CN106466638B - The ruthenium catalyst and its preparation method of the anti-poison guard catalyst formic acid hydrogen manufacturing of efficient cryogenic and application - Google Patents
The ruthenium catalyst and its preparation method of the anti-poison guard catalyst formic acid hydrogen manufacturing of efficient cryogenic and application Download PDFInfo
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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 applications.The catalyst is selected from selected from the metal complex with structure shown in following formula (I), (II):Wherein R includes H, Me or OMe.Catalyst of the invention energy efficient catalytic formic acid under the conditions of low temperature, normal pressure, water phase resolves into hydrogen and carbon dioxide, and any CO etc. is free of in admixture of gas obtained for fuel cell toxic component, simple process, gained hydrogen purity is high and is easy to and CO2Separation, engine, fuel cell etc. can be directly fed, the catalyst has good anti-toxic effects to most of common catalyst poison simultaneously, after long-term continuous use, it can continue to be re-used for Catalyzed by Formic Acid decomposition reaction without separation, and higher stability and activity are still kept, application cost can be greatly reduced.
Description
Technical field
The present invention relates to a kind of homogeneous catalyst, the ruthenium of especially a kind of anti-poison guard catalyst formic acid hydrogen manufacturing of efficient cryogenic is catalyzed
Agent, preparation method and application belong to energy catalysis material, hydrogen manufacturing technology field.
Background technique
Substance of the hydrogen as a kind of high chemical activity and extensive use, occupies importantly in national product and scientific research field
Position, hydrogen have also attracted more and more concerns as the high-efficiency cleaning energy.But the application of hydrogen faces Three Difficult Issues: system
Hydrogen, hydrogen storage, extensive economic application form.
Formic acid is a kind of potential hydrogen carrier, and hydrogen mass content reaches 4.4%, and formic acid is that light oil oxidation prepares carboxylic acid
By-product, it is cheap；Formic acid is liquid, and relative hydrogen density more great Yi storage, transportation safety are convenient；It is suitable that formic acid passes through
Catalysis reaction, decomposition product only has H2And CO2, be free of other impurities gas.
One of the hot topic in current fuel cell field, first are had become currently based on the liquid mobile hydrogen making of chemical process
Acid becomes the research hotspot of mobile hydrogen making due to its high hydrogen content the advantages that, and problem encountered is how in mild item at present
Continuous catalysis formic acid, which decomposes, under part obtains hydrogen.
JP2005-289742, CN101541668B, CN103240108A, which disclose to be decomposed by formic acid, generates H2And CO2Side
Method, but reaction condition is more harsh, is infeasible for practical applications such as fuel cell, portability hydrogen storage equipments.
Have in some researchs in recent years realizes efficient formic acid hydrogen production reaction using some homogeneous catalysts at low temperature,
But reaction medium is organic phase, and in practical application, such as the production use process of fuel cell, fire danger
Danger.
The generally existing hydrogen conversion of every technology before summary is low, containing toxic gas, reaction temperature is higher, required pressure
The defects of power is larger.
Bi et al. (J.Am.Chem.Soc., 2012,134,8926-8933) is disclosed with zirconium oxide supported nano-gold
The method that formic acid generates hydrogen is catalytically decomposed in grain, cluster in a mild condition.The Xing Wei et al. of Changchun Institute of Applied Chemistry of the Chinese Academy of Sciences is used
Nanometer palladium carbon, Technique of Nano Pd silver catalyst, can also efficiently decompose formic acid hydrogen manufacturing.But the catalyst of precious metal simple substance, to very
More substances are easy poisoning, for example, minimal amount of formaldehyde, most of protein-based substance and sulfydryl substance can all cause to be catalyzed
Agent poisoning.Therefore such noble metal heterogeneous catalysis is used, it is necessary to before formic acid decomposition reaction, by poison a small amount of in formic acid
Evil substance removes, but can greatly increase the cost of hydrogen making in this way.
