CN110252311A - A kind of cellulose aqueous-phase reforming produces hydrogen catalyst, preparation and application - Google Patents
A kind of cellulose aqueous-phase reforming produces hydrogen catalyst, preparation and application Download PDFInfo
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- CN110252311A CN110252311A CN201910563063.0A CN201910563063A CN110252311A CN 110252311 A CN110252311 A CN 110252311A CN 201910563063 A CN201910563063 A CN 201910563063A CN 110252311 A CN110252311 A CN 110252311A
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- catalyst
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- phase reforming
- hydrotalcite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
Abstract
A kind of cellulose aqueous-phase reforming produces hydrogen catalyst, preparation and application, belongs to biomass transformation technology and clean energy resource and related chemistry technical field.The catalyst is made of Monodispersed nano nickel particles and Mg-Al composite oxide.Catalyst is made by the topology transformation in situ of nickeliferous hydrotalcite, and advantage is can interface interaction between modulation Ni nano particle and carrier, catalyst alkalinity bit density, base strength by control hydrotalcite precursor preparation method.Catalyst is applied to cellulose liquid phase reforming reaction, 260 DEG C, spontaneous pressure reacts 2h, and producing hydrogen yield may be up to 70%.
Description
Technical field
The invention belongs to biomass catalyzings to convert clean energy resource field, in particular, provide a kind of cellulose aqueous-phase reforming production
Hydrogen catalyst, preparation and application.
Background technique
It is 3 times of gasoline since combustion of hydrogen calorific value is high, and its combustion product only has water, cleanliness without any pollution, therefore,
Hydrogen is known as the 21st century energy, is the key components in future source of energy development pattern.In addition, hydrogen is as a kind of
Important industrial chemicals, large-scale application is in synthesis ammonia and the industries such as petroleum refining and fuel cell.However, complete at present
The hydrogen preparation of ball about 96% derives from traditional fossil energy, and 3.9% derives from electrolysis water.With the continuous consumption of fossil resource
With exhaustion, the technology for developing renewable resource preparation Hydrogen Energy gradually causes to pay close attention to.Biomass as a kind of reproducible carbon resource,
Rich in protium, it is known as preferably producing hydrogen source.However biomass produces hydrogen methods as gasified at present, steam reformation is overcritical
Water the problems such as to reform etc. that there is energy consumptions high, condition is harsh.
2002, Dumesic seminar, the U.S., which delivers, reported a kind of aqueous-phase reforming biomass plateform molecules production hydrogen technology
(J.A.Dumesic et al.Nature,2002,418,964-967).The technology realize mild liquid-phase condition (230 DEG C,
Higher production hydrogen effect under 1.5-5.0MPa), while CO concentration is low (< 500ppm) in product.Currently, about aqueous-phase reforming technology
Focusing primarily upon biomass plateform molecules polyalcohol is raw material.And it is directly also less with the research of biomass cellulose molecule.
Jones seminar report for the first time aqueous-phase reforming cellulose produce hydrogen (C.J.Jones et al.Energy Fuels, 2006,20,
1744-1752), under the conditions of adding dilute sulfuric acid outside, 225 DEG C, Pt/Al2O3Catalytic effect is only 0.96mmol/g cellulose.Tian Zhi
Heavily fortified point professor seminar reports 5wt%Pt/C (Z.Tian et al.Catal.Commun.2010,11,522-526) and CeO2
The aqueous-phase reforming of Raney Ni (Tian et al.Catal.Lett.2011,141,1851-1858) catalyst of modification
Cellulose produces hydrogen, and 260 DEG C, it is respectively 20.3mmol/g cellulose that hydrogen effect is produced under the conditions of spontaneous pressure (producing hydrogen yield is 26.5%)
With 17.8mmol/g cellulose (producing hydrogen yield is 24.0%).
Summary of the invention
The purpose of the present invention is to provide a kind of cellulose aqueous-phase reformings to produce hydrogen catalyst and preparation method thereof, application.
Catalyst of the invention is made of Monodispersed nano nickel particles and Mg-Al composite oxide carrier or aluminum oxide carries
Body composition.The catalyst is by hydrotalcite precursor through H2Topology transformation preparation under atmosphere.
Ni tenor in catalyst is 5-50wt%, and nano nickel particles average grain diameter is in 3-15nm.Ni metallic particles
It interacts with carrier interface adjustable, carrier alkalinity is adjustable, and catalyst is made by hydrotalcite precursor roasting reduction, and advantage is Ni
Interfacial interaction between nano particle and carrier, carrier alkalinity bit quantity and intensity are adjustable, to realize cellulose liquid phase
Reform efficient hydrogen manufacturing.
