar organic solvent, such as methanol.
Wherein, the usage ratio of ruthenium ion and pentamethylcyclopentadiene to be can make both abundant complexation reactions as standard, for example
1 can be preferably：3 mol ratio.
Wherein, described silver ion can be from the silver salt that can be dissolved in water equal solvent, such as silver sulfate etc..
Wherein, step 2) in yellowish-brown intermediate product be advisable so that both can be made fully to react with the usage ratio of soluble silver salt,
For example, wherein in Ag ion and yellowish-brown intermediate product contained ruthenium element mol ratio optimal about 1：1.
Wherein, step 3) in crocus intermediate product and 2,2 '-bipyridyl and/or 2,2 '-connection its derivant of pyrimidine usage ratio
Be advisable so that both can be made fully to react, for example, wherein crocus intermediate product and 2,2 '-bipyridyl and/or 2,2 '-connection pyrimidine its
The mol ratio of derivant optimal about 1：1.
The derivant of described 2,2 '-bipyridyl or 2,2 '-connection pyrimidine preferably has structure shown in following formula：
Wherein, R includes H, Me and/or OMe.
Below in conjunction with some embodiments and accompanying drawing, technical scheme is further described.
Embodiment 1：The preparation of ruthenium catalyst.
1) by ruthenic chloride and pentamethylcyclopentadiene (Cp*) in molar ratio for 1:3 are dissolved in a small amount of methanol, and flow back 37h,
It is cooled to 0 DEG C, filter and obtain yellowish-brown product [Ru using ether washingII(Cp*)(Cl)2]2.
2) by [RuII(Cp*)(Cl)2]2With Ag2SO4It is 1 in molar ratio:2 H being dissolved in 3 times2In O, under room temperature dark
Stirring 5h, filtration washing obtains crocus [RuII(Cp*)(H2O)3](SO4).
3) by [RuII(Cp*)(H2O)3](SO4) with 2,2 '-bipyridyl in molar ratio be 1：1 is blended in water, stirs under room temperature
5h, filters, and vacuum rotary steam obtains a kind of ruthenium catalyst as shown in formula I.This catalyst is in D26.0,25 DEG C of O, pH
Under the conditions of, on the basis of TSP ' H NMR is：δ2.13(s,18H)δ
7.56(t,2H),7.90(t,2H),8.18(d,2H),8.50(d,2H),7.45(s,1H).
Embodiment 2：The process of hydrogen is prepared in catalyst acid decomposition.
By 10-3The obtained ruthenium catalyst of mmol embodiment 1 is dissolved in 1ml 5mol/L formic acid, is passed through N2, in 33 DEG C of oil baths
Stirring is lower to react, and monitors gas value changes by U-tube, can get continuous gas, this gas is by volume ratio 1:1 hydrogen
Gas and carbon dioxide composition.
Embodiment 3：Catalyst acid decomposes formic acid anti-poisoning test.
1) finally add 10ul formaldehyde in the reactant liquor of obtained reactant liquor to having reacted the embodiment 2 of about 3h, blow N2, pass through
U-tube monitors gas value changes, still can get continuously by volume ratio 1:1 hydrogen and the gas of carbon dioxide composition, explanation
This catalyst can anti-formaldehyde poisoning.
2) add about 20Mm NAD in step (1) finally obtained reactant liquor+, blow N2, gas is monitored by U-tube
Value changes, still can get continuously by volume ratio 1:1 hydrogen and the gas of carbon dioxide composition, illustrate that this catalyst can resist
NAD+Poisoning.
3) add about 20Mm NADH in step (2) finally obtained reactant liquor, blow N2, gas is monitored by U-tube
Value changes, still can get continuously by volume ratio 1:1 hydrogen and the gas of carbon dioxide composition, illustrate that this catalyst can resist
NADH is poisoned.
