CN110330991A - A kind of thermal cyclic carrier catalytic pyrolysis biomass improves the devices and methods therefor of hydrogen yield - Google Patents
A kind of thermal cyclic carrier catalytic pyrolysis biomass improves the devices and methods therefor of hydrogen yield Download PDFInfo
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- CN110330991A CN110330991A CN201910751027.7A CN201910751027A CN110330991A CN 110330991 A CN110330991 A CN 110330991A CN 201910751027 A CN201910751027 A CN 201910751027A CN 110330991 A CN110330991 A CN 110330991A
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- pyrolysis
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- hydrogen yield
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
- C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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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
- Y02P20/10—Process efficiency
Abstract
The invention discloses the devices and methods therefors that a kind of thermal cyclic carrier catalytic pyrolysis biomass improves hydrogen yield, wherein: device, including screw feeder, pyrolysis reactor, hot lifting system and rotary furnace, the discharge port of screw feeder is located at the top of pyrolysis reactor feed inlet, the discharge port of pyrolysis reactor bottom connects the feed inlet of rotary furnace by hot lifting system, the discharge port of rotary furnace is communicated with pyrolysis reactor feed inlet, gas outlet at the top of pyrolysis reactor is communicated with the air inlet of rotary furnace, and gas outlet is additionally provided on rotary furnace；The present invention is starting heat carrier using alumina globule, and hydrogen yield improves 10-30%, and tar yield reduces by 20%；It is thermal cyclic carrier using pyrolysis residue, reduces the cost of catalysis heat carrier；High temperature pyrolysis gas are passed into rotary furnace, the tar of 80% or more removing improves hydrogen yield, and can heat heat carrier, improves the thermal efficiency of system.
Description
Technical field
The invention belongs to biomass pyrolytic technical field, in particular to a kind of thermal cyclic carrier catalytic pyrolysis biomass improves
The devices and methods therefor of hydrogen yield.
Background technique
Hydrogen is a kind of highly important chemical industry intermediate products, is mainly used in ammonia, the synthesis of methanol and petrochemical industry
Hydrofinishing.Meanwhile hydrogen or a kind of efficient, clean energy carrier.As the fuel cell technology of green high-efficient is opened
Hair and application, fuel of the hydrogen as fuel cell have the huge market demand.The acquisition of hydrogen is from fossil fuel
Cracking with reform, the electrolysis of water and photocatalysis Decomposition, the decomposition of ammonia etc., due to the decomposing hydrogen-production of water and ammonia still rely at present it is expensive
Metallic catalyst, at present in hydrogen main source, fossil resource accounts for 96%, and the decomposition of water only accounts for 4% or so.In recent years, researcher
A large amount of explorations have been carried out to biomass hydrogen preparation, pass through the methods of catalytic reforming of pyrolytic gasification or biomass coke tar prepare hydrogen-rich
Gas.Since biomass economy process can be considered carbon dioxide " zero-emission ", biomass hydrogen preparation is to supplement fossil fuel hydrogen manufacturing, no
The consumption that fossil resource can only be reduced can also alleviate greenhouse effects bring environmental problem.Biomass resource is from a wealth of sources,
From wood furniture processing, construction and decoration rubbish, garden garbage and agriculture and forestry organic waste material etc., the minimizing of biomass garbage, nothing
Evilization, disposal of resources are the important components of town and country garbage disposal.However product liquid content in biomass pyrolysis process
Height is easy the case where causing to corrode to pyrolysis plant and blocking, usually using noble metal catalyst progress catalytic pyrolysis, however this
A little catalyst are easy carbon deposit, inactivate noble metal.
Summary of the invention
The present invention provides the devices and methods therefors that a kind of thermal cyclic carrier catalytic pyrolysis biomass improves hydrogen yield, should
Method participates in catalytic pyrolysis reaction using cheap aluminium oxide-charcoal as thermal cyclic carrier, reduces tar in pyrolytic process
Yield, improve hydrogen yield, with solves the problems, such as in the prior art pyrolysis plant easily cause corrosion and blocking, reduction catalyst at
This, part inhibits carbon deposit effect.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of thermal cyclic carrier catalytic pyrolysis biomass improves the device of hydrogen yield, including screw feeder 2, pyrolysis reactor
3, hot lifting system 5 and rotary furnace 6, the discharge port of screw feeder 2 are located at the top of 3 feed inlet of pyrolysis reactor, the heat
The discharge port for solving 3 bottom of reactor connects the feed inlet of rotary furnace 6, the discharge port of rotary furnace 6 and pyrolysis by hot lifting system 5
3 feed inlet of reactor communicates, and the gas outlet at 3 top of pyrolysis reactor is communicated with the air inlet of rotary furnace 6, the rotary furnace
Gas outlet is additionally provided on 6.
