CN105618131B - A kind of Composite Double carried catalyst and the preparation method and application thereof - Google Patents
A kind of Composite Double carried catalyst and the preparation method and application thereof Download PDFInfo
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- CN105618131B CN105618131B CN201610047280.0A CN201610047280A CN105618131B CN 105618131 B CN105618131 B CN 105618131B CN 201610047280 A CN201610047280 A CN 201610047280A CN 105618131 B CN105618131 B CN 105618131B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002808 molecular sieve Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 235000021419 vinegar Nutrition 0.000 claims abstract description 36
- 239000000052 vinegar Substances 0.000 claims abstract description 36
- 239000002023 wood Substances 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 25
- 238000001833 catalytic reforming Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 19
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052593 corundum Inorganic materials 0.000 abstract description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 12
- 239000011973 solid acid Substances 0.000 abstract description 10
- 230000007423 decrease Effects 0.000 abstract description 4
- 238000002407 reforming Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000002525 ultrasonication Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 240000001492 Carallia brachiata Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention belongs to catalyst preparation technical fields, disclose a kind of Composite Double carried catalyst and the preparation method and application thereof, the Composite Double carried catalyst is after mixing micro porous molecular sieve or solid acid catalyst with mesopore molecular sieve and carried metal nickel and metallic tin；The micro porous molecular sieve is HBeta or HZSM-5, and the solid acid catalyst is Al2O3, the mesopore molecular sieve is MCM-41；Wood vinegar catalytically reforming hydrogen producing is carried out using this Composite Double carried catalyst, the efficiency that wood vinegar catalytic reforming prepares hydrogen-rich gas not only can be improved, moreover it is possible to reduce the carbon deposit in reaction process, extend the service life of catalyst.The decline of the content of each gas component slightly in 2h.At the same time, the content of best hydrogen and yield have also risen to 60.32% and 22.47mg/g sample respectively.
Description
Technical field
The present invention relates to catalyst preparation technical fields, more particularly, to a kind of Composite Double carried catalyst and its system
Preparation Method and application.
Background technique
Wood vinegar water vapour catalytic reforming prepares the basic course of hydrogen rich gas are as follows: wood vinegar is cracked into Primary product first
(CO, CO2, CH4, C2) and carbon deposit, it is raw that Primary product carries out steam reforming under the effect of the catalyst, with the moisture in wood vinegar
At hydrogen-rich gas, in solid acid catalyst, molecular sieve catalyst because its is cheap, activity it is high and by favor.But due to micro-
Its duct of pore zeolite catalyst is smaller to be easy to be blocked by carbon deposit, causes the service life of catalyst shorter.
Summary of the invention
The technical problem to be solved by the present invention is to overcome wood vinegar water vapour catalytic reforming hydrogen rich gas in the prior art
The easy defect for depositing carbon deposit and causing catalyst service life short of catalyst used in body, provides a kind of Composite Double carrier catalysis
Agent.
A second object of the present invention is to provide the preparation methods of above-mentioned catalyst.
Third object of the present invention is to provide the applications of above-mentioned catalyst.
Fourth object of the present invention is to provide a kind of method of wood vinegar water vapour catalytic reforming preparing hydrogen-rich gas.
The purpose of the present invention is what is be achieved by the following technical programs:
A kind of Composite Double carried catalyst is after mixing micro porous molecular sieve or solid acid catalyst with mesopore molecular sieve
And carried metal nickel and metallic tin；The micro porous molecular sieve is HBeta or HZSM-5, and the solid acid catalyst is Al2O3,
The mesopore molecular sieve is MCM-41.
There are many research of single carrier for reformation hydrogen production, but the carbon deposit of single carrier is serious, influences the service life of catalyst, together
When catalyst regeneration technique it is with high requirements and high cost, molecular sieve catalyst due to its aromatic compound conversion in present it is good
Good shape selectivity, therefore be widely used in Industrial Catalysis.Since the catalytic activity of molecular sieve catalyst is mainly by acidity
The characteristic in site, the structure of molecular sieve, molecular sieve pore passage geometry three-dimensional structure determine.So different molecular sieves is to same reaction
Effect differ greatly, cause the path of reaction and the product of generation to differ greatly.
