CN107128875A - A kind of producing hydrogen, catalyzing system, hydrogen manufacturing system comprising the catalyst system and catalyzing and application thereof - Google Patents
A kind of producing hydrogen, catalyzing system, hydrogen manufacturing system comprising the catalyst system and catalyzing and application thereof Download PDFInfo
- Publication number
- CN107128875A CN107128875A CN201710398415.2A CN201710398415A CN107128875A CN 107128875 A CN107128875 A CN 107128875A CN 201710398415 A CN201710398415 A CN 201710398415A CN 107128875 A CN107128875 A CN 107128875A
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- Prior art keywords
- hydrogen
- catalyzing
- oxygen
- catalyst
- hydrogen manufacturing
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 260
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 260
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 166
- 239000003054 catalyst Substances 0.000 title claims abstract description 141
- -1 catalyzing system Substances 0.000 title claims abstract description 21
- 150000002431 hydrogen Chemical class 0.000 title claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000001301 oxygen Substances 0.000 claims abstract description 144
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 125
- 229910052751 metal Inorganic materials 0.000 claims abstract description 125
- 239000002184 metal Substances 0.000 claims abstract description 125
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- 239000011943 nanocatalyst Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 36
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- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 210000005239 tubule Anatomy 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The present invention provides a kind of producing hydrogen, catalyzing system, hydrogen manufacturing system comprising the catalyst system and catalyzing and application thereof.Described producing hydrogen, catalyzing system includes metal nano catalyst and biomass water solution, described metal nano catalyst biomass water solution hydrogen manufacturing, the hydrogen production efficiency and hydrogen capacity of described catalyst system and catalyzing are controlled by the amount of oxygen, and the hydrogen production efficiency of the catalyst system and catalyzing increases with the rise of oxygen pressure or concentration in hydrogen production reaction system.The present invention controls the generation speed of hydrogen using oxygen molecule first, and the hydrogen production process is efficiently, and equipment is simple, clean environment firendly, easily operation, at low temperature（≥0℃）Water decomposition and biomass decomposition hydrogen manufacturing can be realized simultaneously, the reaction condition of energy consumption, even up to Non-energy-consumption is greatly reduced, and are a kind of sustainable catalysis process, are had broad application prospects.Meanwhile, the catalyst system and catalyzing can be used for hydrogen manufacturing, derived energy chemical, battery, water process, paint, functional textile, indoor air cleaning to eliminate aldehyde, petrochemical industry, carbon-hydrogen bond activation, pharmacy, prepare the fields such as hydrogeneous water.
Description
Technical field
The present invention relates to energy and environment field, more particularly to a kind of producing hydrogen, catalyzing system, the catalyst system and catalyzing is included
Hydrogen manufacturing system and application thereof.
Background technology
With the development of social economy and science and technology, the mankind are increasingly paid close attention to the energy and environmental problem.Exploitation cleaning,
Efficient new energy, solves energy shortage and problem of environmental pollution is increasingly becoming the core mission of current social development.Hydrogen fires
High, the nontoxic odorless of burning value, combustion product are environmentally friendly, are regenerative resources.Hydrogen Energy is meeting the following sustainable energy in the world
Demand side certainly will be played an important role.
Hydrogenous material most abundant is water on the earth, next to that various fossil fuel coals, oil, natural gas and various biologies
Matter etc..Hydrogen source, that is, the method for researching and developing various hydrogen manufacturing must be developed first using Hydrogen Energy.In the long term with water or biomass
It is most promising method for waste hydrogen, raw material is inexhaustible, and hydrogen burning is released and generates product water after energy,
Do not cause environmental pollution.
Many traditional hydrogen production process are unsustainable, because they employ the fossils such as coal, oil, natural gas
The energy is as fuel and raw material, and reaction temperature is typically maintained in hundreds of degrees Celsius, is the course of reaction of high energy consumption, and can discharge
Go out great amount of carbon dioxide and carbon monoxide isothermal chamber gas and toxic gas.Meanwhile, all kinds of fossil energy reserves are limited, with people
The continuous exploitation of class, their exhaustion is inevitable, and most of fossil energy this century will be produced totally.
Specifically, traditional silicol process include the hydrogen manufacturing of (1) water-gas method, (2) by raw material hydrogen manufacturing of natural gas or light oil,
(3) legal system hydrogen and (4) water electrolysis hydrogen production are aoxidized by raw material of heavy oil.
Water-gas method hydrogen manufacturing is to utilize anthracite or coke to be that raw material and vapor react in high temperature and obtains water-gas (C+
H2O→CO+H2), make it make CO therein change into CO by catalyst together with vapor after purification again2(CO+H2O→CO2+H2)
Hydrogen making.This method hydrogen manufacturing yield is big, but equipment is more, and reaction temperature is higher (generally>200 DEG C), limit its extensive
Popularization and application.
It is obtained with steam reaction conversion in the presence of catalyst using natural gas or light oil as waste hydrogen
Hydrogen, course of reaction includes (1) CH4+H2O→CO+H2(2) CnH2n+2+nH2O→nCO+(2n+1)H2.The reaction typically exists
Carried out at 800~820 DEG C, energy consumption is of a relatively high.
Legal system is aoxidized by raw material of heavy oil and takes hydrogen, it is deep that heavy oil feedstock therein includes normal pressure, decompression residuum and oil
Fuel oil after degree processing.Hydrogen-containing gas product is made with water vapour and oxygen reaction in heavy oil.This kind of method is related to heavy oil and water
Steam, reaction temperature and energy consumption are higher and unsustainable.
Water electrolysis hydrogen production is current application relatively one of wide and method of comparative maturity.Water is that raw material hydrogen production process is hydrogen and oxygen
The inverse process of burning generation water, as long as therefore the certain energy of offer certain forms can then make water decomposition.There is provided electric energy makes moisture
The efficiency of hydrogen is made typically 75~85% in solution, and its technical process is simply pollution-free, but consumption electricity is big, and hydrogen production efficiency
Reduced with the rise of oxygen pressure or concentration (because water electrolysis hydrogen producing reaction is reversible reaction), therefore its application is by one
Fixed limitation.
In addition to above-mentioned traditional hydrogen production process, photochemistry silicol process has been risen in current worldwide, has been referred to using water as original
Material, the method for photocatalytic water splitting hydrogen making.Photocatalytic process is, in the reaction system containing catalyst, to promote under light illumination
Hydrogen is made in hydrolysis.This method has certain DEVELOPMENT PROSPECT, but needs the participation of luminous energy just to occur production hydrogen reaction, together
When photocatalysis efficiency it is typically relatively low, and hydrogen production efficiency reduces with the rise of oxygen pressure or concentration (because photocatalysis water
Decomposing hydrogen-production reaction is also reversible reaction), therefore can not large-scale promotion application.
In summary, whether traditional or emerging silicol process, all has that reaction temperature is high, energy consumption is big, process is multiple
It is miscellaneous, need extra additive, transformation efficiency is low, reactant is non-renewable, accessory substance is harmful, hydrogen production efficiency is with oxygen pressure
Or concentration rise and reduce (because water decomposition hydrogen production reaction is reversible reaction, oxygen and hydrogen easily recombine generation water) etc.
Problems, which greatly limits their actual application prospect.Meanwhile, using hydrogen made from traditional hydrogen production process, even if
Using hydrogen as fuel, the present situation that the global warming that thereby results in and fossil fuel are constantly exhausted can not be solved.
It is well known that biomass resource is abundant, it is important regenerative resource.If a kind of catalysis process can be invented,
Biomass and water are carried out simultaneously under gentle reaction condition to be converted into hydrogen, undoubtedly future society enters in terms of the energy
One of optimal selection of row sustainable development.
In hydrogen preparation field, it is necessary to it is important to note that for most hydrogen production reactions, either using natural dehydrogenation
Enzyme or artificial synthesized catalysis material are also either still industrialized in hydrogen production process as production hydrogen catalyst in laboratory,
It is required in advance removing the oxygen in reaction system completely, this, which is primarily due to oxygen, with hydrogen in catalyst surface to occur
Back reaction, generation water or hydroxide (2H2+O2→2H2O), so as to substantially reduce the hydrogen production efficiency of reaction system.Therefore, in order to
Hydrogen production efficiency is improved, the closed of reaction system must be kept at any time in hydrogen production process, it is impossible to be doped into air or oxygen, with
The progress of hydrogen production reaction, in addition it is also necessary to constantly discharge the oxygen of generation, this needs the extra vacuum equipment of increase or storage inertia
The equipment (being passed through inert gas to discharge oxygen) of gas, this can not only increase hydrogen manufacturing cost, can also make operation more complicated,
It is difficult to control to, is unfavorable for industrial application.
The content of the invention
In view of the shortcomings of the prior art, the technical problems to be solved by the invention are to provide a kind of low energy consumption, or even incompetent
The green catalysis hydrogen manufacturing system of consumption；The system utilizes metal nano catalyst, by controlling the pressure or concentration of oxygen to control
Biomass water solution manufactures hydrogen.
