CN110343555A - A kind of liquid alloy catalytic pyrolysis biomass prepares the method and system of high Hydrogen fuel - Google Patents
A kind of liquid alloy catalytic pyrolysis biomass prepares the method and system of high Hydrogen fuel Download PDFInfo
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- CN110343555A CN110343555A CN201910789103.3A CN201910789103A CN110343555A CN 110343555 A CN110343555 A CN 110343555A CN 201910789103 A CN201910789103 A CN 201910789103A CN 110343555 A CN110343555 A CN 110343555A
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- liquid alloy
- biomass
- hydrogen fuel
- reaction kettle
- catalytic pyrolysis
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/20—Apparatus; Plants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of methods that liquid alloy catalytic pyrolysis biomass prepares high Hydrogen fuel, in a nitrogen atmosphere, block tin and nickel powder Hybrid Heating are formed liquid alloy, then addition biomass carries out reaction at 900-1100 DEG C and prepares hydrogen；Wherein, nickel powder additive amount is the 5-15% of liquid alloy weight.Combustible gas, H in output gas of the present invention are prepared relative to conventional biomass cracking2Content significantly rises, and significantly improves whole output GAS QUALITY；It is not in the case where carbon distribution accumulation leads to catalyst inactivation in the present invention.
Description
Technical field
The invention belongs to high Hydrogen fuel preparation technical fields, and in particular to a kind of liquid alloy catalytic pyrolysis biomass preparation
The method and system of high Hydrogen fuel.
Background technique
Hydrogen is a kind of clean energy resource of high and low pollution of efficiency, is widely used, and can be used for directly burning, hydrogen fuel electricity
Pond etc. is one of the focus of current scientific research and application.
Currently, hydrogen is prepared there are many means, wherein mainly have biochemical method, thermochemical method, electrochemical process etc., every class
Method respectively has the advantage and disadvantage of oneself, and wherein thermochemical method preparation hydrogen gas rate is higher than biochemical method, and preparation cost is lower than electrochemistry
Method becomes one of the scientific research hot spot in terms of hydrogen manufacturing.Thermochemical method includes: natural gas steam reformation hydrogen production, chemical chain reformation hydrogen production
Deng these methods generally will use catalyst or the carrier with catalysis, these catalyst are generally solid, therefore such
Producing hydrogen, catalyzing reaction is solid-liquid (raw material is liquid phase) catalysis or solid-gas (raw material is gas phase) catalytic reaction, these reactions are equal
The problems such as there are heat transfer, mass transfer, not high active site utilization efficiency, therefore study new high efficiency method urgently to prepare hydrogen
Gas.
Summary of the invention
Present invention aims to overcome that prior art defect, provides a kind of simple, efficient liquid alloy catalytic pyrolysis life
Substance prepares the method and system of high Hydrogen fuel.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of method that liquid alloy catalytic pyrolysis biomass prepares high Hydrogen fuel, in a nitrogen atmosphere, by block tin and nickel powder
Hybrid Heating forms liquid alloy, and then addition biomass carries out reaction at 900-1100 DEG C and prepares hydrogen；Wherein, nickel powder adds
Amount is the 5-15% of liquid alloy weight.
Further, the biomass is wooden unit or stalk；It is fed using screw-feeder intermittence, i.e., persistently feeds one
After the section time, stop charging, repeats to test.The biomass total volume of single charging is no more than 5 times of liquid alloy volume, i.e., and two
The ratio between person's volume, which is no more than after 5:1(biomass inlet amount reaches this ratio, stops charging about 1 ~ 10 minute, to the end of reacting, row
Substance in reaction kettle out).Specifically, wooden unit can be pine, Eucalyptus etc., stalk can select wheat stalk or corn stover
And its stalk briquette or compressed particle.
High Hydrogen fuel is prepared using above method progress liquid alloy catalytic pyrolysis biomass the present invention provides a kind of
System comprising reaction kettle, the first screw-feeder being connected with reaction kettle top by pipeline, the second screw-feeder and
Third screw-feeder, the nitrogen gas tank being connected by air inlet pipeline with reaction kettle, the outlet pipe being connected with reaction kettle and
Spray column and dehydrater are arranged in sequence on outlet pipe, blender is equipped in the reaction kettle, reaction kettle outer wall is equipped with electric heating
Set.