After the present invention is by mixing micro porous molecular sieve or solid acid catalyst with mesopore molecular sieve, then screen negative
The active material of load obtains the Composite Double carried catalyst that can greatly improve catalyst ability and service life, this is multiple
The catalytic capability for closing complex carries catalyst is strong, and anti-carbon deposition ability is strong.
Preferably, the mass ratio of the micro porous molecular sieve or solid acid catalyst and mesopore molecular sieve is 1~5:1.
It is highly preferred that the mass ratio of the micro porous molecular sieve or solid acid catalyst and mesopore molecular sieve is 3~4:1.
Preferably, the molar ratio of the metallic nickel and metallic tin is 1~5:1.
The present invention also provides the preparation methods of the Composite Double carried catalyst, comprising the following steps:
(1) pre-treatment of molecular sieve: being warming up to 200~300 DEG C of 0.5~1h of holding for molecular sieve, it is continuously heating to 300~
400 DEG C of 0.5~1h of holding, then 500~700 DEG C of 3~8h of holding are warming up to, finally it is down to room temperature；
(2) impregnate: by treated, molecular sieve is placed in containing Sn2+And Ni2+Predecessor in, be ultrasonically treated, stir
After drying, roast to obtain the final product.
As a kind of specific embodiment, the preparation method of Composite Double carried catalyst of the present invention, including it is following
Step: (1) calcining (Fig. 6) of carrier: first raw molecule sieve carrier is placed in Muffle furnace in the way of the heating of following substep
It is calcined under air atmosphere to remove impurity.
(2) it impregnates: by SnCl2With Ni (NO3)2It is dissolved in hydrochloric acid solution, according to water absorption rate calculated result, by certain matter
Calcined carrier impregnation is measured in certain density SnCl2With Ni (NO3)2In the predecessor of active material, control solution in Ni with
Sn molar ratio is 3:1.Ultrasonication 0.5h is carried out in the ultrasonic cleaning equipment that frequency is 27KW, is followed by stirring for 2h, with
After place impregnation drying 4h at room temperature.
(3) dry: step (2) processed carrier moves to 70 DEG C of Constant Temp. Oven forced air drying for 24 hours.
(4) it roasts: step (3) processed carrier being put into Muffle furnace, in air atmosphere, with the liter of 20 DEG C/min
Warm rate rises to 500 DEG C, and constant temperature 3h, is down to room temperature naturally later, catalyst needed for being made.
The present invention also provides application of the Composite Double carried catalyst in wood vinegar catalytically reforming hydrogen producing.
The present invention also provides a kind of methods of wood vinegar water vapour catalytic reforming preparing hydrogen-rich gas, are that wood vinegar gasifies,
Under the catalysis of the Composite Double carried catalyst under normal pressure, 2~4h is reacted.
Compared with prior art, the invention has the following advantages:
The present invention provides a kind of Composite Double carried catalyst, be by micro porous molecular sieve or solid acid catalyst with it is mesoporous
Molecular sieve mixing after and carried metal nickel and metallic tin；The micro porous molecular sieve is HBeta or HZSM-5, and the solid acid is urged
Agent is Al2O3, the mesopore molecular sieve is MCM-41；Wood vinegar catalytic reforming is carried out using this Composite Double carried catalyst
The efficiency that wood vinegar catalytic reforming prepares hydrogen-rich gas not only can be improved, moreover it is possible to reduce the carbon deposit in reaction process, prolong in hydrogen manufacturing
The service life of long catalyst.In 2h the content of each gas component slightly under.At the same time, the content and yield of best hydrogen
60.32% and 22.47mg/g sample has been risen to respectively.
Detailed description of the invention
Fig. 1 is wood vinegar water vapour catalytically reforming hydrogen producing apparatus figure.
Fig. 2 is that wood vinegar list carrier catalysis reformation each component changes over time tendency chart, and C2 is C in figure2H4And C2H6System
Claim, uses C2It is the sum of the content for indicating the two.
Fig. 3 is that Composite Double carrier catalysis reformation wood vinegar each component changes over time tendency chart, and C2 is C in figure2H4And C2H6
General designation, use C2It is the sum of the content for indicating the two.
Fig. 4 is that Composite Double carrier catalysis reformation wood vinegar each component changes over time tendency chart.
Fig. 5 is the SEM spectrum of reaction front and back catalyst.
Fig. 6 is the flow chart of carrier calcining.