To solve the technical problem of the present invention, the present invention is adopted the following technical scheme that：
A kind of producing hydrogen, catalyzing system, described catalyst system and catalyzing includes metal nano catalyst and biomass water solution, described
Metal nano catalyst biomass water solution hydrogen manufacturing, the hydrogen production efficiency and hydrogen capacity of described catalyst system and catalyzing are by oxygen
Amount control, the hydrogen production efficiency of the catalyst system and catalyzing increases with the rise of oxygen pressure or concentration in hydrogen production reaction system,
The amount of the oxygen includes the amount of oxygen and the amount for the oxygen that is dissolved in the water in gas phase, and described metal nano catalyst is load
Type metal nano catalyst or unsupported metals nanocatalyst, the unsupported metals nanocatalyst is by metal nano
Material is constituted, and the load type metal nanocatalyst includes metal nano material and carrier.
It is of the invention that for existing in traditional hydrogen-making reaction procedure, reaction temperature is high, energy consumption is big, process is complicated, need additionally
Additive, transformation efficiency are low, reactant is non-renewable, accessory substance is harmful, hydrogen production efficiency is with the rise of oxygen pressure or concentration
And the problem of (because water decomposition hydrogen production reaction is reversible reaction) etc. is many to be unfavorable for industrial applications is reduced, develop a kind of height
The low temperature producing hydrogen, catalyzing system of effect.
Applicants have unexpectedly found that, the hydrogen production efficiency and hydrogen capacity of described catalyst system and catalyzing are controlled by the amount of oxygen, tool
For body, the hydrogen production efficiency of the catalyst system and catalyzing increases with the rise of oxygen pressure or concentration in reaction system, wherein, oxygen
The amount of gas includes the amount of oxygen and the amount for the oxygen that is dissolved in the water in gas phase.Meanwhile, according to Henry's law (Henry's law),
The amount of oxygen of being dissolved in the water is proportional to the amount of oxygen in gas phase, and especially at ambient temperature, ratio is about 769.2L
atm/mol.This has been broken traditional hydrogen manufacturing theory by the hydrogen manufacturing phenomenon of Oxygen control, because being existed between oxygen and hydrogen
Back reaction, i.e. 2H2+O2→2H2O, generally under conditions of with the presence of oxygen, the generation speed or amount of hydrogen can be with oxygen
The increase of amount and reduce.
More it has surprisingly been found that in zero degree (0 DEG C) hydrogen production reaction can occur for described catalyst system and catalyzing, meanwhile, it is described
Protium in the hydrogen of catalyst system and catalyzing generation is from not only the hydrogen in water, the hydrogen also in biomass.That is,
Under so low reaction temperature, water can also decompose hydrogen manufacturing.The area of earth surface about 70% is all covered with water, using water as
Waste hydrogen is most promising method, and raw material is inexhaustible, and hydrogen burning is released and generates product water after energy again, no
Cause environmental pollution.Therefore, the catalyst system and catalyzing is a kind of sustainable hydrogen manufacturing system, is had broad application prospects.
Protium in the hydrogen of the catalyst system and catalyzing generation is also tried from not only the hydrogen in water from as sacrifice
Hydrogen in the biomass of agent.Oxygen and hydrone are generated in metal nano catalyst surface in the presence of biomass, first and lived
Property oxygen species (including peroxyl species, superoxide species), this kind of active oxygen species can should generate hydrogen and other with biomass reverse again
Accessory substance, acid, ester, salt, carbon carbon coupled product, carbon dioxide etc..
Further, the catalyst system and catalyzing can decompose aquatic products hydrogen without external energy, but be not excluded for utilizing additional energy
Measure to improve reaction rate.Term " external energy " includes but is not limited to one kind of mechanical energy, heat energy, electric energy, luminous energy and ultrasound
Or it is a variety of.
Although at 0 DEG C hydrogen production reaction can occur for the catalyst system and catalyzing, in order to reach optimal hydrogen generation efficiency, hydrogen production reaction
Temperature can be 0 DEG C~100 DEG C；It is preferred that, the reaction temperature of the catalyst system and catalyzing is 0 DEG C~30 DEG C；It is preferred that, the catalysis
The reaction temperature of system is room temperature；It is furthermore preferred that the reaction temperature of the catalyst system and catalyzing is 0 DEG C~10 DEG C；It is furthermore preferred that described
The reaction temperature of catalyst system and catalyzing is 0 DEG C.Described room temperature can be normal room temperature (room temperature, 23 ± 5 DEG C),
Real indoor temperature can be referred to.The catalyst system and catalyzing of the present invention has high catalytic efficiency, it might even be possible in maximum conditions
Lower catalytic water hydrogen manufacturing, described maximum conditions are 0 DEG C.
Further, metal nano material group VIII and/or IB group 4 transition metals in the periodic table of elements
Metal simple-substance, metal alloy, metal oxide, core shell structure, metal sulfide and metal carbides any one or it is any
It is a variety of.It is, the metal nano material can be first kind material (group VIII transition metal any one or it is any
The material of a variety of formation, described material is selected from metal simple-substance, metal alloy, metal oxide, metal sulfide and metal carbon
Compound any one or it is any a variety of) or Equations of The Second Kind material (group ib transition metal any one or it is any many
The material formed is planted, described material is selected from metal simple-substance, metal alloy, metal oxide, metal sulfide and metallic carbide
Thing any one or it is any a variety of), can also be the mixture of first kind material and Equations of The Second Kind material.
Further, the carrier of the load type metal nanocatalyst includes group ia and/or IIA in the periodic table of elements
The oxide of race's element, hydroxide, carbide, oxycarbide, molecular sieve, salt any one or it is any a variety of.It is,
The carrier of the load type metal nanocatalyst can comprising the first material (a Group IA element any one or it is any many
Kind of the material formed, described material be selected from oxide, hydroxide, carbide, oxycarbide, molecular sieve, salt it is any one
Kind or it is any a variety of), can also comprising second material (material of any one or any a variety of formation of group iia element,
Described material be selected from oxide, hydroxide, carbide, oxycarbide, molecular sieve, salt any one or it is any a variety of),
The mixture of first kind material and Equations of The Second Kind material can also be included.Described carrier does not include strontium titanates.
Further, the metal nano material size that the metal nano catalyst is included is below 100 nanometers.
Further, described metal nano material is elemental metals, described elemental metals be selected from Cu, Ag, Au, Co,
Rh, Ir, Fe, Ru, Ni, Pt, Pd any one or it is any a variety of.
Further, described metal nano material is selected from alloy, core shell structure and the oxide that metal is constituted, described
Metal be selected from Cu, Ag, Au, Co, Rh, Ir, Fe, Ru, Ni, Pt, Pd any one or it is any a variety of.
Further, described metal nano material is selected from the metal of Ag, Au, Cu any one or any a variety of formation
Simple substance, metal alloy, metal oxide, core shell structure, metal sulfide and metal carbides.
Further, described metal nano material is selected from the material of Ag, Au, Cu any one or any a variety of formation
Material, described material is selected from metal simple-substance, metal alloy, metal oxide, core shell structure, metal sulfide and metal carbides
Any one or it is any a variety of.It is, described metal nano material is selected from the first material, (Ag, Au, Cu's is any one
Kind or any a variety of formation metal simple-substance), second material (metal of Ag, Au, Cu any one or any a variety of formation
Alloy), the third material (metal oxides of Ag, Au, Cu any one or any a variety of formation), the 4th kind of material (Ag,
The core shell structure of Au, Cu any one or any a variety of formation), the 5th kind of material (Ag, Au, Cu any one or it is any
The metal sulfide of a variety of formation), the 6th kind of material (metallic carbide of Ag, Au, Cu any one or any a variety of formation
Thing), described metal nano material can be selected from the first material, second material, the third material, the 4th kind of material, the
Five kinds of materials, the 6th kind of material any one or it is any a variety of.
Further, the load type metal nanocatalyst can be included relative to overall catalyst weight gauge about 0.002
~0.5wt%, 0.2~2wt% or 0.5~5wt% metal nano material.
Further, the mol ratio of the metal nano catalyst and biomass water solution is：Metal nano material: biological
Matter: water=1~8: 200~30000: 80000~150000.
Further, the quality proportioning of metal nano material and carrier is in the load type metal nanocatalyst：0.2
~5: 80~200.
Further, described carrier is selected from the oxide of any one or any various metals of group iia element；It is preferred that
, described carrier includes magnesia；Further preferably, described carrier is magnesia；It is furthermore preferred that described carrier is oxidation
The weight of magnesia in the mixture of magnesium and other inorganic matters, the mixture is than at least 10wt%, or is at least
50wt%, or at least 80wt%.Magnesia is particularly preferred as cheap, readily available carrier material.
Further, carrier of the present invention may be selected from Mg (OH)2、Ca(OH)2、CaCO3、MgCO3And MgTiO3Appoint
Meaning is a kind of or any a variety of.
Further, described carrier is selected from any one of described carrier selected from Mg ions, Ca ions or any two
The material of kind of modification, described material be selected from oxide and molecular sieve any one or it is any two kinds.It is, described load
Body is selected from the molecule of molecular sieve, the molecular sieve of Ca ion modifications, Mg ions and the Ca ion modifications of MgO, CaO, Mg ion modification
Sieve any one or it is any a variety of.
It is furthermore preferred that the carrier is selected from MgO and Mg (OH)2Any one or it is any two kinds.
Further, described carrier exists in the form of arbitrary dimension and the formed body of geometry, preferably with
The geometry of big specific surface area is present.It is furthermore preferred that the specific surface area of the carrier can be 10~400m2/ g or 60
~800m2/ g or 50~550m2/g。
Further, described biomass be selected from alcohol, aldehyde, acid, ketone, ether, ester any one or it is any a variety of.