It is further preferred that the air inlet pipeline where nitrogen gas tank is equipped with the mass flowmenter to adjust nitrogen flow.
It is further preferred that spray tower bottom is equipped with drain pipe, drain pipe is equipped with valve.
Liquid alloy, which refers to, mixes various metals, is heated to molten condition, selection indium (In) in the present invention,
It is mixed that the metal of the low melting points such as gallium (Ga), tin (Sn) and the metal of the high catalytic activities such as nickel (Ni), platinum (Pt) carry out certain proportion
Heating melting after conjunction, liquid alloy catalyst as of the present invention.It reacts if immersing biomass into liquid alloy.
Liquid alloy both serves as catalyst, also becomes the carrier of reaction.The high heat density of liquid alloy, can be obviously improved reaction
Heat transfer efficiency, while liquid alloy, with respect to the catalyst of solid, mass transfer, active site utilization efficiency, which also have, significantly to be mentioned
It is high.Based on this, the invention proposes the method and systems that a kind of liquid alloy catalytic pyrolysis biomass prepares hydrogen.With existing skill
Art is compared, beneficial effects of the present invention:
1) combustible gas, H in output gas of the present invention are prepared relative to conventional biomass cracking2Content significantly rises, and makes whole
Body output GAS QUALITY significantly improves；
2) combustible gas is prepared relative to conventional biomass solid metal catalytic cracking, carbon distribution is since density is lower than liquid in the present invention
State alloy, and emersion liquid level, from the case where leading to catalyst inactivation without carbon distribution accumulation；
3) combustible gas is prepared relative to conventional biomass solid metal catalytic cracking, ash content is since density is lower than liquid in the present invention
The case where state alloy, and emersion liquid level, ash content blocking metallic catalyst leads to inactivation from without biomass.
Detailed description of the invention
Fig. 1 is the phasor of Sn-Ni alloy；
Fig. 2 is the structural schematic diagram that liquid alloy catalytic pyrolysis biomass of the present invention prepares high Hydrogen fuel system；
Fig. 3 is to carry out the experiment that liquid alloy catalytic pyrolysis biomass prepares high Hydrogen fuel using the method for the invention and system
As a result.
Specific embodiment
Technical solution of the present invention is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
As shown in Fig. 2, a kind of system that liquid alloy catalytic pyrolysis biomass prepares high Hydrogen fuel comprising reaction kettle 8 passes through
The first screw-feeder 1, the second screw-feeder 5 and the third screw-feeder 6 that pipeline is connected with 8 top of reaction kettle lead to
Cross the nitrogen gas tank 2 that air inlet pipeline is connected with reaction kettle 8, on the outlet pipe and outlet pipe being connected with reaction kettle 8 sequentially
Equipped with spray column 13 and dehydrater 14, blender 11 is equipped in the reaction kettle 8,8 outer wall of reaction kettle is equipped with electric heating cover 9.This
In embodiment, the second screw-feeder 5 and third screw-feeder 6 are arranged in parallel and share a feed pipe, feed pipe
It is equipped with the first valve 7.First screw-feeder, 1 place line end is connected with air inlet pipeline, and the first screw-feeder 1
Feeding pipe between reaction kettle 8 is equipped with the second valve 4(further for preferable blanking effect is obtained, and actually makes
Used time additionally sets up three branches separately as feed bin on the pipeline after mass flowmenter 3 and balances gas circuit, the pipeline end of three branches
End is connected with the first screw-feeder 1, the second screw-feeder 5 and third screw-feeder 6 respectively.Three feeders are as schemed
Shown in, valve arranged at top, and when experiment is first put into more metallic particles or biomass material, it is then shut off top valve,
Under the action of Balance Air, it can be realized smooth blanking and sealing be air tight, this is this field routine techniques, so no longer superfluous in detail
It states.)
Air inlet pipeline where nitrogen gas tank 2 is equipped with the mass flowmenter 3 to adjust nitrogen flow, and mass flowmenter 3
On air inlet pipeline between the first screw-feeder 1 and nitrogen gas tank 2.13 bottom of spray column is equipped with drain pipe, sets on drain pipe
There is third valve 15.Pipeline between spray column 13 and reaction kettle 8 is equipped with the 4th valve 12.8 bottom of reaction kettle is equipped with liquid
Pipe, outlet tube are equipped with the 5th valve 10.