The preparation of the catalyst: the catalyst is with hydrotalcite (Layered Double Hydroxides, letter containing Ni
It is written as LDHs) it is made for precursor, neatly stone veneer bivalent cation selects Ni2+Or Ni2+And Mg2+, Tricationic select Al3+,
Its molar ratio is Mg2+/Al3+=(0~5): 1, then by hydrotalcite catalyst precursor in H2It is restored in atmosphere, reduction temperature control
At 500-900 DEG C, the control of reduction soaking time is 2-10 DEG C/min in 1min-5h, heating rate, obtains corresponding catalyst；
Ni metallic particles and carrier interface interaction are adjustable, and carrier alkalinity is adjustable, and then it is different to obtain catalytic performance
Described above adjustable of catalyst can be obtained by the different preparation methods of hydrotalcite catalyst precursor.
The preparation method of hydrotalcite catalyst precursor includes constant pH method, nucleation crystallization isolation method, urea method preparation, machine
Tool stirs fast nucleation method preparation etc..
When using the preparation of constant pH method and the preparation of mechanical stirring fast nucleation method, pH in the hydrotalcite precursor preparation process
Value is 9-11.
When using nucleation crystallization isolation method preparation；Colloid mill slit width is 100nm-10000nm.Colloid mill revolving speed is
3000r/min-15000r/min.Colloid mill mixing time is 1min-10min.
The catalyst produces hydrogen for aqueous-phase reforming cellulose, produces hydrogen particularly for water aqueous-phase reforming cellulose.
The method that the above-mentioned catalyst of the present invention produces hydrogen for aqueous-phase reforming cellulose, is added substrate cellulose in aqueous solution
And catalyst, the mass ratio of catalyst charge and added cellulose are 1:10~1:500, reaction temperature is 200-280 DEG C, instead
Answering pressure is spontaneous pressure, reaction time 0.5-8h.
Remarkable advantage of the invention is the interfacial interaction between Ni nano particle and carrier, carrier alkalinity bit quantity and
Intensity is adjustable, and aqueous-phase reforming cellulose production hydrogen effect is good, and producing hydrogen yield may be up to 70%.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
Step A: constant pH method prepares catalyst precarsor；
Quantitative deionized water is measured to four-hole boiling flask.Accurately weigh quantitative Ni (NO3)2·6H2O, Mg (NO3)2·
6H2O,Al(NO3)3·9H2O is simultaneously dissolved in deionized water, forms solution A；Accurately weigh quantitative Na2CO3, NaOH is simultaneously dissolved in
In ionized water, solution B is formed, solution A, B are instilled into four mouthfuls of co-precipitation in four-hole boiling flask simultaneously, keep system pH constant not
Become, is warming up to certain temperature, magnetic agitation crystallization.It is in neutrality after reaction with deionized water filtering and washing to filtrate, it is anhydrous
Ethyl alcohol filtering and washing 1 time, it is dry to be put into oven overnight.Obtain NiMgAl-LDHs.
Step B: by above-mentioned NiMgAl-LDHs precursor in H2Reduction is under middle certain temperature to get catalyst.
Weighed catalyst, cellulose and deionized water water are accurately weighed into stainless steel reactor,
Closed, air in inflated with nitrogen metathesis reactor is repeated 10 times, after fill a certain amount of nitrogen as interior standard gas.From room temperature
It is warming up to reaction temperature, starts clock reaction.At the end of reaction, it is cooled to room temperature,
Reaction gas volume is measured with wet gas flow meter, using gas chromatographic analysis.Producing hydrogen yield is 30.2%.
Embodiment 2
Step A: constant pH method prepares catalyst precarsor；
Quantitative deionized water is measured to four-hole boiling flask.Accurately weigh quantitative Ni (NO3)2·6H2O, Mg (NO3)2·
6H2O,Al(NO3)3·9H2O is simultaneously dissolved in deionized water, forms solution A；Accurately weigh quantitative Na2CO3, NaOH is simultaneously dissolved in
In ionized water, solution B is formed, solution A, B are added rapidly in the colloid mill of high-speed stirred, stirred after a certain period of time, by institute
It obtains slurries to pour into the polytetrafluoroethyllining lining of water heating kettle, crystallization in the baking oven of certain temperature is placed in after sealing.After reaction
It is in neutrality with deionized water filtering and washing to filtrate, dehydrated alcohol filtering and washing 1 time, it is dry to be put into oven overnight.It obtains
NiMgAl-LDHs。
Step B: by above-mentioned NiMgAl-LDHs precursor in H2Reduction is under middle certain temperature to get catalyst.