Further, described alcohol is selected from any one of C1 to C12 fatty alcohol, aromatic alcohol and unsaturated alcohol or appointed
Meaning is a variety of.It is preferred that, described alcohol be selected from methanol, ethanol, isopropanol, ethylene glycol, glycerine any one or it is any a variety of.
Further, any one of fatty aldehyde of the described aldehyde selected from C1 to C12, ester ring aldehyde, aromatic aldehyde, terpene aldehyde
Or it is any a variety of.It is preferred that, described aldehyde be selected from formaldehyde, acetaldehyde, propionic aldehyde, hutanal, isobutylaldehyde, cyclohexanecarboxaldehyde, benzaldehyde,
Phenylacetaldehyde any one or it is any a variety of.
Further, described acid be selected from C1 to C12 aliphatic acid and aromatic acid any one or it is any a variety of, it is excellent
Choosing, described acid be selected from formic acid, ascorbic acid, ethylenediamine tetra-acetic acid any one or it is any a variety of.
Second object of the present invention is to provide described catalyst system and catalyzing in hydrogen manufacturing, derived energy chemical, battery, water process, oil
Paint coating, functional textile, indoor air cleaning are eliminated aldehyde, petrochemical industry, carbon-hydrogen bond activation, pharmacy, prepared in hydrogeneous water
Purposes.Further, the hydrogen that the catalyst system and catalyzing can be produced be used in derived energy chemical and petrochemical process as
High-grade fuel.Further, can by catalyst preparation into coating, or be carried on textile, leather, ceramics, carbon material,
It is used to the depollution of environment on the carriers such as glass handle, aldehydes molecule more particularly in air, such as the decomposition of formaldehyde.Further
Ground, the catalyst system and catalyzing can be used for medical field, such as prepare medical hydrogeneous water.
Third object of the present invention is to provide a kind of hydrogen manufacturing system, and described hydrogen manufacturing system includes a kind of any of the above described shape
The catalyst system and catalyzing and oxygen of formula, described hydrogen manufacturing system can also include the components such as reactor, Second support.The Second support
For carried metal nanocatalyst, described Second support is organic matter or inorganic matter with loading functional, described
Two carriers be selected from ceramics, glass, fiber, cloth, plastics, coating, molecular sieve any one or arbitrarily it is a variety of.The reactor
Refer to the device that the catalyst after load can be fixed, described reactor is selected from Photoreactor, electrode system, heat energy utilization
System any one or it is any a variety of, described Photoreactor is to refer to occur light-catalyzed reaction and photochemically reactive anti-
Device is answered, described electrode system is to refer to the system using hydrogen gas generation, and the heat energy utilization system is to refer to utilize hydrogen
The system of gas heat supply.
When the metal nano catalyst is load type metal nanocatalyst, its preparation comprises the following steps：
1) metal nano material is prepared, and prepares carrier；
2) by step 1) prepare metal nano material be carried on carrier surface or its inside, be made metal nano catalysis
Agent, then by the stable described catalyst of heat-treating methods, while removing part and the pollution on metal nano material surface
Thing.
Different from step 1) and 2), can also be using different metal precursors in step 1) selected by pass through on carrier material
Local reduction way carried metal nano material.In one or more embodiments, selected metal precursor can be transition gold
Nitrate, sulfate, chlorate, oxalates, carbonate, citric acid, nitrate or the combinations thereof of category.One or more
In embodiment, selected reducing agent can be sodium borohydride, borine and boron amide.
Further, described metal nano material size is below 100 nanometers.
Further, described metal nano material is elemental metals, described elemental metals be selected from Cu, Ag, Au, Co,
Rh, Ir, Fe, Ru, Ni, Pt, Pd any one or it is any a variety of.
Further, described metal nano material is selected from alloy, core shell structure and the oxide that metal is constituted, described
Metal be selected from Cu, Ag, Au, Co, Rh, Ir, Fe, Ru, Ni, Pt, Pd any one or it is any a variety of.
Further, described metal nano material is selected from the metal of Ag, Au, Cu any one or any a variety of formation
Simple substance, metal alloy, metal oxide, core shell structure, metal sulfide and metal carbides.
Further, described metal nano material is selected from the material of Ag, Au, Cu any one or any a variety of formation
Material, described material is selected from metal simple-substance, metal alloy, metal oxide, core shell structure, metal sulfide and metal carbides
Any one or it is any a variety of.It is, described metal nano material is selected from the first material, (Ag, Au, Cu's is any one
Kind or any a variety of formation metal simple-substance), second material (metal of Ag, Au, Cu any one or any a variety of formation
Alloy), the third material (metal oxides of Ag, Au, Cu any one or any a variety of formation), the 4th kind of material (Ag,
The core shell structure of Au, Cu any one or any a variety of formation), the 5th kind of material (Ag, Au, Cu any one or it is any
The metal sulfide of a variety of formation), the 6th kind of material (metallic carbide of Ag, Au, Cu any one or any a variety of formation
Thing), described metal nano material can be selected from the first material, second material, the third material, the 4th kind of material, the
Five kinds of materials, the 6th kind of material any one or it is any a variety of.
Further, the load type metal nanocatalyst can be included relative to overall catalyst weight gauge about 0.002
~0.5wt%, 0.2~2wt% or 0.5~5wt% metal nano material.
Further, described carrier is selected from the oxide of any one or any various metals of group iia element；It is preferred that
, described carrier includes magnesia；Further preferably, described carrier is magnesia；It is furthermore preferred that described carrier is oxidation
The weight of magnesia in the mixture of magnesium and other inorganic matters, the mixture is than at least 10wt%, or is at least
50wt%, or at least 80wt%.Magnesia is particularly preferred as cheap, readily available carrier material.
Further, carrier of the present invention may be selected from Mg (OH)2、Ca(OH)2、CaCO3、MgCO3And MgTiO3Appoint
Meaning is a kind of or any a variety of.
Further, described carrier is selected from any one of described carrier selected from Mg ions, Ca ions or any two
The material of kind of modification, described material be selected from oxide and molecular sieve any one or it is any two kinds.It is, described load
Body is selected from the molecule of molecular sieve, the molecular sieve of Ca ion modifications, Mg ions and the Ca ion modifications of MgO, CaO, Mg ion modification
Sieve any one or it is any a variety of.
It is furthermore preferred that the carrier is selected from MgO and Mg (OH)2Any one or it is any two kinds.
The catalyzing manufacturing of hydrogen reaction of hydrogen manufacturing system of the present invention is as follows：
Under conditions of certain temperature and oxygen are present, the hydrogen manufacturing to any of the above form of the present invention is urged
Change system is stirred or shaken, that is, has hydrogen constantly to be produced from the hydrogen manufacturing system, and described catalyst system and catalyzing includes gold
Belong to nanocatalyst and biomass water solution, described metal nano catalyst biomass water solution hydrogen manufacturing, described system
The hydrogen production efficiency and hydrogen capacity of hydrogen system are controlled by the amount of oxygen, and the hydrogen production efficiency of the hydrogen manufacturing system is with hydrogen production reaction body
The rise of oxygen pressure or concentration in system and increase, the amount of the oxygen includes the amount of oxygen and the oxygen that is dissolved in the water in gas phase
Amount, described metal nano catalyst is load type metal nanocatalyst or unsupported metals nanocatalyst, described
Unsupported metals nanocatalyst is made up of metal nano material, and the load type metal nanocatalyst includes metal nano
Material and carrier.
Further, metal nano material group VIII and/or IB group 4 transition metals in the periodic table of elements
Metal simple-substance, metal alloy, metal oxide, core shell structure, metal sulfide and metal carbides any one or it is any
It is a variety of.
Further, the carrier of the load type metal nanocatalyst includes group ia and/or IIA in the periodic table of elements
The oxide of race's element, hydroxide, carbide, oxycarbide, molecular sieve, salt any one or it is any a variety of, it is described
Carrier does not include strontium titanates.
Further, described carrier is selected from the oxide of any one or any various metals of group iia element；It is preferred that
, described carrier includes magnesia；Further preferably, described carrier is magnesia；It is furthermore preferred that described carrier is oxidation
The weight of magnesia in the mixture of magnesium and other inorganic matters, the mixture is than at least 10wt%, or is at least
50wt%, or at least 80wt%.
Further, the metal nano material size that the metal nano catalyst is included is below 100 nanometers.
Further, described metal nano material is elemental metals, described elemental metals be selected from Cu, Ag, Au, Co,
Rh, Ir, Fe, Ru, Ni, Pt, Pd any one or it is any a variety of.
Further, described metal nano material is selected from alloy, core shell structure and the oxide that metal is constituted, described
Metal be selected from Cu, Ag, Au, Co, Rh, Ir, Fe, Ru, Ni, Pt, Pd any one or it is any a variety of.
Further, described metal nano material is selected from the material of Ag, Au, Cu any one or any a variety of formation
Material, described material is selected from metal simple-substance, metal alloy, metal oxide, core shell structure, metal sulfide and metal carbides
Any one or it is any a variety of.
Further, described carrier is selected from the oxide of any one or any various metals of group iia element；It is preferred that
, described carrier includes magnesia；Further preferably, described carrier is magnesia；It is furthermore preferred that described carrier is oxidation
The weight of magnesia in the mixture of magnesium and other inorganic matters, the mixture is than at least 10wt%, or is at least
50wt%, or at least 80wt%.