Instance method process: by taking tin-nickel (Sn-Ni) liquid alloy as an example.
1, the nitrogen from nitrogen gas tank 2 is controlled by mass flowmenter 3, is blown into follow-up system, displaces inner air,
Only the second valve 4 and the 4th valve 12 are opened at this time, other valves are turned off.
2, it under the premise of persistently providing nitrogen, first opens the second screw-feeder 5 and a certain amount of tin is added in the first valve 7
Grain or fritter open electric heating cover 9 and are heated to 300 degree or so thawings, a certain amount of nickel is added using third screw-feeder 6 at this time
Powder opens blender 11, heats while stirring, be heated to 900 ~ 1100 degree or so, can form liquid alloy at this time.
3, it under the premise of persistently providing nitrogen, opens the first screw-feeder 1 and is pushed into biomass (various wooden units, all kinds of stalks
Briquetting or compressed particle), i.e. generation gasification reaction, the combustible gas based on hydrogen of output be discharged from the 4th valve 12, warp
13 spraying cooling of spray column (particulate matter is washed away, and metallic vapour is condensed, and is precipitated to 13 bottom of spray column) is crossed, with hydrogen
Based on combustible gas flow into dehydrater 14 remove moisture can store use.
4, after reaction continues for some time, the complete solid residue of unreacted can be floated on since density is lower than liquid alloy
Liquid alloy surface reaches certain proportion to volume ratio between biomass total feed and liquid alloy, at this time close spiral into
Glassware 1 stops charging, to after reaction, close valve 12, opens valve 18 and molten metal is discharged.
The present invention is tested by multiple groups, technological parameter is optimized, conclusion is as follows:
1) according to experimental result, when reaction temperature reaches 900 degree or more, it is preferable reaction temperature: to produce hydrogen effect.Also, with temperature
The increase of degree, better effect, but when temperature reaches 1200 DEG C or more hydrogen output increase it is unobvious, it is therefore proposed that reaction temperature is
900~1200℃。
2) alloying component matches: synthetic ratio is according to metal binary, ternary phase diagrams.
Citing: the proportion of liquid alloy in Sn-Ni alloy catalytic gasification.According to data in " alloy phase diagram handbook " it is found that
Sn-Ni alloy phase diagram is as shown in Figure 1.
Y-axis point is determined according to reaction temperature first, does horizontal line and curve intersection, the numerical value of crosspoint is that bianry alloy is solid
The critical point that liquid phase becomes, according to this critical point, the content of Ni is no more than this proportion when alloyage.It is specific to be equipped with step: first
It is first added low-melting-point metal (being Sn in this example), is proportionally added into refractory metal (Ni powder) after heating melting, stirring melting shape
At alloy.Ternary alloy three-partalloy preparation method is similar, inquires corresponding ternary alloy phase diagram first, determines matching for three kinds of metals
According to fusing point height when than, preparation, low-melting-point metal is first added, refractory metal (it is required that powdered) is added afterwards.
Embodiment 2
It is following by taking tin-nickel (Sn-Ni) liquid alloy as an example, using system described in embodiment 1 carry out produce hydrogen design parameter:
Alloying component and proportion: Sn(95%)-Ni(5%) alloy, mass ratio；
Reaction temperature: 950 DEG C；
Biomass material: pine block (charging 3g, volume about 6cm3)；
Detection: output gas uses Agilent 7890A gas chromatographic detection.