4) add about 5ul hydrogenlyase in step (3) finally obtained reactant liquor, blow N2, gas is monitored by U-tube
Body value changes, still can get continuously by volume ratio 1:1 hydrogen and the gas of carbon dioxide composition, illustrate that this catalyst can resist
Formate dehydrogenase poisoning by enzyme.
Postscript, the anti-poisoning test chart of the obtained ruthenium catalyst of embodiment 1 see Fig. 1.
The synthesis step of other compounds shown in formula I, (II) is similar to the preparation process of ruthenium catalyst in embodiment 1.
And with reference to embodiment 2-3, these catalyst are tested, it can be found that its have close with the obtained catalyst of embodiment 1 low
Formic acid can be efficiently catalyzed under the conditions of temperature, normal pressure, aqueous phase and decompose the performance generating hydrogen.
The above is only the part preferred embodiment of the present invention it is noted that for those skilled in the art,
Under the premise without departing from the principles of the invention, some variations in detail can also be made, these variations in detail also should be regarded as the present invention
Protection domain.
Claims (10)
1. a kind of ruthenium catalyst of the anti-poison guard catalyst formic acid hydrogen manufacturing of efficient cryogenic is it is characterised in that described catalyst is selected under having
Formula I, the metal complex of structure shown in (II)：
Wherein, R is at least selected from H, Me or OMe.
2. a kind of preparation method of the ruthenium catalyst of the anti-poison guard catalyst formic acid hydrogen manufacturing of efficient cryogenic is it is characterised in that include：
1) ruthenium ion and pentamethylcyclopentadiene are mixed in polar organic solvent and fully after back flow reaction, post-treated obtain
Obtain the first intermediate product；
2) by won the first place for step (1) intermediate product, mixed being incorporated under room temperature dark condition in water is fully reacted with Ag ion,
Post-treated obtain the second intermediate product；
3) by least one or at least in won the second place for step (2) intermediate product and 2,2 '-bipyridyl, 2,2 '-connection pyrimidine
Kind derivant mix in water and fully react at room temperature, more post-treated obtain target product.
3. a kind of formic acid hydrogen production process is it is characterised in that include：Formic acid is made to exist using the ruthenium catalyst described in claim 1
Decompose under conditions of -20～100 DEG C, thus obtaining hydrogen.
4. formic acid hydrogen production process according to claim 3 is it is characterised in that include：Described ruthenium catalyst is soluble in the aqueous phase
In system, and make formic acid by described ruthenium catalyst catalytic decomposition in described aqueous phase system, thus obtaining hydrogen.
5. the formic acid hydrogen production process according to claim 3 or 4 is it is characterised in that include：Described ruthenium catalyst is dissolved in
In aqueous phase system, and directly formic acid is continuously added to described aqueous phase system, thus continuously obtaining hydrogen.
6. the formic acid hydrogen production process according to claim 3 or 4 is it is characterised in that include：Formic acid is in described ruthenium catalyst
Catalytic action under decompose the material of generation only to contain volume ratio be 1:1 hydrogen and carbon dioxide.
7. formic acid hydrogen production process according to claim 3 is it is characterised in that include：In not higher than 50 DEG C of condition of temperature
Under, using water as the solvent of described ruthenium catalyst, make formic acid by catalytic decomposition, thus obtaining hydrogen.
8. formic acid hydrogen production process according to claim 7 is it is characterised in that include：Under normal temperature condition, using water as
The solvent of described ruthenium catalyst, makes formic acid by catalytic decomposition, thus obtaining hydrogen.
9. formic acid hydrogen production process according to claim 8 is it is characterised in that include：Under conditions of temperature is 33 DEG C,
Using water as the solvent of described ruthenium catalyst, make formic acid by catalytic decomposition, thus obtaining hydrogen.
10. the formic acid hydrogen production process according to any one of claim 7-9 is it is characterised in that described ruthenium catalyst is catalyzed first
The TOF that acid is decomposed is up to 420h-1.
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