Further, described carrier is selected from Mg (OH)2、Ca(OH)2、CaCO3、MgCO3And MgTiO3Any one or
It is any a variety of.
Further, described carrier be selected from Mg ions, Ca ions any one or it is any two kinds modification material, institute
The material stated be selected from oxide and molecular sieve any one or it is any two kinds.
Further, the carrier is selected from MgO and Mg (OH)2Any one or it is any two kinds.
Further, described carrier exists in the form of arbitrary dimension and the formed body of geometry, preferably with
The geometry of big specific surface area is present；It is furthermore preferred that the specific surface area of the carrier can be 10~400m2/ g or 60
~800m2/ g or 50~550m2/g。
Further, the load type metal nanocatalyst include relative to overall catalyst weight gauge 0.002~
0.5wt%, 0.2~2wt% or 0.5~5wt% metal nano material.
Further, described biomass be selected from alcohol, aldehyde, acid, ketone, ether, ester any one or it is any a variety of.
Further, described alcohol be selected from C1 to C12 fatty alcohol, aromatic alcohol and unsaturated alcohol any one or it is any
It is a variety of；It is preferred that, described alcohol be selected from methanol, ethanol, isopropanol, ethylene glycol, glycerine any one or it is any a variety of.
Further, described aldehyde be selected from C1 to C12 fatty aldehyde, ester ring aldehyde, aromatic aldehyde, terpene aldehyde any one or
It is any a variety of；It is preferred that, described aldehyde is selected from formaldehyde, acetaldehyde, propionic aldehyde, hutanal, isobutylaldehyde, cyclohexanecarboxaldehyde, benzaldehyde, benzene
Acetaldehyde any one or it is any a variety of.
Further, described acid be selected from C1 to C12 aliphatic acid and aromatic acid any one or it is any a variety of；It is preferred that
, described acid be selected from formic acid, ascorbic acid, ethylenediamine tetra-acetic acid any one or it is any a variety of.
Further, the reaction temperature of the hydrogen manufacturing system is 0 DEG C~100 DEG C；It is preferred that, the reaction of the hydrogen manufacturing system
Temperature is 0 DEG C~30 DEG C；It is preferred that, the reaction temperature of the hydrogen manufacturing system is room temperature；It is furthermore preferred that the hydrogen manufacturing system is anti-
It is 0 DEG C~10 DEG C to answer temperature；It is furthermore preferred that the reaction temperature of the hydrogen manufacturing system is 0 DEG C.Described room temperature can be standard chamber
Temperature (room temperature, 23 ± 5 DEG C) or refer to real indoor temperature.The hydrogen manufacturing system of the present invention has pole
High hydrogen production efficiency, it might even be possible to catalytic water hydrogen manufacturing under extreme conditions, described maximum conditions are 0 DEG C.
In one or more embodiments, the concentration of the metal nano catalyst be about 0.1~20 g/l or
15~120 g/l, or 90~500 g/l.
In one or more embodiments, the biomass material is aldehyde, wherein, the concentration of selected aldehyde is about 0.01~
2 mol/Ls or 1~10 mol/L or 5~20 mol/Ls.
In one or more embodiments, the reaction temperature is 0 DEG C or 23 ± 5 DEG C or 80 DEG C.
In one or more embodiments, the oxygen pressure is about 0.01~0.5 MPa or 0.3~1 MPa,
Or 0.5~10 MPa.
In one or more embodiments, every gram of metal nano catalyst produces the mmoles of speed about 0.1~20 of hydrogen
That/hour or 15~100 mMs/hour or 80~200 mMs/hour.
Protium in the hydrogen of the hydrogen manufacturing system generation is also tried from not only the hydrogen in water from as sacrifice
Hydrogen in the biomass of agent.Oxygen and hydrone are generated in metal nano catalyst surface in the presence of biomass, first and lived
Property oxygen species (including peroxyl species, superoxide species), this kind of active oxygen species can should generate hydrogen and other with biomass reverse again
Accessory substance, acid, ester, salt, carbon carbon coupled product, carbon dioxide etc..In the hydrogen manufacturing system of the present invention, oxygen, which is served, to be helped
The effect of catalyst.
Further, the hydrogen manufacturing system can decompose aquatic products hydrogen without external energy, but be not excluded for utilizing additional energy
Measure to improve reaction rate.Term " external energy " includes but is not limited to one kind of mechanical energy, heat energy, electric energy, luminous energy and ultrasound
Or it is a variety of.
Further, the hydrogen manufacturing system need not add extra auxiliary agent, but being not precluded within to add in reaction system helps
Agent improves reaction rate, and described auxiliary agent is selected from KOH, NaOH, K2CO3、Na2CO3, sodium formate, ethylenediamine any one or
It is any a variety of.
Fourth object of the present invention is to provide the catalyst system and catalyzing of any form described above in hydrogen manufacturing, energy
Work, battery, water process, paint, functional textile, indoor air cleaning eliminate aldehyde, petrochemical industry, carbon-hydrogen bond activation, system
Medicine, the purposes prepared in hydrogeneous water.
The 5th purpose of the present invention is to provide the hydrogen manufacturing system of any form described above in hydrogen manufacturing, energy
Work, battery, water process, paint, functional textile, indoor air cleaning eliminate aldehyde, petrochemical industry, carbon-hydrogen bond activation, system
Medicine, the purposes prepared in hydrogeneous water.
Beneficial effects of the present invention are as follows：
1) the present invention relates to a kind of catalyst system and catalyzing of utilization biomass water solution hydrogen manufacturing, the catalyst system and catalyzing possesses following excellent
Point：Hydrogen production efficiency is high, raw material is cheap and easy to get, catalytic process cleaning environmental protection, harmless to environment and human body and can be to containing aldehyde
Waste water and gas carries out twice laid.Meanwhile, the protium in the hydrogen of preparation is from not only biomass, also from water；Mirror
All it is reproducible raw material in biomass and water, the catalytic process is a kind of sustainable hydrogen production process, is suitable for industrialization
Production；2) new hydrogen production system of the present invention is compared with traditional hydrogen manufacturing system, there is unexpected effect.Pass
The hydrogen manufacturing system of system, the presence of oxygen serves negative to hydrogen manufacturing, shows that the yield and speed of hydrogen can be with systems
The rise of oxygen pressure or concentration and reduce；And the oxygen of the present invention serves the effect of co-catalyst, table in hydrogen production process
The yield and speed of present hydrogen can increase with the rise of oxygen pressure in system or concentration；Because oxygen feed is easy to get,
Wide material sources, and it is safe and reliable, this can promote the upgrading and energy revolution of following hydrogen production process；3) present invention is a kind of low energy
Consumption, in addition Non-energy-consumption green catalysis hydrogen manufacturing system, without by heat energy, luminous energy, electric energy and ultrasound, at low temperature (>=0 DEG C)
Aquatic products hydrogen can be decomposed indirectly, be a kind of hydrogen manufacturing system of energy-conservation；4) present invention extends to depollution of environment process field, special
It is not related to the decomposition and harmless treatment of formaldehyde；5) reaction raw materials and reaction scheme energy-conserving and environment-protective of the present invention, to the energy of China
Development in terms of source science and technology and environmental protection has great impetus；6) catalyst system and catalyzing of the present invention can be used for making
Hydrogen, derived energy chemical, battery, water process, paint, functional textile, indoor air cleaning eliminate aldehyde, petrochemical industry, hydrocarbon
Bond activation, pharmacy, prepare the fields such as hydrogeneous water.
Brief description of the drawings
Fig. 1 is Ag/MgO HAADF-STEM pictures (embedded picture is monodispersed Ag nano particles), HR-TEM pictures
And XRD spectra.
Fig. 2 is the TEM pictures of Ag/MgO, Au/MgO, Pd/MgO and Pt/MgO catalyst.
Fig. 3 is the influence that oxygen partial pressure (low pressure to normal pressure) is catalyzed formalin hydrogen manufacturing to Ag/MgO.
Fig. 4 is the influence that oxygen partial pressure (high pressure) is catalyzed formalin hydrogen manufacturing to Ag/MgO.
Fig. 5 is that log-log graph shows that the catalytic activity and oxygen partial pressure of Ag/MgO catalyst are directly proportional.
Fig. 6 is the design sketch that Ag/MgO is catalyzed different aldehyde solution hydrogen manufacturing.
During Fig. 7 is Ag/MgO catalyst formalins, O2, H2, CO2With CO variation tendency.
Fig. 8 is the deuterated experiment that Ag/MgO is catalyzed acetaldehyde solution hydrogen manufacturing.
Fig. 9 is the influence that reaction temperature is catalyzed formalin hydrogen manufacturing to Ag/MgO.
Figure 10 is the influence that concentration of formaldehyde is catalyzed formalin hydrogen manufacturing to Ag/MgO.
Figure 11 is the catalytic effect figure that group VIII and/or IB group 4 transition metals load MgO are catalyzed formalin hydrogen manufacturing.
Figure 12 is the catalytic effect figure that group VIII and/or IB group 4 transition metals load MgO are catalyzed acetaldehyde solution hydrogen manufacturing.
Figure 13 be Ag/MgO catalysis formalin during DMPO (dimethyl pyridine N-oxide) capture free radical with
The change procedure of time.