Specific embodiment
The invention patent is further described with specific embodiment with reference to the accompanying drawings of the specification.Wherein, attached drawing
Only for illustration, expression is only schematic diagram, rather than pictorial diagram, should not be understood as the limitation to this patent；In order to more
Illustrate the embodiment of the invention patent well, the certain components of attached drawing have omission, zoom in or out, and do not represent actual product
Size；It will be understood by those skilled in the art that the omitting of some known structures and their instructions in the attached drawings are understandable.
Fig. 1 is the Experimental equipment of wood vinegar water vapour catalytic reforming reaction.Wood vinegar water vapour catalytic reforming reaction exists
It is carried out in atmospheric fixed bed quartz tube reactor, quartzy bore is 26mm, long 700mm.In experiment, each catalyst amount is
10g.Catalyst lower end is fixed with wire netting, and about 50mm Gao Zhu is filled with silica wool in upper end, in order to which volatile matter is uniformly through urging
Agent bed.In the performance test of catalyst, catalyst is placed among quartz reactor first, and is passed through thereto high-purity
Nitrogen is at this time heated up tube type resistance furnace with driving air, and by K-type thermocouple measurement bed temperature, temperature controller temperature control is risen
Warm rate is about 30 DEG C/min, when rising to 750 DEG C, is passed through also Primordial Qi (90%H2/ 10%He) reaction 1h, also Primordial Qi is by glass
Spinner flowmeter coutroi velocity is 500ml/min, after reduction, closes also Primordial Qi, the temperature was then adjusted to reaction temperatures, are used in combination
Nitrogen, which is blown, is cooled to reaction temperature.
The conical flask for filling wood vinegar is placed on magnetic stirring apparatus in an experiment, is heated while stirring.Magnetic stir bar
Revolving speed 200r/min, heating panel temperature is adjusted to 100 DEG C.Wood vinegar through peristaltic pump with the flow velocity of 0.3g/min into reactor
It is pumped into.It with nitrogen is carrier gas, flow velocity 100ml/min in reaction process.React the gas and unreacted biomass thermal generated
Volatile matter outflow reactor together is solved, at condenser pipe, condensable bio oil and water are collected by liquid header, product gas
After soap film flowmeter measures flow velocity, collected by Storage Time in Gas Collecting Bag.Collected liquid carries out GS-MS after weighing extraction
Detection, collected gaseous product is also by gas-chromatography offline inspection.After reaction, reaction unit is dropped under nitrogen atmosphere
To room temperature, collection catalyst remains late detection indices.
The preparation of 1 catalyst of embodiment
Molecular sieve carrier used in the present embodiment (catalyst) characteristic such as table 1, the present embodiment use incipient impregnation legal system
Standby various catalyst.
The correlation properties of each molecular sieve carrier of table 1
Two molecular sieve analog carriers are prepared altogether, and (single carrier is HBeta, HZSM-5, Al for single carrier and complex carries2O3Supported active
Substance Ni and Sn.Complex carries are by single carrier HBeta, HZSM-5, Al2O3Respectively with mesopore molecular sieve carrier MCM-41 according to matter
The ratio mixing of 1:1 is measured, stirring 2h is until carrying active substance Ni and Sn after mixing), comprising the following steps: (1) carrier
Calcining (Fig. 6): first by raw molecule sieve carrier place Muffle furnace in by following substep heating in the way of under air atmosphere
It is calcined to remove impurity.
(2) measurement of carrier water absorption rate: certain mass is placed among container through calcined molecular sieve carrier, gradually plus
Enter deionized water, until carrier reaches just wet condition, the quality that deionized water is added is calculated, with this numerical value divided by carrier
The water absorption rate of unit mass carrier can be obtained in quality.
(3) it impregnates: by SnCl2With Ni (NO3)2It is dissolved in hydrochloric acid solution, according to water absorption rate calculated result, by certain matter
Calcined carrier impregnation is measured in certain density SnCl2With Ni (NO3)2In the predecessor of active material, control solution in Ni with
Sn molar ratio is 3:1.Ultrasonication 0.5h is carried out in the ultrasonic cleaning equipment that frequency is 27KW, is followed by stirring for 2h, with
After place impregnation drying 4h at room temperature.
(4) dry: step (3) processed carrier moves to 70 DEG C of Constant Temp. Oven forced air drying for 24 hours.