Summary of the invention
The main purpose of the present invention is to provide a kind of ruthenium catalyst of the anti-poison guard catalyst formic acid hydrogen manufacturing of efficient cryogenic and its
Preparation method and application, to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
A kind of anti-poisoning formic acid hydrogen manufacturing ruthenium catalyst of low temperature, selected from the metal network with structure shown in following formula (I), (II)
Close object:
Wherein, R includes H, Me or OMe.
The present invention also provides a kind of methods for preparing the ruthenium catalyst, may include:
1) after ruthenium ion to be mixed in polar organic solvent to simultaneously abundant back flow reaction with pentamethylcyclopentadiene, after
Reason obtains the first intermediate product；
2) step (1) won the first place intermediate product mixed in water with Ag ion and sufficiently anti-under room temperature dark condition
It answers, it is post-treated to obtain the second intermediate product；
3) by least one of the won the second place intermediate product of step (2) and 2,2 '-bipyridyls, 2,2 '-connection pyrimidines or extremely
Few a kind of derivative mix in water and it is abundant at room temperature react, then post-treated obtain target product.
The present invention also provides the purposes of the ruthenium catalyst.
For example, providing a kind of formic acid hydrogen production process among an embodiment comprising: use the ruthenium catalyst
Decompose formic acid under conditions of -20 DEG C~100 DEG C of temperature, to obtain hydrogen.
Among one more preferred embodiment, the formic acid hydrogen production process includes: to be dissolved in the ruthenium catalyst
In aqueous phase system, and formic acid is catalytically decomposed in the aqueous phase system by the ruthenium catalyst, to obtain hydrogen.
Among a highly preferred embodiment, the formic acid hydrogen production process includes: to be dissolved in the ruthenium catalyst
In aqueous phase system, and formic acid is directly continuously added to the aqueous phase system, to continuously obtain hydrogen.
Further, among the formic acid hydrogen production process, formic acid decomposes under the catalytic action of the ruthenium catalyst
The substance of generation contains only the hydrogen and carbon dioxide that volume ratio is 1:1.
Among one more preferred embodiment, it is -20 DEG C~100 that the formic acid hydrogen production process, which includes: in temperature,
Under conditions of DEG C, using water as the solvent of the ruthenium catalyst, formic acid is catalytically decomposed, to obtain hydrogen.
Among a highly preferred embodiment, the formic acid hydrogen production process includes: in temperature not higher than 50 DEG C
Under the conditions of, using water as the solvent of the ruthenium catalyst, formic acid is catalytically decomposed, to obtain hydrogen.
Among an embodiment particularly preferably, the formic acid hydrogen production process includes: under normal temperature conditions, to be made with water
For the solvent of the ruthenium catalyst, formic acid is catalytically decomposed, to obtain hydrogen.
Among a highly preferred embodiment, the formic acid hydrogen production process includes: the condition for being 33 DEG C in temperature
Under, using water as the solvent of the ruthenium catalyst, formic acid is catalytically decomposed, to obtain hydrogen.
Further, the TOF that the ruthenium catalyst catalysis formic acid decomposes is up to 420h-1。
Compared with prior art, the invention has the advantages that
(1) ruthenium catalyst provided energy efficient catalytic formic acid under the conditions of low temperature, normal pressure, water phase resolves into volume ratio
For the hydrogen and carbon dioxide of 1:1, TOF is up to 420h-1, and any CO etc. is free of for fuel in admixture of gas obtained
Battery toxic component, simple process, gained hydrogen purity is high and is easy to and CO2Separation can directly feed engine, fuel electricity
Pond etc.；
(2) ruthenium catalyst provided has good anti-toxic effects to most of common catalyst poison；
(3) ruthenium catalyst provided can continue to be re-used for Catalyzed by Formic Acid point without separation after long-term continuous use
Solution reaction, and higher stability and activity are still kept, application cost can be greatly reduced.
Detailed description of the invention
Fig. 1 is the anti-poisoning test chart of the obtained ruthenium catalyst of the embodiment of the present invention 1.