Figure 14 is rotating ring disk electrode (r.r.d.e) system testing curve of the Ag/MgO and Pt/MgO catalyst in 0.1M KOH solutions
With current-responsive curve.
Figure 15 is various concentrations hydrogen peroxide (H2O2) solution catalyzing formaldehyde hydrogen manufacturing.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of instruction of the present invention has been read, this area skill
Art personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims institute
The scope of restriction.
Embodiment 1
Embodiment 1-18 illustrates the hydrogen manufacturing of the present invention so that Ag/MgO catalyst, formalin are biomass solution as an example
Effect, the pattern and structural characterization of Ag/MgO catalyst are as shown in figure 1, the specific surface area of the catalyst is 80m2/ g, Ag are born
Carrying capacity is 0.8wt%.Fig. 1 a-d are Ag/MgO HAADF-STEM pictures (embedded picture is monodispersed Ag nano particles), are shown
Ag nano particles being uniformly distributed on MgO surfaces is shown；The HR-TEM pictures that Fig. 1 e are Ag/MgO (are embedded in picture for Selected area electron
Diffraction pattern), it is shown that Ag (111) crystal faces and MgO (200) crystal face；Scheme the XRD spectra that f is Ag/MgO, it is shown that Ag's and MgO
Diffraction maximum.HAADF-STEM refers to angle of elevation annular dark-scanning transmission electron microscope, and HR-TEM refers to high power transmission electricity
Mirror, XRD refers to X-ray diffraction.
20 milligrams of Ag/MgO catalyst are taken to insert in the formalin that 5 milliliters of concentration are 1mol/L, reaction temperature is set
For 25 DEG C of normal temperature, (oxygen partial pressure is about 0.22atm in air atmosphere；Atm refers to standard atmospheric pressure, i.e. 0.101MPa) stirring
Reaction solution, H2Constantly produced from the aqueous solution, and H2Generating rate be 2.5mmol/hg, wherein unit mmol/hg refers to
The growing amount (mM) of every gram of catalyst hydrogen per hour.
Wherein, (gas-chromatography packed column utilizes Porapak Q posts using GC-TCD detections for oxygen partial pressure and hydrogen growing amount
Son or 5A molecular sieves pillar), the product utilization GC-MS in liquid phase is determined.All embodiments of the present invention and the comparative example party
Method determines gas content and product liquid.
Embodiment 2-13 oxygen pressures, dissolved oxygen content and hydrogen output the results are shown in Table 1.
| Sequence number | Gas phase oxygen pressure/MPa | Dissolved oxygen content/micro- is rubbed | Hydrogen output/micro- rubs |
| Embodiment 2 | 0.00 | 0 | 0 |
| Embodiment 3 | 0.01 | 0.39 | 96.0 |
| Embodiment 4 | 0.02 | 1.24 | 273.6 |
| Embodiment 5 | 0.03 | 1.43 | 309.7 |
| Embodiment 6 | 0.04 | 2.34 | 460.4 |
| Embodiment 7 | 0.06 | 3.77 | 691.2 |
| Embodiment 8 | 0.07 | 4.75 | 803.1 |
| Embodiment 9 | 0.10 | 6.50 | 1116.5 |
| Embodiment 10 | 0.20 | 13.0 | 734.3 |
| Embodiment 11 | 0.30 | 19.5 | 1095.0 |
| Embodiment 12 | 0.41 | 26.0 | 1180.6 |
| Embodiment 13 | 0.51 | 32.5 | 1254.1 |
Embodiment 2-13 have studied different oxygen pressure/concentration in hydrogen manufacturing system and be catalyzed formalin hydrogen manufacturing to Ag/MgO
Influence.Reaction condition：Room temperature (25 DEG C), concentration of formaldehyde is 1mol/L, and volume is 5 milliliters, and Ag load capacity is 0.8wt%, Ag/
MgO mass is 20 milligrams；For embodiment 2-10 reaction, the reaction time is 6 hours, for embodiment 11-13 reaction, instead
It is 2 hours between seasonable.It can be seen that when oxygen pressure is 0 (embodiment 2), almost produced without hydrogen from embodiment 2-13,
When oxygen pressure rises to 0.51 MPa from 0, hydrogen output illustrates that oxygen has decision to hydrogen also with linear rise
The influence of property.Meanwhile, by controlling oxygen pressure, we can also control the speed and total amount that hydrogen is produced.As can be seen from Figure 3,
During Ag/MgO catalysis formalin hydrogen manufacturing, with the rise of oxygen partial pressure, hydrogen generation rate is also increased.From
Fig. 4 is understood, under hyperbaric environment, and Ag/MgO catalysis formalin hydrogen production rate is raised also with the rise of oxygen partial pressure, institute
State hyperbaric environment and refer to oxygen partial pressure>1 atmospheric pressure (1atm).From Fig. 3 and Fig. 4 it can also be seen that being catalyzed formaldehyde in Ag/MgO
During solution hydrogen manufacturing, oxygen partial pressure served it is vital, when oxygen partial pressure from low pressure (minimum is 0) rises to normal pressure
When finally rising to high pressure (0.5 MPa) again, the hydrogen generating quantity in the unit interval is increasing always.Meanwhile, we are to catalyst
Hydrogen production activity and oxygen partial pressure do and found after double logarithmic curve, the production hydrogen activity of catalyst is proportional to oxygen partial pressure (Fig. 5).From
Fig. 5 is understood, in the range of the oxygen partial pressure verified (0~0.5 MPa), and Ag/MgO catalysis formalin hydrogen production rate is proportional to
Oxygen partial pressure.
Embodiment 14
It is the different aldehyde of 1mol/L (formaldehyde, acetaldehyde, propionic aldehyde, just to take 20 milligrams of Ag/MgO catalyst to be respectively implanted 5 milliliters of concentration
Butyraldehyde, isobutylaldehyde, cyclohexanecarboxaldehyde, benzaldehyde, phenylacetaldehyde) the aqueous solution in, reaction temperature is set to 25 DEG C of normal temperature, in air
(oxygen partial pressure is about 0.22atm) stirring reaction liquid, H under atmosphere2Constantly produced from the aqueous solution, H2Generating rate such as Fig. 6 institutes
Show.As can be seen from Figure 6, Ag/MgO catalyst can be catalyzed the aldehyde solution hydrogen manufacturing of all kinds, wherein, the hydrogen production efficiency of formalin
With respect to highest, the hydrogen production efficiency of benzaldehyde is relatively worst, and total hydrogen production efficiency is arranged in the following order：
Formaldehyde>>Acetaldehyde ≈ propionic aldehyde ≈ hutanal ≈ isobutylaldehydes>Cyclohexanecarboxaldehyde>Phenylacetaldehyde>Benzaldehyde.
The different aldehyde of the present embodiment different time corresponding hydrogen outputs data referring to table 2 (Fig. 6 data)
Embodiment 15
20 milligrams of Ag/MgO catalyst are taken to insert in the formalin that 5 milliliters of concentration are 1mol/L, reaction temperature is set
For 25 DEG C of normal temperature, (oxygen partial pressure is about 0.22atm) stirring reaction liquid in air atmosphere, O in research gas phase2, H2, CO2And CO
Variation tendency.As can be seen from Figure 7, during Ag/MgO catalysis formalin hydrogen manufacturing, H2Growing amount it is continuous over time
Increase, and the content of oxygen is kept approximately constant.Meanwhile, oxycarbide is not almost detected.This is confirmed in Ag/MgO catalysis
During formaldehyde hydrogen manufacturing, oxygen serves the effect of cocatalyst.
Embodiment 16
20 milligrams of Ag/MgO catalyst are taken to be respectively implanted different types of acetaldehyde solution that 2 milliliters of concentration are 0.1mol/L
In (wherein comprising acetaldehyde solution, deuterated acetaldehyde solution, the deuterated aqueous solution of acetaldehyde and the deuterated aqueous solution four of deuterated acetaldehyde
Plant reaction solution), reaction temperature is set to 25 DEG C of normal temperature, in air atmosphere (oxygen partial pressure is about 0.22atm) stirring reaction liquid,
Detect the generation speed of hydrogen.As it can be observed in the picture that α-hydrogen (hydrogen on methyl) is catalyzed in Ag/MgO in hydrogen and acetaldehyde molecule in water
During aldehyde solution hydrogen manufacturing, very big effect is played, reason is exactly the H of generation2α-hydrogen of hydrogen and aldehyde in water.Together
When, we have also been made identical contrast experiment with reference to acetaldehyde, find alcohol (methanol), sour (formic acid), ketone (acetone), ether (ether),
Ester (methyl formate) also has similar effect, i.e. H2From not only water, α-hydrogen also in biomass.
Embodiment 17
20 milligrams of Ag/MgO catalyst are taken to insert in the formalin that 5 milliliters of concentration are 1mol/L, in air atmosphere
(oxygen partial pressure is about 0.22atm) stirring reaction liquid, H2Generating rate change (Fig. 9) with the change of reaction temperature, from
Fig. 9 is understood, during Ag/MgO catalysis formalin hydrogen manufacturing, H2Generating rate change with the change of reaction temperature
Become, still, Ag/MgO still keeps very high hydrogen production efficiency at 0 DEG C.