Further, biomass material 1 is from after the feed inlet entrance of screw feeder 2, from the discharge port of screw feeder 2
Into pyrolysis reactor 3, pyrolysis reactor 3 generates high temperature pyrolysis gas 8 and pyrolysis residue 4, and pyrolysis residue 4 is through hot lifting system 5
It is delivered to rotary furnace 6, heat carrier 7 is re-used as and is delivered to pyrolysis reactor 3, high temperature pyrolysis gas 8 enter in rotary furnace 6 to be carried with heat
Body 7 mixes, and reaction obtains high hydrogen content gas 9, and high hydrogen content gas 9 is discharged through the gas outlet of rotary furnace 6.
Further, the volumn concentration of hydrogen is 70-85% in the high hydrogen content gas 9.
A kind of method that thermal cyclic carrier catalytic pyrolysis biomass improves hydrogen yield, comprising the following steps:
After S1, alumina balls heat in rotary furnace 6, it is delivered to pyrolysis reactor 3；
S2, biomass material 1 are added in pyrolysis reactor 3 by screw feeder 2；
S3, in pyrolysis reactor 3, biomass material 1 is sufficiently mixed with aluminium oxide, reaction obtain high temperature pyrolysis gas 8 and pyrolysis
Residue 4；
Pyrolysis residue 4 obtained in S4, step S3 is delivered in rotary furnace 6 after heating, is re-used as heat carrier 7 and is delivered to pyrolysis
Reactor 3 repeats step S1-S3；
High temperature pyrolysis gas 8 obtained in S5, step S3 are passed into rotary furnace 6, and are mixed with heat carrier 7, and reaction obtains Gao Qing
Gas content gas 9.
Further, in the step S1, alumina balls are heated to 600-900 DEG C in rotary furnace 6.
Further, in the step S2, the control of screw feeder 2 enters biomass material 1 in pyrolysis reactor 3
Amount.
Further, in the step S3, the shape of aluminium oxide is sphere.
Further, in the step S3, the mass ratio of biomass material 1 and alumina balls is 1:1.
Further, in the step S3, reaction time 30-60min.
Further, in the step S3, obtained pyrolysis residue 4 to ash content less than 5% when, the catalysis of pyrolysis residue 4 is living
Property reduce, pyrolysis residue 4 stops circulation, and as activated carbon application in soil remediation or water body purification.
Further, in the step S4, pyrolysis residue 4 is delivered in rotary furnace 6 and is heated to 600-900 DEG C.
Further, in the step S5, the volumn concentration of hydrogen is 70- in obtained high hydrogen content gas 9
85%。
Compared with prior art, the invention has the following advantages:
1, it is starting heat carrier using alumina globule, hydrogen yield can be improved into 10-30% in pyrolytic process, tar produces
Rate reduces by 20% or so；
2, it is thermal cyclic carrier using pyrolysis residue, the cost of catalysis heat carrier is effectively reduced, also has catalysis to live pyrolytic process
Property；
3, high temperature pyrolysis gas are passed into rotary furnace, can have both removed 80% or more tar, improve hydrogen yield, and can be with
Heat carrier is heated, the thermal efficiency of system is improved.
4,30-50% is improved using the hydrogen yield of two catalytic process production, charcoal quality is better than the mark of wood activated charcoal
It is quasi-.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of device in the present invention；
Wherein: 1- biomass material, 2- screw feeder, 3- pyrolysis reactor, 4- pyrolysis residue, the hot lifting system of 5-, 6- are returned
Converter, 7- heat carrier, 8- high temperature pyrolysis gas, 9- high hydrogen content gas.
Specific embodiment
Below with reference to embodiment, the present invention will be further explained.