(5) it roasts: step (4) processed carrier being put into Muffle furnace, in air atmosphere, with the liter of 20 DEG C/min
Warm rate rises to 500 DEG C, and constant temperature 3h, is down to room temperature naturally later, catalyst needed for being made.
The single carrier Ni/Sn catalyst wood vinegar water vapour catalytic reforming characteristic research of embodiment 3
Experiment condition: 600 DEG C of reaction temperature；Wood vinegar sample volume 0.25g/min；Carrier gas N2Flow velocity 100mL/min；It urges
Agent dosage 10g.List carried catalyst used is respectively Ni/Sn/HBeta, Ni/Sn/HZSM-5, Ni/Sn/Al2O3。
Wood vinegar water vapour catalytic reforming reaction is carried out using single carried catalyst, the variation feelings of each component in gas
Condition is as shown in Figure 2.When using Ni/Sn/HBeta catalyst, in 1h originally, the volumn concentration of hydrogen is always maintained at
65% or so.When reaction continues, the content of hydrogen is remarkably decreased, and drops to 30% or so from 65%.The content of CO is but
35%, CH is risen to from 5%4Content also rise to 16% from 5%.
When using catalyst n i/Sn/HZSM-5, the content of hydrogen gradually drops to 40% from 65% originally, and
CO, CH4, C2H4Content have a degree of rising, most notable one is that the content of CO rises from 10% or so of beginning
To 25%.
Compared to first two catalyst, Ni/Sn/Al2O3Catalytic activity it is more longlasting.With the progress of reaction, the content of hydrogen
Variation is more unobvious, only drops to 45% from beginning 65%.Unlike the content of CO first have slight decline then again
Present rise trend, just with CO2Variation tendency it is opposite.And CH4And C2H4Have the tendency that constantly rising.
Table 2 shows the yield of each gas component.From Table 2, it can be seen that when using Ni/Sn/HBeta catalyst, wood
In mixed gas after vinegar liquid water vapour catalytic reforming, the content of hydrogen is not highest, but gas yield highest, is reached
114.75ml/min.Finally within the reaction time of 2h, the production of the obtained each gas component of Ni/Sn/HBeta catalyst is utilized
Rate is relatively high, and the yield of especially hydrogen has reached 21.58mg/g sample.Because of the HBeta in three kinds of catalyst carriers
The Lewis acidic site content highest of molecular sieve surface.
2 wood vinegar list carrier catalysis of table reforms each component content and its yield
Many researchers have found that the acids that Ni base catalyst can effectively in conversion of biomass tar, aldehydes, ketone etc. have
Machine small-molecule substance generates hydrogen.Adding Ni, Sn isoreactivity substance, there are two the influence of aspect, a sides to catalyst surface acidity
Face active material can cover the acidic site (including Bronsted acid and Lewis acid) of molecular sieve surface, lead to catalyst table
The total acid content in face declines.On the other hand, catalyst surface plays the cation of the unsaturated Ni of synergistic effect, will be formed newly
The acid site lewis makes up originally capped lewis acidic site.From the results, it was seen that Ni, Sn isoreactivity substance cover
Lid effect, even more than Ni cation make up effect.
The property of carrier also plays an important role to the steam reforming reaction of tar, as can be seen from Table 2, different
Influence of the carrier to the selectivity of hydrogen is successively are as follows: Al2O3>HBeta>HZSM-5。
4 Composite Double carrier catalysis of embodiment reforms the catalytic reforming characteristic research of wood vinegar wood vinegar water vapour
Composite Double carrier catalysis reformation wood vinegar experiment condition: 600 DEG C of reaction temperature；Wood vinegar sample volume 0.25g/min；
Carrier gas N2Flow velocity 100mL/min；Catalyst amount 10g (gross masses of complex carries).
Used catalyst is respectively Ni/Sn/HBeta+MCM-41；Ni/Sn/HZSM-5+MCM-41；Ni/Sn/Al2O3+
MCM-41。
Under the action of Composite Double carried catalyst, the situation of change of each component is as shown in Figure 3 in gas.When use Ni/
When Sn/HBeta+MCM-41 complex carries catalyst, after 2h reaction, the content of hydrogen drops to 53% by original 60%,
Compared with single carried catalyst is used, the down ratio of hydrogen content is substantially reduced.It can be seen that mesoporous molecular sieve catalyst is added
MCM-41, it will be apparent that extend the service life of catalyst.