Weighed catalyst, cellulose and deionized water water are accurately weighed into stainless steel reactor, closed, inflated with nitrogen is set
Change air in reactor, be repeated 10 times, after fill a certain amount of nitrogen as interior standard gas.From room temperature to reaction temperature, start to count
Shi Fanying.It at the end of reaction, is cooled to room temperature, reaction gas volume is measured with wet gas flow meter, using gas-chromatography point
Analysis.Producing hydrogen yield is 70%.
Embodiment 3
Step A: nucleation crystallization isolation method prepares precursor
Quantitative deionized water is measured to four-hole boiling flask.Accurately weigh quantitative Ni (NO3)2·6H2O, Mg (NO3)2·
6H2O,Al(NO3)3·9H2O is simultaneously dissolved in deionized water, forms solution A；Accurately weigh quantitative Na2CO3, NaOH is simultaneously dissolved in
In ionized water, solution B is formed, solution A, B are added rapidly in the colloid mill of high-speed stirred, stirred after a certain period of time, by institute
It obtains slurries to pour into the polytetrafluoroethyllining lining of water heating kettle, gained slurries pour into the polytetrafluoroethyllining lining of water heating kettle, sealing
It is placed in crystallization in the baking oven of certain temperature afterwards.Gained filter cake is distributed to containing quantitative Mg (NO3)2·6H2In the solution of O, adjust
Solution ph stirs certain time, then is in neutrality with deionized water filtering and washing to filtrate, and it is dry to be put into oven overnight.It obtains
NiMgAl-LDHs。
Step B: by above-mentioned NiMgAl-LDHs precursor in H2Reduction is under middle certain temperature to get catalyst.
Weighed catalyst, cellulose and deionized water water are accurately weighed into stainless steel reactor, closed, inflated with nitrogen is set
Change air in reactor, be repeated 10 times, after fill a certain amount of nitrogen as interior standard gas.From room temperature to reaction temperature, start to count
Shi Fanying.It at the end of reaction, is cooled to room temperature, reaction gas volume is measured with wet gas flow meter, using gas-chromatography point
Analysis.Producing hydrogen yield is 20.2%.
Embodiment 4
Step A: constant pH method prepares catalyst precarsor；
Quantitative deionized water is measured to four-hole boiling flask.Accurately weigh quantitative Ni (NO3)2·6H2O, Mg (NO3)2·
6H2O,Al(NO3)3·9H2O is simultaneously dissolved in deionized water, forms solution A；Accurately weigh quantitative Na2CO3, NaOH is simultaneously dissolved in
In ionized water, solution B is formed, solution A, B are added rapidly in the colloid mill of high-speed stirred, solution A, B are added rapidly to
In four-hole boiling flask equipped with churned mechanically high-speed stirred, gained slurries after a certain period of time, are poured into poly- the four of water heating kettle by stirring
In vinyl fluoride liner, crystallization in the baking oven of certain temperature is placed in after sealing.After reaction with deionized water filtering and washing to filter
Liquid is in neutrality, and dehydrated alcohol filtering and washing 1 time, it is dry to be put into oven overnight.Obtain NiMgAl-LDHs.
Step B: by above-mentioned NiMgAl-LDHs precursor in H2Reduction is under middle certain temperature to get catalyst.
Weighed catalyst, cellulose and deionized water water are accurately weighed into stainless steel reactor, closed, inflated with nitrogen is set
Change air in reactor, be repeated 10 times, after fill a certain amount of nitrogen as interior standard gas.From room temperature to reaction temperature, start to count
Shi Fanying.It at the end of reaction, is cooled to room temperature, reaction gas volume is measured with wet gas flow meter, using gas-chromatography point
Analysis.Producing hydrogen yield is 65%.
Claims (10)
1. a kind of cellulose aqueous-phase reforming produces hydrogen catalyst, which is characterized in that catalyst is by Monodispersed nano nickel particles and magnalium
Composite oxide carrier composition or aluminum oxide carrier composition, the catalyst is by hydrotalcite precursor through H2Topology transformation under atmosphere
Preparation.
2. a kind of cellulose aqueous-phase reforming described in accordance with the claim 1 produces hydrogen catalyst, which is characterized in that the Ni in catalyst
Tenor is 5-50wt%, and nano nickel particles average grain diameter is in 3-15nm.
3. a kind of cellulose aqueous-phase reforming described in accordance with the claim 1 produces hydrogen catalyst, which is characterized in that Ni metallic particles with
Carrier interface interaction is adjustable, and carrier alkalinity is adjustable, and catalyst is made by hydrotalcite precursor roasting reduction, is Ni nanometers
Interfacial interaction between grain and carrier, carrier alkalinity bit quantity and intensity are adjustable, to realize that cellulose aqueous-phase reforming is high
Imitate hydrogen manufacturing.