The production hydrogen effect data of the present embodiment different temperatures is referring to table 3 (Fig. 9 data)
Embodiment 18
20 milligrams of Ag/MgO catalyst are taken to insert in the formalin of 5 milliliters of various concentrations, reaction temperature is set to often
25 DEG C of temperature, in air atmosphere (oxygen partial pressure is about 0.22atm) stirring reaction liquid, H2Constantly produced from the aqueous solution.From figure
10 understand, during Ag/MgO catalysis formalin hydrogen manufacturing, work as concentration of formaldehyde<During 1mol/L, H2Speed is produced with first
The increase of aldehyde concentration and increase quickly；Work as concentration of formaldehyde>During 1mol/L, H2Speed is produced with the increase of concentration of formaldehyde to change
Less.The fact that illustrate that Ag/MgO catalyst can be resistant to the formalin of higher concentration, it is adaptable to industrial applications.
The production hydrogen effect data of the present embodiment various concentrations formaldehyde is referring to table 4 (Figure 10 data)
From embodiment 1-18, Ag/MgO catalyst has following feature during aldehyde solution hydrogen manufacturing is catalyzed：1)
Oxygen serves the effect of co-catalyst during catalyzing manufacturing of hydrogen, it is, oxygen partial pressure is higher, hydrogen generation rate is got over
It hurry up, yield is higher, meanwhile, oxygen partial pressure is kept approximately constant with reaction；2) Ag/MgO catalyst is in catalysis aldehyde solution
During hydrogen manufacturing, oxycarbide is nearly free from；3) Ag/MgO catalyst can be catalyzed all aldehyde solution hydrogen manufacturing, but hydrogen manufacturing
Efficiency is different, and its order is：Formaldehyde>>Acetaldehyde ≈ propionic aldehyde ≈ hutanal ≈ isobutylaldehydes>Cyclohexanecarboxaldehyde>Phenylacetaldehyde>Benzaldehyde；
4) Ag/MgO catalyst can be catalyzed aldehyde solution hydrogen manufacturing at ambient temperature, and minimum temperature is up to 0 DEG C；5) Ag/MgO catalyst exists
In catalytic alcohol, aldehyde, acid, ketone, ether, ester solution hydrogen production process, the protium in the hydrogen of generation is also derived from from not only water
Hydrogen in alcohol, aldehyde, acid, ketone, ether, ester, by taking aldehyde as an example, mainly α-hydrogen of aldehyde, that is, the carbon atom being connected with aldehyde groups
On hydrogen；6) Ag/MgO catalyst can be resistant to the aldehyde solution hydrogen manufacturing of higher concentration, it is, (the ratio in high concentration aldehyde solution
Such as 10mol/L formalin), Ag/MgO has remained in that high hydrogen production efficiency.
Embodiment 19
Take 20 milligrams of group VIIIs and/or IB group 4 transition metals load MgO catalyst (Ag/MgO, Au/MgO, Cu/MgO,
Ru/MgO, Rh/MgO, Ir/MgO, Pd/MgO and Pt/MgO) to insert in 5 milliliters of 1mol/L formalin, reaction temperature is set
25 DEG C of normal temperature is set to, in air atmosphere (oxygen partial pressure is about 0.22atm) stirring reaction liquid, H2Constantly produced from the aqueous solution
It is raw.Wherein, the TEM of tetra- kinds of catalyst of Ag/MgO, Au/MgO, Pd/MgO and Pt/MgO is schemed as shown in Fig. 2 Fig. 2 a-d figures are shown
Ag, Au, Pd, uniform load of the Pt nano particles on MgO surfaces.As can be seen from Figure 11, in catalysis formalin production hydrogen experiment
In contrast, catalytic activity size is arranged as follows：Ag/MgO>Rh/MgO>Ru/MgO>Cu/MgO>Au/MgO>Pd/MgO>Ir/MgO>
Pt/MgO。
The data of the present embodiment different metal load MgO catalyst catalysis formalin production hydrogen are referring to (Figure 11 number of table 5
According to)
Embodiment 20
20 milligrams of group VIIIs and/or IB group 4 transition metals is taken to load the acetaldehyde water that MgO catalyst inserts 5 milliliters of 1mol/L
In solution, reaction temperature is set to 25 DEG C of normal temperature, in air atmosphere (oxygen partial pressure is about 0.22atm) stirring reaction liquid, H2
Constantly produced from the aqueous solution.As can be seen from Figure 12, in the contrast of catalysis acetaldehyde solution production hydrogen experiment, Au/MgO, Cu/MgO,
The catalysis production hydrogen activity of Ag/MgO catalyst is all relatively good.
The data of the present embodiment different metal load MgO catalyst catalysis acetaldehyde solution production hydrogen are referring to (Figure 12 number of table 6
According to)
Embodiment 21-35 and comparative example 1-4 reaction condition and hydrogen evolution rate is referring to table 7
Above example and comparative example are all to take 20 milligrams of catalyst to insert in the formalin of 5 milliliters of various concentrations,
The stirring reaction liquid at different temperature and oxygen partial pressure, determines H2Generation speed.Can by above comparative example and embodiment
Drawn a conclusion with drawing：Group VIII and/or IB group 4 transition metals particulate load be on certain carrier in the periodic table of elements, than
, can decomposing formaldehyde aqueous solution system in the presence of oxygen in certain temperature range after composition catalyst on MgO
Hydrogen, and hydrogen production efficiency increases with the rise of oxygen pressure.But, when carrier is strontium titanates, its hydrogen production efficiency can be with
The rise of oxygen pressure and reduce, or even be intended to zero (see comparative example 1-4).Comparative example 5-10 shows gold load strontium titanates
Catalyst, can be with catalyst formalin hydrogen manufacturing when reaction temperature is higher than 35 DEG C, but the hydrogen manufacturing system needs to protect in nitrogen
Shield is lower to be carried out, and its purpose is to starvation, oxygen-barrier is allowed as far as possible in the hydrogen manufacturing system, because oxygen can cause hydrogen manufacturing to be imitated
The decline of rate.And relatively low (the TOF of gold load strontium titanates catalyst activity<15h-1), well below the catalyst of the present invention
Catalytic activity (embodiment 21-35).
Embodiment 37
50 milligrams of Ag/MgO catalyst (Ag load capacity is 2.0wt%) are taken to insert the formaldehyde that 100 milliliters of concentration are 1mol/L
In the aqueous solution, reaction temperature is set to 50 DEG C, in air atmosphere stirring reaction liquid, H2Constantly produced from the aqueous solution, and H2's
Generating rate is 3.2mmol/hg.
Embodiment 38
10 milligrams of Ag/MgO and 15 milligram of Au/MgO catalyst are taken to insert the formaldehyde that 20 milliliters of concentration are 0.1mol/L respectively
In the aqueous solution, reaction temperature is set to 0 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 2 MPas of atmosphere2Constantly from the aqueous solution
Produce, and H2Generating rate be 6.8mmol/hg.
Embodiment 39
20 milligrams of Au/MgO catalyst (Au load capacity is 1.8wt%) are taken to insert the formaldehyde that 500 milliliters of concentration are 3mol/L
In the aqueous solution, reaction temperature is set to 40 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 2 MPas of atmosphere2Constantly from the aqueous solution
It is middle to produce, and H2Generating rate be 5.6mmol/hg.
Embodiment 40
20 milligrams of Au/MgO catalyst are taken to insert in the acetaldehyde solution that 500 milliliters of concentration are 3mol/L, reaction temperature is set
40 DEG C are set to, stirring reaction liquid, H in the case where oxygen pressure is 4 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Generating rate
For 10.3mmol/hg.
Embodiment 41
Take 50 milligrams of Ag/Mg (OH)2(specific surface area is 92m to catalyst2/ g) 1000 milliliters of concentration are inserted for 1.5mol/L first
In the mixed aqueous solution of aldehyde and 1mol/L acetaldehyde, reaction temperature is set to 30 DEG C, stirs anti-in the case where oxygen pressure is 1 MPa of atmosphere
Answer liquid, H2Constantly produced from the aqueous solution, and H2Generating rate be 8.6mmol/hg.
Embodiment 42
Take 20 milligrams of Ag/Mg (OH)2It is 5mol/L's that catalyst (Ag load capacity is 3.8wt%), which inserts 1000 milliliters of concentration,
In the propionic aldehyde aqueous solution, reaction temperature is set to 80 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 3 MPas of atmosphere2Constantly from water
Produced in solution, and H2Generating rate be 7.9mmol/hg.
Embodiment 43
10 milligrams of Ag/MgO catalyst are taken to insert in the propionic aldehyde aqueous solution that 50 milliliters of concentration are 2mol/L, reaction temperature is set
For 80 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 2 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Generating rate be
6.5mmol/h·g。
Embodiment 44
10 milligrams of Ag/MgO catalyst are taken to insert in the acetaldehyde solution that 50 milliliters of concentration are 2mol/L, reaction temperature is set
For 80 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 2 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Generating rate be
26.5mmol/h·g。
Embodiment 45
500 milligrams of Ag/MgO catalyst are taken to insert in the formalin that 2000 milliliters of concentration are 0.5mol/L, reaction temperature
Degree is set to 99 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 4 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Generation
Speed is 18.5mmol/hg.
Embodiment 46
It is 1.5mol/ to take 400 milligrams of AgAu/MgO catalyst (AgAu load capacity is 4.8wt%) to insert 2500 milliliters of concentration
In L formalin, reaction temperature is set to 0 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 2 MPas of atmosphere2Constantly from
Produced in the aqueous solution, and H2Generating rate be 36.8mmol/hg.