Specific embodiment
As previously mentioned, inventor practices through long-term in-depth study and largely in view of many defects of the prior art,
It is able to propose technical solution of the present invention, illustrate as follows.
One aspect of the present invention provides a kind of ruthenium catalyst, can by generated in-situ catalyst, source metal and
Ligand or pretreated metal complex are constituted.
Another aspect of the present invention provides the preparation method of the ruthenium catalyst.
An additional aspect of the present invention provides the Catalyzed by Formic Acid hydrogen production process based on the ruthenium catalyst.
Among some embodiments, the ruthenium catalyst is selected from the metal complex with structure shown in following formula (I), (II)
Object:
Wherein, R includes H, Me (methyl) or OMe (methoxyl group).
Further, the active component of the ruthenium catalyst is ruthenium, can be dissolved in water.
Further, the ruthenium catalyst can efficiently be catalyzed formic acid under the conditions of low temperature, normal pressure, water phase and decompose generation
Hydrogen and carbon dioxide, and any CO etc. is free of in admixture of gas obtained for fuel cell toxic component.
Further, ruthenium catalyst of the invention can exist steadily in the long term in air, and keep it is good activity and
Stability.
Further, the ruthenium catalyst can be such that formic acid decomposes and according to the ratio (H of 1:12: CO2=50:50 body
Product %) release H2And CO2.Thus, by the 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 the ruthenium catalyst is preferably -20 DEG C~100 DEG C.
It is further preferred that the ruthenium catalyst is not higher than 50 DEG C of condition in temperature, such as can be grown under normal temperature condition
Time continual and steady catalysis formic acid hydrogen manufacturing, such as in formic acid solution after continuous catalysis hydrogen manufacturing 20 days, still have good
Catalytic performance.
More preferably, the reaction temperature of the Catalyzed by Formic Acid hydrogen production process based on the ruthenium catalyst is room temperature condition, most
Good is 33 DEG C, and TOF is greater than 400h with this condition-1, reach as high as 420h-1, and do not need to add other additives again.
Further, the preferred water of the solvent of the ruthenium catalyst.
Further, formic acid can be added continuously in the aqueous phase reactions device dissolved with the ruthenium catalyst, and can in a steady stream not
Disconnected generation hydrogen.And catalyst is not necessarily to the reaction that separation can be directly to next stage after reaction in a stage
In.
Further, since the anti-poisoning capability of the ruthenium catalyst is good, especially PARA FORMALDEHYDE PRILLS(91,95), protein, amino acid etc. are normal
See that toxicant has extraordinary anti-poisoning characteristic.Therefore not high to the purity requirement of formic acid, also had using commercially pure formic acid
The catalytic effect having had.
Among some embodiments, the preparation method of the ruthenium catalyst may include:
1) after ruthenium ion to be mixed in polar organic solvent to simultaneously abundant back flow reaction with pentamethylcyclopentadiene, cooling,
It is filtered, washed and obtains yellowish-brown intermediate product；
2) the obtained yellowish-brown product of step (1) mixed in water with Ag ion and sufficiently anti-under room temperature dark condition
It answers, refilters, washs and obtain crocus intermediate product；
3) derivative of the obtained crocus intermediate product of step (2) and 2,2 '-bipyridyls and/or 2,2 '-connection pyrimidines is existed
Mixing and sufficiently reaction at room temperature, refilter, vacuum rotary steam obtains target product in water.
Among some more specifically embodiments, the preparation method of the ruthenium catalyst may include:
1) after ruthenium ion to be mixed in polar organic solvent to simultaneously abundant back flow reaction with pentamethylcyclopentadiene, cooling,
It is filtered, washed and obtains yellowish-brown intermediate product；
2) the obtained yellowish-brown intermediate product of step (1) mixed in water with Ag ion and under room temperature dark condition sufficiently
Reaction refilters, washs and obtain crocus intermediate product；
3) derivative of the obtained crocus intermediate product of step (2) and 2,2 '-bipyridyls and/or 2,2 '-connection pyrimidines is existed
Mixing and sufficiently reaction at room temperature, refilter, vacuum rotary steam obtains target product in water.