4. the described in any item catalyst of claim 1-3 obtain preparation method, which is characterized in that the catalyst is with the neatly containing Ni
Stone (Layered Double Hydroxides, be abbreviated as LDHs) is made for precursor, the selection of neatly stone veneer bivalent cation
Ni2+Or Ni2+And Mg2+, Tricationic select Al3+, molar ratio Mg2+/Al3+=(0~5): 1, then hydrotalcite is urged
Agent precursor is in H2It is restored in atmosphere, reduction temperature is controlled at 500-900 DEG C, and the control of reduction soaking time is in 1min-5h, heating
Rate is 2-10 DEG C/min, obtains corresponding catalyst.
5. according to the method for claim 4, which is characterized in that Ni metallic particles and carrier interface interaction are adjustable, carry
Body alkalinity is adjustable, and then obtains the different catalyst of catalytic performance, described above adjustable to pass through hydrotalcite catalyst precursor
Different preparation methods obtain.
6. according to the method for claim 5, which is characterized in that the preparation method of hydrotalcite catalyst precursor includes constant pH
Value method, nucleation crystallization isolation method, urea method preparation, the preparation of mechanical stirring fast nucleation method.
7. according to the method for claim 6, which is characterized in that using the preparation of constant pH method and mechanical stirring fast nucleation
When prepared by method, pH value is 9-11 in the hydrotalcite precursor preparation process；When using nucleation crystallization isolation method preparation, colloid mill slit
Width is 100nm-10000nm, and colloid mill revolving speed is 3000r/min-15000r/min, and colloid mill mixing time is 1min-
10min。
8. the application of the described in any item catalyst of claim 1-3, the catalyst produces hydrogen for aqueous-phase reforming cellulose.
9. producing hydrogen for water aqueous-phase reforming cellulose according to the application of claim 8.
10. according to the application of claim 8 or 9, be added substrate cellulose and catalyst in aqueous solution, catalyst charge with
The mass ratio of added cellulose is 1:10~1:500, and reaction temperature is 200-280 DEG C, and reaction pressure is spontaneous pressure, reaction time
For 0.5-8h.
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| CN201910563063.0A CN110252311A (en) | 2019-06-26 | 2019-06-26 | A kind of cellulose aqueous-phase reforming produces hydrogen catalyst, preparation and application |
| PCT/CN2019/096268 WO2020258409A1 (en) | 2019-06-26 | 2019-07-17 | Catalyst for producing hydrogen by liquid phase reforming of cellulose, preparation and use thereof |
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| CN201910563063.0A CN110252311A (en) | 2019-06-26 | 2019-06-26 | A kind of cellulose aqueous-phase reforming produces hydrogen catalyst, preparation and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111545202A (en) * | 2020-04-28 | 2020-08-18 | 东南大学 | Cheap metal catalyst for lignin oligomer hydrogenation depolymerization synchronous quality improvement and preparation method and application thereof |
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| CN104148075A (en) * | 2014-06-19 | 2014-11-19 | 北京化工大学 | Catalyst for moderately and efficiently decomposing cellulose to prepare hydrogen and preparation method thereof |
| CN106000406A (en) * | 2016-05-23 | 2016-10-12 | 北京化工大学 | Ni-based composite metal oxide catalyst and application thereof |
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| KR101732120B1 (en) * | 2010-05-11 | 2017-05-04 | 동양하이테크산업주식회사 | Method of producing hydrogen from cellulose |
| EP2637783A1 (en) * | 2010-11-12 | 2013-09-18 | Air Products and Chemicals, Inc. | Supported catalyst and use thereof for reforming of steam and hydrocarbons |
| CN106867574B (en) * | 2015-12-14 | 2019-08-13 | 北京化工大学 | A kind of efficient catalytic sorbierite liquid phase is restructured as C6The method of hydrocarbon |
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- 2019-07-17 WO PCT/CN2019/096268 patent/WO2020258409A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104148075A (en) * | 2014-06-19 | 2014-11-19 | 北京化工大学 | Catalyst for moderately and efficiently decomposing cellulose to prepare hydrogen and preparation method thereof |
| CN106000406A (en) * | 2016-05-23 | 2016-10-12 | 北京化工大学 | Ni-based composite metal oxide catalyst and application thereof |
Non-Patent Citations (1)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111545202A (en) * | 2020-04-28 | 2020-08-18 | 东南大学 | Cheap metal catalyst for lignin oligomer hydrogenation depolymerization synchronous quality improvement and preparation method and application thereof |
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Application publication date: 20190920 |