As shown in Figure 1, a kind of thermal cyclic carrier catalytic pyrolysis biomass improves the device of hydrogen yield, including screw feeder
The discharge port of device 2, pyrolysis reactor 3, hot lifting system 5 and rotary furnace 6, screw feeder 2 is located at 3 feed inlet of pyrolysis reactor
Top, the discharge port of 3 bottom of pyrolysis reactor connects the feed inlet of rotary furnace 6, rotary furnace 6 by hot lifting system 5
Discharge port communicated with 3 feed inlet of pyrolysis reactor, the gas outlet at 3 top of the pyrolysis reactor and the air inlet of rotary furnace 6
It communicates, is additionally provided with gas outlet on the rotary furnace 6；In particular, biomass material 1 from the feed inlet of screw feeder 2 into
After entering, enter pyrolysis reactor 3 from the discharge port of screw feeder 2, pyrolysis reactor 3 generates high temperature pyrolysis gas 8 and pyrolysis is residual
Slag 4, pyrolysis residue 4 are delivered to rotary furnace 6 through hot lifting system 5, are re-used as heat carrier 7 and are delivered to pyrolysis reactor 3, high temperature
Pyrolysis gas 8 enters in rotary furnace 6 to be mixed with heat carrier 7, and reaction obtains high hydrogen content gas 9, and high hydrogen content gas 9 passes through back
The gas outlet of converter 6 is discharged, and the volumn concentration of hydrogen is 70-85% in the high hydrogen content gas 9.
A kind of method that thermal cyclic carrier catalytic pyrolysis biomass improves hydrogen yield, comprising the following steps:
S1, alumina balls are heated to 600-900 DEG C in rotary furnace 6, are delivered to pyrolysis reactor 3；
S2, biomass material 1 are added in pyrolysis reactor 3 by the way that screw feeder 2 is quantitative；
S3, in pyrolysis reactor 3, biomass material 1 and alumina globule are sufficiently mixed with mass ratio for 1:1, react 30-
60min obtains high temperature pyrolysis gas 8 and pyrolysis residue 4；Preferably, the pyrolysis residue 4 obtained to ash content less than 5% when, be pyrolyzed it is residual
The catalytic activity of slag 4 reduces, and pyrolysis residue 4 stops circulation, and as activated carbon application in soil remediation or water body purification；
Pyrolysis residue 4 obtained in S4, step S3, which is delivered in rotary furnace 6, is heated to 600-900 DEG C, is re-used as heat carrier 7
It is delivered to pyrolysis reactor 3, repeats step S1-S3；
High temperature pyrolysis gas 8 obtained in S5, step S3 are passed into rotary furnace 6, and are mixed with heat carrier 7, and reaction obtains Gao Qing
Gas content gas 9, the volumn concentration of hydrogen is 70-85% in high hydrogen content gas 9.
Embodiment 1
1kg/h aluminium oxide is heated to 600-900 DEG C by rotary furnace 6, is delivered to pyrolysis reactor 3, the biomass material of 1kg/h
1 is quantitatively transferred to pyrolysis reactor 3 by screw feeder 2.45min, available 1.3kg/ are reacted in pyrolysis reactor 3
The pyrolysis residue 4,0.6m of h3The high temperature pyrolysis gas 8 of/h, pyrolysis residue 4, which is overheated lifting system 5 and is delivered in rotary furnace 6, to be continued
It is heated to 600-900 DEG C, heat carrier 7, which is delivered in pyrolysis reactor 3, continues as the heating of subsequent bio matter raw material 1, and heat in this way carries
Body 7 can be recycled, and the ash content in pyrolysis residue 4 is not influenced by aluminium oxide, when being recycled to ash content less than 5%, heat carrier 7
Catalytic activity reduce, pyrolysis residue 4 can be used as activated carbon application in soil remediation, water body purification etc., meets in national standard
Defined wood activated charcoal standard.In obtained high hydrogen content gas 9, the gas of the volumn concentration of 70-85% is hydrogen
Gas improves 20-40% relative to inert heat carrier, and hydrogen yield increases 30-50%.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. the device that a kind of thermal cyclic carrier catalytic pyrolysis biomass improves hydrogen yield, which is characterized in that including screw feeder
Device (2), pyrolysis reactor (3), hot lifting system (5) and rotary furnace (6), it is anti-that the discharge port of screw feeder (2) is located at pyrolysis
The top of device (3) feed inlet is answered, the discharge port of pyrolysis reactor (3) bottom connects rotary furnace by hot lifting system (5)
(6) discharge port of feed inlet, rotary furnace (6) is communicated with pyrolysis reactor (3) feed inlet, at the top of the pyrolysis reactor (3)
Gas outlet communicated with the air inlet of rotary furnace (6), be additionally provided with gas outlet on the rotary furnace (6).