Ni/Sn/HZSM-5+MCM-41 catalyst also uses same effect.The apparent speed for reducing catalyst inactivation.Its
Middle extension catalytic activity, effect most preferably Ni/Sn/Al2O3+ MCM-41 mixed catalyst, in the stage of reaction of 2h, hydrogen
Content only has dropped 4% from original 65%, and is always maintained at efficient conversion ratio.It is other in the reaction process of 2h
Each gas component content is also without significantly raising or reduced trend.
Comparison sheet 2 and table 3 are as can be seen that utilize complex carries catalyst n i/Sn/HBeta+MCM-41 and Ni/Sn/HZSM-5
After+MCM-41, the flow of gas is decreased obviously.Respectively by original 114.75ml/min and 90.78ml/min, drop to
79.97ml/min and 53.55ml/min, has dropped close to one third, and then the yield of hydrogen is caused to be remarkably decreased.But this is imitated
Complex carries catalyst n i/Sn/Al should be not present in2O3On+MCM-41, the flow velocity of opposite mixed gas is from original
96.68ml/min rising slightly to 104.29ml/min.
3 Composite Double carrier catalysis of table reforms wood vinegar each component content and its yield
The changes of contents situation for further analyzing each gas component, which can be seen that work as, uses Ni/Sn/HZSM-5+MCM-41
And Ni/Sn/Al2O3After+MCM-41 catalyst, H2And CO2Content be all improved to some extent, but CH4, CO and C2H4's
Content has dropped.This be in wood vinegar catalytic organism cracking after, water vapour weight has occurred between the micro-molecular gas of generation
Whole effect.Such as CH4Steam reforming reacts (CH4+2H2O=CO2+4H2), the Water-gas shift reaction (CO+H of CO2O=CO2+H2) and
C2H4Steam reforming reaction (C2H4+H2O=1.5CH4+0.5CO2), eventually lead to H2And CO2Content rise.
5 Composite Double carrier catalysis of embodiment reforms wood vinegar life experiment
As Fig. 4 catalyst life experiment the result shows that, in 0.5h originally, H2And CO2Content be decreased obviously, CH4
Rise to a certain degree with the content of CO.This is because stable state has not been reached yet in reaction initial stage, entire reaction process.It
Afterwards in 4.5h reaction process, the content of each gaseous product is held essentially constant.To 5h, H2And CO2Content occur again significantly
Decline, this shows that the activity of this stage catalyst is begun to decline, and the service life of catalyst is probably in 4h or so.
The catalyst of selection different carriers reaction front and back has carried out electron-microscope scanning characterization, as a result such as Fig. 5.It is urged before comparison reaction
Before agent surface topography and post catalyst reaction area carbon pattern can be seen that reaction, fresh complex carries catalyst
The surface Ni/Sn/HBeta+MCM-41, it is at random to be dispersed with micropore, it is uneven, use rear catalyst Ni/Sn/HBeta+MCM-
41 surfaces, gathered a thick layer of carbon distribution.
And some short grained substances of distribution that fresh Ni/Sn/HZSM-5+MCM-41 catalyst surface is scattered, this is
Because in dipping process, being adsorbed on the active material or short grained ZSM or MCM-41 particle of catalyst surface.After use
Catalyst surface be spherical carbon particle, 1~2um of diameter is piled into tufted.
For fresh Ni/Sn/Al2O3+ MCM-41 catalyst, surface are uneven, but there are high-visible on surface
Duct, diameter is in 0.4um or so.And used catalyst, surface form one layer of loose, irregular carbon deposit, though
Right quantity is more, but still there are the gap of part, duct, reactant can still enter catalytic inner；This also explains Ni/
After 2h reacts, the yield of hydrogen declines compared with Ni/Sn/Al Sn/HBeta+MCM-412O3+ MCM-41 catalyst becomes apparent from.
Heat differential thermogravimetric analysis situation after table 4 describes different carriers catalyst reforming reaction, under hot-air.