Embodiment 47
400 milligrams of Ag@Au/MgO catalyst are taken to insert in the formalin that 2500 milliliters of concentration are 1.5mol/L, reaction
Temperature setting is 0 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 2 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Life
It is 23.1mmol/hg into speed.
Embodiment 48
40 milligrams of Cu/MgO catalyst are taken to insert in the formalin that 250 milliliters of concentration are 2mol/L, reaction temperature is set
0 DEG C is set to, stirring reaction liquid, H in the case where oxygen pressure is 0.5 MPa of atmosphere2Constantly produced from the aqueous solution, and H2Generation speed
Rate is 8.6mmol/hg.
Embodiment 49
30 milligrams of CuO/MgO catalyst are taken to insert in the formalin that 50 milliliters of concentration are 3.5mol/L, reaction temperature
80 DEG C are set to, stirring reaction liquid, H in the case where oxygen pressure is 2.5 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Generation
Speed is 10.6mmol/hg.
Embodiment 50
Take 30 milligrams of Ag2O/MgO catalyst is inserted in the formalin that 50 milliliters of concentration are 2.5mol/L, reaction temperature
50 DEG C are set to, stirring reaction liquid, H in the case where oxygen pressure is 1.5 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Generation
Speed is 28.3mmol/hg.
Embodiment 51
Take 20 milligrams of Ag2O/MgO catalyst is inserted in the acetaldehyde solution that 60 milliliters of concentration are 1.5mol/L, reaction temperature
60 DEG C are set to, stirring reaction liquid, H in the case where oxygen pressure is 3.5 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Generation
Speed is 35.5mmol/hg.
Embodiment 52
20 milligrams of AgPt/MgO catalyst are taken to insert in the acetaldehyde solution that 60 milliliters of concentration are 1.5mol/L, reaction temperature
60 DEG C are set to, stirring reaction liquid, H in the case where oxygen pressure is 3.5 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Generation
Speed is 68.6mmol/hg.
Embodiment 53
20 milligrams of Ag are taken respectively2O/MgO and 15 milligram of Cu/MgO catalyst inserts the second that 60 milliliters of concentration are 1.5mol/L
In the aldehyde aqueous solution, reaction temperature is set to 60 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 3.5 MPas of atmosphere2Constantly from water
Produced in solution, and H2Generating rate be 36.5mmol/hg.
Embodiment 54
10 milligrams of AgCu/MgO and 30 milligram of Pd/MgO catalyst are taken to insert 60 milliliters of concentration for 1.5mol/L formaldehyde respectively
In 3mol/L acetaldehyde mixed aqueous solution, reaction temperature is set to 60 DEG C, stirs anti-in the case where oxygen pressure is 3.5 MPas of atmosphere
Answer liquid, H2Constantly produced from the aqueous solution, and H2Generating rate be 28.5mmol/hg.
Embodiment 55
30 milligrams of Pd/MgO and AuNi/MgO catalyst are taken to insert the formaldehyde that 40 milliliters of concentration are 1.5mol/L respectively water-soluble
In liquid, reaction temperature is set to 20 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 1.5 MPas of atmosphere2Constantly from the aqueous solution
Produce, and H2Generating rate be 36.6mmol/hg.
Embodiment 56
Taking 20 milligrams of Li-ZSM-5 molecular sieve catalysts respectively, (specific surface area is 120m2/ g) insert 20 milliliters of concentration and be
In 1mol/L formalin, reaction temperature is set to 40 DEG C, the stirring reaction liquid in the case where oxygen pressure is 0.1 MPa of atmosphere,
H2Constantly produced from the aqueous solution, and H2Generating rate be 0.6mmol/hg.
Embodiment 57
40 milligrams of Ca-ZSM-5 molecular sieve catalysts are taken to insert the formalin that 50 milliliters of concentration are 2.8mol/L respectively
In, reaction temperature is set to 25 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 0.5 MPa of atmosphere2Constantly produced from the aqueous solution
It is raw, and H2Generating rate be 0.9mmol/hg.
Embodiment 58
10 milligrams of K-ZSM-5 molecular sieve catalysts are taken to insert the formalin that 10 milliliters of concentration are 0.8mol/L respectively
In, reaction temperature is set to 65 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 0.2 MPa of atmosphere2Constantly produced from the aqueous solution
It is raw, and H2Generating rate be 0.3mmol/hg.
Embodiment 59
10 milligrams of Ba-ZSM-5 molecular sieve catalysts are taken to insert the formalin that 60 milliliters of concentration are 20mol/L respectively
In, reaction temperature is set to 85 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 0.9 MPa of atmosphere2Constantly produced from the aqueous solution
It is raw, and H2Generating rate be 0.78mmol/hg.
Embodiment 60
80 milligrams of Pd/MgCO are taken respectively3(specific surface area is 62m to catalyst2/ g) 20 milliliters of concentration are inserted for 15mol/L
In formalin, reaction temperature is set to 45 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 0.1 MPa of atmosphere2Constantly from
Produced in the aqueous solution, and H2Generating rate be 0.15mmol/hg.
Embodiment 61
50 milligrams of Ag/MgO catalyst are taken to insert in the methanol aqueous solution that 100 milliliters of concentration are 1mol/L, reaction temperature is set
80 DEG C are set to, in air atmosphere stirring reaction liquid, H2Constantly produced from the aqueous solution, and H2Generating rate be 0.25mmol/
h·g。
Embodiment 62
Take 50 milligrams of Ag/Mg (OH)2Catalyst is inserted in the aqueous formic acid that 100 milliliters of concentration are 10mol/L, reaction temperature
Degree is set to 90 DEG C, in air atmosphere stirring reaction liquid, H2Constantly produced from the aqueous solution, and H2Generating rate be
0.12mmol/h·g。
Embodiment 63
Take 50 milligrams of Ag/SiO2Catalyst and MgO powder are inserted in the formalin that 20 milliliters of concentration are 5mol/L, instead
It is 60 DEG C to answer temperature setting, in air atmosphere stirring reaction liquid, H2Constantly produced from the aqueous solution, and H2Generating rate be
88.2mmol/h·g。
Embodiment 64
Take 50 milligrams of Cu/SiO2Catalyst and Mg (OH)2Powder inserts the formalin that 50 milliliters of concentration are 20mol/L
In, reaction temperature is set to 99 DEG C, in air atmosphere stirring reaction liquid, H2Constantly produced from the aqueous solution, and H2Generation speed
Rate is 78.6mmol/hg.
Embodiment 65
Take 50 milligrams of Au/SiO2Catalyst and Mg (OH)2Powder inserts the formalin that 20 milliliters of concentration are 1mol/L
In, reaction temperature is set to 99 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 5.5 MPas of atmosphere2Constantly produced from the aqueous solution
It is raw, and H2Generating rate be 106.3mmol/hg.
Embodiment 66
Take 80 milligrams of Ag/SiO2Catalyst and Mg (OH)2It is water-soluble that powder inserts the isopropanol that 100 milliliters of concentration are 2mol/L
In liquid, reaction temperature is set to 99 DEG C, stirring reaction liquid, H in the case where oxygen pressure is 0.1 MPa of atmosphere2Constantly from the aqueous solution
Produce, and H2Generating rate be 0.3mmol/hg.
Embodiment 67
Take 80 milligrams of Au/SiO2Catalyst and Mg (OH)2It is water-soluble that powder inserts the ethylene glycol that 100 milliliters of concentration are 10mol/L
In liquid, reaction temperature is set to 99 DEG C, in air atmosphere stirring reaction liquid, H2Constantly produced from the aqueous solution, and H2Generation
Speed is 26.3mmol/hg.
Embodiment 68
80 milligrams of Ag/MgO catalyst are taken to insert in the aqueous ascorbic acid that 100 milliliters of concentration are 1mol/L, reaction temperature
Degree is set to 90 DEG C, in air atmosphere stirring reaction liquid, H2Constantly produced from the aqueous solution, and H2Generating rate be
0.4mmol/h·g。
Embodiment 69
10 milligrams of Ag/MgO catalyst are taken to insert in the formalin that 5 milliliters of concentration are 15mol/L, in air atmosphere
Stirring reaction liquid, reaction temperature is set to 25 DEG C, by adjusting oxygen pressure, H2Generating rate therewith oxygen pressure increase and
Increase.
Embodiment 70
10 milligrams of Ag/MgO catalyst are taken to insert in 5 milliliters of different formalins of concentration, reaction temperature is set to 25
DEG C, stirring reaction liquid, H in air atmosphere2Generating rate changes with the change of concentration of formaldehyde.
Embodiment 71
10 milligrams of Ag/MgO catalyst are taken to insert in the formalin that 5 milliliters of concentration are 1mol/L, in air atmosphere
Stirring reaction liquid, H2Generating rate changes with the change of reaction temperature.
Embodiment 72
10 milligrams of Ag/MgO catalyst are taken to insert in the formalin that 5 milliliters of concentration are 1mol/L, in air atmosphere
Oxygen concentration in stirring reaction liquid, reaction system is as the extension in reaction time is without occurring big change.
Embodiment 73
10 milligrams of Ag/MgO catalyst are taken to insert in the formalin that 5 milliliters of concentration are 1mol/L, in air atmosphere
Hydrogen generation rate in stirring reaction liquid, reaction system changes with the change of reaction temperature.