Wherein, the ruthenium ion can be from the ruthenium salt that can be dissolved in the polar organic solvent, such as ruthenic chloride etc..
Wherein, the polar organic solvent can be what industry was known, can dissolve the ruthenium salt and pentamethyl ring penta 2
The small molecular alcohols such as the polar organic solvent of alkene, such as methanol.
Wherein, the usage ratio of ruthenium ion and pentamethylcyclopentadiene to be both can make sufficiently complexation reaction standard,
It such as can be preferably the molar ratio of 1:3.
Wherein, the silver ion can be from the silver salt that can be dissolved in water equal solvent, such as silver sulfate etc..
Wherein, with the usage ratio of soluble silver salt the two can sufficiently reacted yellowish-brown intermediate product in step 2)
It is advisable, for example, the wherein molar ratio most preferably about 1:1 of Ag ion and contained ruthenium element in yellowish-brown intermediate product.
Wherein, crocus intermediate product and 2 in step 3), 2 '-bipyridyls and/or 2, the use of 2 '-connection its derivative of pyrimidine
Amount ratio is can make the two sufficiently reaction be advisable, for example, wherein crocus intermediate product and 2,2 '-bipyridyls and/or 2,2 '-
Join the molar ratio most preferably about 1:1 of its derivative of pyrimidine.
The derivative of the 2,2 '-bipyridyl or 2,2 '-connection pyrimidines preferably has structure shown in following formula:
Wherein, R includes H, Me and/or OMe.
Below in conjunction with several examples and drawings, further description of the technical solution of the present invention.
Embodiment 1: the preparation of ruthenium catalyst.
1) ruthenic chloride and pentamethylcyclopentadiene (Cp*) are dissolved in a small amount of methanol for 1:3 in molar ratio, flow back 37h,
It is cooled to 0 DEG C, filtering washs to obtain yellowish-brown product [Ru using etherII(Cp*)(Cl)2]2。
2) by [RuII(Cp*)(Cl)2]2With Ag2SO43 times of H is dissolved in for 1:2 in molar ratio2In O, in the case where room temperature is dark
5h is stirred, filtration washing obtains crocus [RuII(Cp*)(H2O)3](SO4)。
3) by [RuII(Cp*)(H2O)3](SO4) with 2,2 '-bipyridyls be in molar ratio 1:1 mixing in water, stir at room temperature
5h is mixed, is filtered, vacuum rotary steam obtains a kind of ruthenium catalyst as shown in formula (I).The catalyst is in D26.0,25 DEG C of conditions of O, pH
Under, on the basis of TSP ' H NMR are as follows: and δ 2.13 (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: catalyst acid decomposition prepares the process of hydrogen.
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
The lower reaction of stirring monitors the variation of gas value by U-tube, continuous gas can be obtained, the gas by volume ratio 1:1 hydrogen and
Carbon dioxide composition.
Embodiment 3: catalyst acid decomposes the anti-poisoning test of formic acid.
1) 10ul formaldehyde finally is added in the reaction solution of obtained reaction solution to having reacted the embodiment 2 of about 3h, blows N2, pass through
U-tube monitors the variation of gas value, and the gas being continuously made of the hydrogen and carbon dioxide of volume ratio 1:1, explanation still can be obtained
The catalyst can anti-formaldehyde poisoning.
2) about 20Mm NAD is added into step (1) finally obtained reaction solution+, blow N2, gas value is monitored by U-tube and is become
Change, the gas being continuously made of the hydrogen and carbon dioxide of volume ratio 1:1 still can be obtained, illustrate that the catalyst can anti-NAD+In
Poison.