Single carried catalyst surface carbon deposit accounts between the 3.28~3.53% of catalyst total amount, three kinds of different carriers, surface carbon deposit
Content is without apparent difference.HBeta catalyst surface carbon deposit is slightly lower than other two kinds of carriers, this is because HBeta molecule
The cellular structure (its shape selectivity) of sieve, more suitable for the catalytic reforming of wood vinegar organic molecule.Catalyst surface carbon deposit it is total
Amount is between 2.4~3.53%.The total amount of complex carries catalyst surface carbon deposit is significantly lower than corresponding single carried catalyst.This
Single carried catalyst is apparently higher than with the active duration of front complex carries catalyst to be consistent.It can also speculate single carrier
The reason of catalyst activity reduction should be catalyst surface carbon deposit blocking molecular sieve pore passage or covering catalyst surface
Caused by active site.And in complex carries catalyst, mesostructured material, first catalytic reforming segment space structure are larger
Organic matter, to reduce the organic matter of this type due to not easily passing through or entering microporous molecular sieve catalyst cellular structure
And in catalyst surface or the internal content for generating carbon deposit.
Mass loss corresponding to different peaks in 4 carbon deposit of table
Once it had been reported that and detects that catalyst surface carbon deposit weightless peak occurs in four different temperature sections using TPO technology.
The corresponding 4 kinds of different types of carbon deposits (table 4, Bayraktar, 2002) in these four different peaks.First peak is carbon deposit absorption
Hydrocarbon decompose caused by weightless peak；Second peak generated carbon deposit, third are reacted with metal active catalysis
Peak is carbon deposit caused by acid catalyzed reaction.Different carbon deposits is caused, mainly due to different organic matters, they are anti-with oxygen
Answer different, such as aromatic compound, the polymer or graphitic carbon of organic matter, the speed that they and oxygen react,
Temperature needed for burning is significantly different, and then leads to different carbon deposit weightless peaks.From table 4, it can be seen that single carrier is urged
The corresponding complex carries catalyst of agent respectively at the first, the second and third weightless peak mass change amount substantially close to, only
It is the corresponding temperature section of weightless peak of complex carries catalyst significantly to low-temperature space transfer, such as second of single carrier HBeta
Temperature at the corresponding maximum weightless peak of weightless peak is 368 DEG C, and the corresponding temperature in this peak of complex carries catalyst is transferred to
292.8 DEG C, it will be apparent that it has dropped.This is more advantageous to later period catalyst and is regenerated and calcining in air.
It can be seen that on the one hand complex carries catalyst can reduce catalyst carbon deposit content, it is on the other hand effective to inhibit not
Conducive to the generation of the carbon deposit type of catalyst regeneration.In addition to this, after using complex carries catalyst, fourth stage is due to acidity
The weightless peak of carbon deposit caused by being catalyzed disappears, this is because MCM-41 surface acidity is very weak, reduces after mixing total
Surface acidity (just for molecular sieve catalyst).γ-Al2O3In carrier after addition MCM-41, however it remains fourth stage is weightless
Peak, but after being mixed with MCM-41 catalyst, fourth stage weightless peak obviously weakens and (drops to 0.33% from original 0.53%).
Compare each carrier surface carbon deposit distribution situation, it can be seen that γ-Al2O3Carbon deposit in catalyst in the phase III contains
Amount is maximum.Compare Ni/Sn/Al2O3After+MCM-41 complex carries catalyst reaction 2h and reaction 5h after carbon deposit content results it is found that
The content of carbon deposit is not 2.5 times of 2h after reaction 5h.It can be seen that the carbon deposit content of catalyst is not with the reaction time at line
Sexual intercourse is influenced by a lot of other factors, this is the incipient stage that reaction carries out, and catalyst can be easier to generate product
Charcoal, after reaction carries out a period of time, catalyst produces the patience to carbon deposit, and then the content of newly-generated carbon deposit gradually subtracts
Slowly.
Claims (1)
1. a kind of method of wood vinegar water vapour catalytic reforming preparing hydrogen-rich gas, which is characterized in that wood vinegar gasifies, compound
Under the catalysis of complex carries catalyst under normal pressure, 600 DEG C of reaction temperature；0.25 g/min of wood vinegar sample volume；Carrier gas N2Stream
Fast 100mL/min；Catalyst amount 10g, react 2~4h, the Composite Double carried catalyst be by micro porous molecular sieve with it is mesoporous
Molecular sieve mixing after and carried metal nickel and metallic tin；The micro porous molecular sieve is HBeta or HZSM-5, described mesoporous
Molecular sieve is MCM-41；The mass ratio of the micro porous molecular sieve and mesopore molecular sieve is 1~5:1；The metallic nickel and metal
The molar ratio of tin is 1~5:1.
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