2. thermal cyclic carrier catalytic pyrolysis biomass according to claim 1 improves the device of hydrogen yield, feature exists
In biomass material (1) enters pyrolysis from the discharge port of screw feeder (2) from after the feed inlet entrance of screw feeder (2)
Reactor (3), pyrolysis reactor (3) generate high temperature pyrolysis gas (8) and pyrolysis residue (4), and pyrolysis residue (4) is through hot lifting system
(5) rotary furnace (6) are delivered to, heat carrier (7) is re-used as and is delivered to pyrolysis reactor (3), high temperature pyrolysis gas (8) enter revolution
It is mixed in furnace (6) with heat carrier (7), reaction obtains high hydrogen content gas (9), and high hydrogen content gas (9) is through rotary furnace (6)
Gas outlet discharge.
3. thermal cyclic carrier catalytic pyrolysis biomass according to claim 1 improves the device of hydrogen yield, feature exists
In the volumn concentration of hydrogen is 70-85% in the high hydrogen content gas (9).
4. a kind of method that thermal cyclic carrier catalytic pyrolysis biomass improves hydrogen yield, which comprises the following steps:
S1, alumina balls after heating, are delivered to pyrolysis reactor (3) in rotary furnace (6)；
S2, biomass material (1) are added in pyrolysis reactor (3) by screw feeder (2)；
S3, in pyrolysis reactor (3), biomass material (1) is sufficiently mixed with aluminium oxide, reaction obtain high temperature pyrolysis gas (8)
With pyrolysis residue (4)；
Pyrolysis residue (4) obtained in S4, step S3 is delivered in rotary furnace (6) after heating, is re-used as heat carrier (7) conveying
To pyrolysis reactor (3), step S1-S3 is repeated；
High temperature pyrolysis gas (8) obtained in S5, step S3 are passed into rotary furnace (6), and are mixed with heat carrier (7), are reacted
To high hydrogen content gas (9).
5. the method that thermal cyclic carrier catalytic pyrolysis biomass according to claim 4 improves hydrogen yield, feature exist
In in the step S1, alumina balls are heated to 600-900 DEG C in rotary furnace (6).
6. the method that thermal cyclic carrier catalytic pyrolysis biomass according to claim 4 improves hydrogen yield, feature exist
In in the step S2, screw feeder (2) control enters the amount of biomass material (1) in pyrolysis reactor (3).
7. the method that thermal cyclic carrier catalytic pyrolysis biomass according to claim 4 improves hydrogen yield, feature exist
In in the step S3, the mass ratio of biomass material (1) and alumina balls is 1:1；Reaction time is 30-60min；Oxidation
The shape of aluminium is sphere.
8. the method that thermal cyclic carrier catalytic pyrolysis biomass according to claim 4 improves hydrogen yield, feature exist
In, in the step S3, obtained pyrolysis residue 4 to ash content less than 5% when, the catalytic activity of pyrolysis residue (4) reduces, pyrolysis
Residue (4) stops circulation, and as activated carbon application in soil remediation or water body purification.
9. the method that thermal cyclic carrier catalytic pyrolysis biomass according to claim 4 improves hydrogen yield, feature exist
In in the step S4, pyrolysis residue (4) is delivered in rotary furnace (6) and is heated to 600-900 DEG C.
10. the method that thermal cyclic carrier catalytic pyrolysis biomass according to claim 4 improves hydrogen yield, feature exist
In in the step S5, the volumn concentration of hydrogen is 70-85% in obtained high hydrogen content gas (9).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110938448A (en) * | 2019-12-03 | 2020-03-31 | 新奥生物质能(天津)有限公司 | Control method and device of biomass pyrolysis device |
| CN112158805A (en) * | 2020-09-08 | 2021-01-01 | 新奥生物质能(天津)有限公司 | Method and system for preparing hydrogen by using biomass |
| CN113372961A (en) * | 2021-06-21 | 2021-09-10 | 浙江工业大学 | High-temperature calcination and re-catalysis utilization system and process for biomass gasification ash |
| CN113462435A (en) * | 2021-06-25 | 2021-10-01 | 浙江工业大学 | Resource recycling catalytic utilization method for biomass gasification ash |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938448A (en) * | 2019-12-03 | 2020-03-31 | 新奥生物质能(天津)有限公司 | Control method and device of biomass pyrolysis device |
| CN112158805A (en) * | 2020-09-08 | 2021-01-01 | 新奥生物质能(天津)有限公司 | Method and system for preparing hydrogen by using biomass |
| CN113372961A (en) * | 2021-06-21 | 2021-09-10 | 浙江工业大学 | High-temperature calcination and re-catalysis utilization system and process for biomass gasification ash |
| CN113462435A (en) * | 2021-06-25 | 2021-10-01 | 浙江工业大学 | Resource recycling catalytic utilization method for biomass gasification ash |
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