Embodiment 74
20 milligrams of PdAg/MgO catalyst are taken to insert in the formalin that 5 milliliters of concentration are 0.5mol/L, in air gas
Hydrogen generation rate in stirring reaction liquid under atmosphere, reaction system changes with the change of reaction temperature.
Embodiment 75
25 milligrams of Pd/MgO catalyst are taken to insert in the formalin that 10 milliliters of concentration are 1mol/L, in air atmosphere
Oxygen concentration in stirring reaction liquid, reaction system declines with the extension in reaction time.
Embodiment 76
80 milligrams of Cu/MgO catalyst are taken to insert in the formalin that 50 milliliters of concentration are 5mol/L, in air atmosphere
Stirring reaction liquid, reaction temperature is set to 25 DEG C, by adjusting oxygen pressure, H2Generating rate changes therewith.
Embodiment 77
60 milligrams of CoS/MgO catalyst are taken to insert in the formalin that 10 milliliters of concentration are 20mol/L, reaction temperature is set
55 DEG C are set to, stirring reaction liquid, H in the case where oxygen pressure is 1.5 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Generation speed
Rate is 3.3mmol/hg.
Embodiment 78
Take 20 milligrams of MoS2/ MgO catalyst is inserted in the formalin that 5 milliliters of concentration are 10mol/L, and reaction temperature is set
85 DEG C are set to, stirring reaction liquid, H in the case where oxygen pressure is 2.5 MPas of atmosphere2Constantly produced from the aqueous solution, and H2Generation speed
Rate is 6.5mmol/hg.
Embodiment 79
Take 40 milligrams of Ag@Au/MgO catalyst (Ag@Au refer to using Ag be shell Au as core nucleocapsid catalyst) insert 10 millis
Concentration is risen in 2mol/L formalin, reaction temperature is set to 65 DEG C, is stirred in the case where oxygen pressure is 2.5 MPas of atmosphere
Reaction solution, H2Constantly produced from the aqueous solution, and H2Generating rate be 202.5mmol/hg.
Embodiment 79
Take 60 milligrams of Au@Pd/MgO catalyst (Au@Pd refer to using Au be shell Pd as core nucleocapsid catalyst) insert 20 millis
Concentration is risen in 10mol/L formalin, reaction temperature is set to 45 DEG C, is stirred in the case where oxygen pressure is 0.5 MPa of atmosphere
Mix reaction solution, H2Constantly produced from the aqueous solution, and H2Generating rate be 103.2mmol/hg.
Embodiment 80
A certain amount of Ag/MgO is taken as 1mol/L formalin, and adds a certain amount of DMPO (lutidines N-
Oxide) solution (0.1mol/L), after being stirred 5 minutes under room temperature and air, take a certain amount of suspension to be placed in quartz wool
In tubule, it is placed in electron spin resonanceapparatus (EPR) and surveys free radical and change with time process.Figure 13 is DMPO captures Ag/MgO
The spectrogram of free radical is generated during catalysis formalin.It can be seen that Ag/MgO can be acted on formalin and oxygen,
All kinds of active oxygen species are generated in catalyst surface, such as (black bars refer to super oxygen certainly in figure for superoxide species and peroxyl species
Star-like to refer to hydroperoxyl radical by base, bullet refers to peroxyl species).This kind of active oxygen species can be acted on formaldehyde and water, raw
Into hydroperoxyl radical, hydrogen is ultimately generated.
Embodiment 81
Take rotating ring disk electrode (r.r.d.e) system of a certain amount of Ag/MgO and Pt/MgO catalyst in 0.1M KOH solutions
(PRDE) test I-V curve and current-responsive curve.Figure 14 is Ag/MgO and Pt/MgO catalyst in 0.1M KOH solutions
Rotating ring disk electrode (r.r.d.e) system (PRDE) test I-V curve (master map) and current-responsive curve (embedded figure).From Figure 14, Ag/
MgO can ultimately form peroxyl species with the electron reduction of catalytic oxygen two, and four electron reductions of Pt/MgO major catalytic oxygen are given birth to
Cheng Shui.Therefore, Ag/MgO can be catalyzed formalin hydrogen manufacturing, and the ability of Pt/MgO catalysis formalin hydrogen manufacturing is relatively poor.
Embodiment 82
Take various concentrations hydrogen peroxide (H2O2) solution catalyzing formalin (1mol/L) hydrogen manufacturing.Figure 15 is various concentrations dioxygen
Water (H2O2) solution catalyzing formalin (1mol/L) hydrogen manufacturing spectrogram.From Figure 15, it is molten that hydrogen peroxide solution can be catalyzed formaldehyde
Liquid hydrogen manufacturing, and the quantity that produces of hydrogen and hydrogen peroxide concentration are directly proportional (embedded figure).Meanwhile, active oxygen species can be learnt,
Such as peroxyl species, really can be with formaldehyde/water effect generation hydrogen.
Claims (10)
1. a kind of producing hydrogen, catalyzing system, it is characterised in that：Described catalyst system and catalyzing includes metal nano catalyst and biomass water
Solution, described metal nano catalyst biomass water solution hydrogen manufacturing, the hydrogen production efficiency of described catalyst system and catalyzing and hydrogen manufacturing
Ability is controlled by the amount of oxygen, and the hydrogen production efficiency of the catalyst system and catalyzing is with oxygen pressure or the liter of concentration in hydrogen production reaction system
High and increase, the amount of the oxygen includes the amount of oxygen and the amount for the oxygen that is dissolved in the water in gas phase, and described metal nano is urged
Agent is load type metal nanocatalyst or unsupported metals nanocatalyst, the unsupported metals nanocatalyst
It is made up of metal nano material, the load type metal nanocatalyst includes metal nano material and carrier.
2. catalyst system and catalyzing according to claim 1, it is characterised in that：The reaction temperature of the catalyst system and catalyzing is 0 DEG C~100
℃；It is preferred that, the reaction temperature of the catalyst system and catalyzing is 0 DEG C~30 DEG C；It is preferred that, the reaction temperature of the catalyst system and catalyzing is room
Temperature；It is furthermore preferred that the reaction temperature of the catalyst system and catalyzing is 0 DEG C~10 DEG C；It is furthermore preferred that the reaction temperature of the catalyst system and catalyzing
For 0 DEG C.
3. catalyst system and catalyzing according to claim 1 or 2, it is characterised in that：The metal nano material is selected from period of element
The metal simple-substance of group VIII and/or IB group 4 transition metals, metal alloy, metal oxide, core shell structure, metal vulcanization in table
Thing and metal carbides any one or it is any a variety of.
4. the catalyst system and catalyzing according to claim any one of 1-3, it is characterised in that：The load type metal nanocatalyst
Carrier include the oxide of group ia and/or Group IIA element in the periodic table of elements, hydroxide, carbide, oxycarbide,
Molecular sieve, salt any one or it is any a variety of, described carrier does not include strontium titanates.
5. catalyst system and catalyzing according to claim 4, it is characterised in that：It is any one that described carrier is selected from group iia element
The oxide of kind or any various metals；It is preferred that, described carrier includes magnesia；Further preferably, described carrier is oxygen
Change magnesium；It is furthermore preferred that described carrier is the mixture of magnesia and other inorganic matters, the weight of the magnesia in the mixture
Measure ratio at least 10wt%, either at least 50wt% or at least 80wt%.
6. a kind of hydrogen manufacturing system, it is characterised in that：Described hydrogen manufacturing system includes the catalytic body described in claim any one of 1-5
System and oxygen, the hydrogen production efficiency and hydrogen capacity of the hydrogen manufacturing system are controlled by the amount of oxygen, the hydrogen manufacturing effect of the hydrogen manufacturing system
Rate increases with the rise of oxygen pressure or concentration in hydrogen production reaction system, and the amount of the oxygen includes the amount of oxygen in gas phase
With the amount for the oxygen that is dissolved in the water.
7. hydrogen manufacturing system according to claim 6, it is characterised in that：Described hydrogen manufacturing system still further comprises reactor
And Second support, the Second support is for carried metal nanocatalyst.
8. hydrogen manufacturing system according to claim 7, it is characterised in that：Described Second support is having with loading functional
Machine thing or inorganic matter, described Second support are selected from any one of ceramics, glass, fiber, cloth, plastics, coating, molecular sieve
Or it is any a variety of.
9. the catalyst system and catalyzing described in claim any one of 1-5 is in hydrogen manufacturing, derived energy chemical, battery, water process, paint, work(
Energy property textile, indoor air cleaning eliminate aldehyde, petrochemical industry, carbon-hydrogen bond activation, pharmacy, the purposes prepared in hydrogeneous water.
10. the hydrogen manufacturing system described in claim any one of 6-8 is in hydrogen manufacturing, derived energy chemical, battery, water process, paint, work(
Energy property textile, indoor air cleaning eliminate aldehyde, petrochemical industry, carbon-hydrogen bond activation, pharmacy, the purposes prepared in hydrogeneous water.
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| CN110498392A (en) * | 2018-05-18 | 2019-11-26 | 中国科学院理化技术研究所 | A kind of photocatalytic system and its application |
| CN114644320A (en) * | 2022-03-18 | 2022-06-21 | 浙江理工大学 | Photocatalytic hydrogen production system and application thereof |
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| CN107128875B (en) | 2021-04-06 |
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