3) about 20Mm NADH is added into step (2) finally obtained reaction solution, blows N2, gas value is monitored by U-tube and is become
Change, the gas being continuously made of the hydrogen and carbon dioxide of volume ratio 1:1 still can be obtained, illustrates that the catalyst can be in anti-NADH
Poison.
4) about 5ul hydrogenlyase is added into step (3) finally obtained reaction solution, blows N2, gas is monitored by U-tube
Value variation, still can be obtained the gas being continuously made of the hydrogen and carbon dioxide of volume ratio 1:1, illustrates that the catalyst can anti-first
Acidohydrogenase poisoning.
The anti-poisoning test chart of postscript, the obtained ruthenium catalyst of embodiment 1 sees Fig. 1.
The preparation process phase of the synthesis step of other compounds shown in formula (I), (II) and ruthenium catalyst in embodiment 1
Seemingly.And these catalyst are tested referring to embodiment 2-3, it can be found that it is with close with the obtained catalyst of embodiment 1
Low temperature, normal pressure, can efficiently be catalyzed formic acid under the conditions of water phase and decompose the performance for generating hydrogen.
The above is only part preferred embodiment of the invention, it is noted that for the ordinary skill people of the art
Member, without departing from the principle of the present invention, can also make several variations in detail, these variations in detail also should be regarded as this hair
Bright protection scope.
Claims (8)
1. a kind of application of ruthenium catalyst of the anti-poison guard catalyst formic acid hydrogen manufacturing of efficient cryogenic in catalysis formic acid hydrogen manufacturing, feature exist
In: the catalyst is selected from the metal complex with structure shown in following formula (I) or (II),
Wherein, R is selected from H, Me or OMe.
2. a kind of formic acid hydrogen production process, characterized by comprising: ruthenium catalyst is soluble in the aqueous phase in system, and makes formic acid in -20
It is catalytically decomposed in the aqueous phase system by the ruthenium catalyst under conditions of~100 DEG C, to obtain hydrogen；
The catalyst is selected from the metal complex with structure shown in following formula (I) or (II),
Wherein, R is selected from H, Me or OMe.
3. formic acid hydrogen production process according to claim 2, characterized by comprising: the ruthenium catalyst is soluble in the aqueous phase body
In system, and formic acid is directly continuously added to the aqueous phase system, to continuously obtain hydrogen.
4. formic acid hydrogen production process according to claim 2, characterized by comprising: catalysis of the formic acid in the ruthenium catalyst
The lower substance generated that decomposes of effect contains only the hydrogen and carbon dioxide that volume ratio is 1:1.
5. formic acid hydrogen production process according to claim 2, characterized by comprising: be not higher than 50 DEG C of condition in temperature
Under, using water as the solvent of the ruthenium catalyst, formic acid is catalytically decomposed, to obtain hydrogen.
6. formic acid hydrogen production process according to claim 5, characterized by comprising: under normal temperature conditions, using water as institute
Formic acid is catalytically decomposed in the solvent for stating ruthenium catalyst, to obtain hydrogen.
7. formic acid hydrogen production process according to claim 6, characterized by comprising: under conditions of temperature is 33 DEG C, with
Solvent of the water as the ruthenium catalyst, is catalytically decomposed formic acid, to obtain hydrogen.
8. the formic acid hydrogen production process according to any one of claim 5-7, it is characterised in that: the ruthenium catalyst is catalyzed first
The TOF that acid decomposes is up to 420h-1。
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| CN108298499B (en) * | 2018-03-06 | 2021-04-20 | 大连理工大学 | Method for decomposing and releasing hydrogen by catalyzing formic acid with water-soluble metal complex |
| CN114759202B (en) * | 2022-04-15 | 2023-12-15 | 中南大学 | Catalyst for catalyzing formic acid to prepare hydrogen and preparation method and application thereof |
| CN114832812A (en) * | 2022-05-10 | 2022-08-02 | 北京华璞科技有限公司 | Method for preparing hydrogen catalyst from graphene-Ru formic acid |
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