Experimental procedure:
1, the nitrogen from nitrogen gas tank 2 is controlled by mass flowmenter 3, nitrogen flow 500ml/min is blown into follow-up system
It is interior, inner air is displaced, only the second valve 4 and the 4th valve 12 are opened at this time, other valves are turned off；
2, it under the premise of persistently providing nitrogen, first opens the second screw-feeder 5 and small block tin 380g is added in the first valve 7, open
Electric heating cover 9 be heated to 350 degree until metallic tin melt completely, at this time using third screw-feeder 6 be added nickel powder 20g,
Blender 11 is opened, is heated while stirring, is heated to 950 degree and keeps 30min, forms liquid alloy (about at this time
56cm3).The secondary response biomass and liquid alloy volume ratio are 0.11:1, lower than the limiting value of 5:1 described previously；
3, it under the premise of persistently providing nitrogen, opens the first screw-feeder 1 and is pushed into pine block, is i.e. generation gasification reaction, output
Combustible gas based on hydrogen is discharged from the 4th valve 12, and by 13 spraying cooling of spray column, (particulate matter is washed away, metallic vapour
It is condensed, is precipitated to 13 bottom of spray column), the combustible gas based on hydrogen flows into the removing moisture of dehydrater 14 and can store
It uses；
4, after reaction continues for some time, the complete solid residue of unreacted can float on liquid since density is lower than liquid alloy
Alloy surface.Sustained response time about 3min opens valve 18 and liquid alloy is discharged to after reaction, close valve 12.
5, experimental result: experiment output gas componant and the comparing result that liquid alloy is not added are as shown in Figure 3.It is deep in figure
Grey legend shows the experiment that liquid alloy is not added, reacts in raw material push-in reaction kettle 8, reaction condition and addition melt
It is reacted after liquid alloy identical.From the figure 3, it may be seen that after liquid alloy is added, not only H2Yield has apparent rising, from 240mL/g
It is increased to 546mL/g, while the yield of CO also increases, shows that the addition of liquid alloy can not only promote H2Generation, also
The efficiency of carbon con version of reaction can be promoted.
Claims (5)
1. a kind of method that liquid alloy catalytic pyrolysis biomass prepares high Hydrogen fuel, which is characterized in that in a nitrogen atmosphere, will
Block tin and nickel powder Hybrid Heating form liquid alloy, and then addition biomass carries out reaction at 900-1100 DEG C and prepares hydrogen；Its
In, nickel powder additive amount is the 5-15% of liquid alloy weight.
2. the method that liquid alloy catalytic pyrolysis biomass as described in claim 1 prepares high Hydrogen fuel, which is characterized in that described
Biomass is wooden unit or stalk；Biomass and the volume ratio of liquid alloy are no more than 5:1.
3. the system that liquid alloy catalytic pyrolysis biomass prepares high Hydrogen fuel is carried out using 2 the method for claims 1 or 2,
It is characterized in that, including reaction kettle, the first screw-feeder, the second screw-feeder that are connected by pipeline with reaction kettle top
With third screw-feeder, the nitrogen gas tank being connected by air inlet pipeline with reaction kettle, the outlet pipe being connected with reaction kettle
And spray column and dehydrater are arranged in sequence on outlet pipe, blender is equipped in the reaction kettle, reaction kettle outer wall is equipped with electricity and adds
Hot jacket.
4. carrying out the system that liquid alloy catalytic pyrolysis biomass prepares high Hydrogen fuel as claimed in claim 3, which is characterized in that
Air inlet pipeline where nitrogen gas tank is equipped with the mass flowmenter to adjust nitrogen flow.
5. carrying out the system that liquid alloy catalytic pyrolysis biomass prepares high Hydrogen fuel as claimed in claim 4, which is characterized in that
It sprays tower bottom and is equipped with drain pipe, drain pipe is equipped with valve.
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| CN201910789103.3A CN110343555A (en) | 2019-08-26 | 2019-08-26 | A kind of liquid alloy catalytic pyrolysis biomass prepares the method and system of high Hydrogen fuel |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113249144A (en) * | 2021-05-10 | 2021-08-13 | 广州环峰能源科技股份有限公司 | Biomass gasification system with high gasification rate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190055173A1 (en) * | 2017-08-21 | 2019-02-21 | Palo Alto Research Center Incorporated | System and method for pyrolysis using a liquid metal catalyst |
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- 2019-08-26 CN CN201910789103.3A patent/CN110343555A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190055173A1 (en) * | 2017-08-21 | 2019-02-21 | Palo Alto Research Center Incorporated | System and method for pyrolysis using a liquid metal catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113249144A (en) * | 2021-05-10 | 2021-08-13 | 广州环峰能源科技股份有限公司 | Biomass gasification system with high gasification rate |
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