CN106833759A - A kind of device and method of removing biomass gasification tar of being reformed based on chemical chain - Google Patents
A kind of device and method of removing biomass gasification tar of being reformed based on chemical chain Download PDFInfo
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- CN106833759A CN106833759A CN201710102734.4A CN201710102734A CN106833759A CN 106833759 A CN106833759 A CN 106833759A CN 201710102734 A CN201710102734 A CN 201710102734A CN 106833759 A CN106833759 A CN 106833759A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 51
- 238000002309 gasification Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000126 substance Substances 0.000 title claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000001301 oxygen Substances 0.000 claims abstract description 123
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 119
- 239000000567 combustion gas Substances 0.000 claims abstract description 58
- 238000002407 reforming Methods 0.000 claims abstract description 37
- 238000002485 combustion reaction Methods 0.000 claims abstract description 27
- 238000006057 reforming reaction Methods 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 239000002737 fuel gas Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 abstract description 10
- 230000008929 regeneration Effects 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 239000011269 tar Substances 0.000 description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 15
- 238000009826 distribution Methods 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- 239000011286 gas tar Substances 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
- C10K1/026—Dust removal by centrifugal forces
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
Abstract
The present invention discloses a kind of device and method of removing biomass gasification tar of being reformed based on chemical chain, wherein, including the first cyclone separator for the thick combustion gas of gasification of biomass separate dedusting being sequentially connected, for the preheater preheated to the thick combustion gas of gasification of biomass, reforming reactor and the air burning reactor for the carrier of oxygen after reforming reaction and air to be carried out combustion reaction for the thick combustion gas of gasification of biomass after preheating and the carrier of oxygen to be carried out reforming reaction, the air burning reactor with the second cyclone separator for the carrier of oxygen after oxidized separate dedusting is connected between reforming reactor, the reforming reactor is also associated with the 3rd cyclone separator for reacted combustion gas separate dedusting.Tar macromolecule fraction is oxidized to CO, H by the present invention using the Lattice Oxygen and catalytic action of the carrier of oxygen2Deng small-molecule substance；Carrier of oxygen circular regeneration between reforming reactor and combustion reactor, carrier of oxygen regeneration is simple.
Description
Technical field
Gasification of biomass is removed the present invention relates to the energy and chemical technology field, more particularly to a kind of reformation based on chemical chain
The device and method of tar.
Background technology
Biomass are resourceful regenerative resources.Biomass high volatile（About 70%）The characteristics of content, determines it
Gasification Land use systems have economy and technical advantage.Biomass gasification technology can with follow-up synthetic liquid fuel, generating, heat supply with
And the production unit such as chemical products is mutually connected, so as to the clean and effective for realizing biomass resource is utilized with variation.But current nothing
By being using the biomass gasification technology of air, water vapour or oxygen and fixed bed or fluidized-bed reactor, because of biomass
High volatile and cause in combustion gas containing more tar accessory substance, tar is gaseous state in high temperature, and can be coagulated at below about 200 DEG C
Become liquid.The presence of tar such as reduces gasification efficiency, blocks pipe to gasification of biomass and its using producing serious influence
Road, the follow-up synthetic catalyst of murder by poisoning, infringement combustion gas are using equipment etc., while will also increase gas-purification difficulty, cause environment dirt
Dye.Therefore, tar content is one of deciding factor of restriction biomass gasification technology large-scale application in combustion gas, how to be eliminated
Tar in gasification is current biomass gasification technology most problem demanding prompt solution.Although taking raising running temperature etc. to arrange
The yield of tar when can to a certain extent reduce gasification of biomass is applied, even if in this way, tar content is still relative in combustion gas
It is higher to be required, it is necessary to further remove and meet downstream utilization.The removing sulfuldioxide of tar includes Physical and chemistry in combustion gas
Method.Physical is to be removed tar in combustion gas by washing or absorbent, and method simply but easily causes secondary pollution.Chemical method
It by catalytic pyrolysis by tar destruction is micro-molecular gas to be, does not have secondary pollution and simultaneously trans-utilization tar, is current
The more tar removal methods of research.Traditional catalytic pyrolysis point two ways：One kind be dolomite, alkaline earth metal compound with
Biomass in gasification furnace together catalytic gasification so as to reduce the generation of tar；After one kind is the outer decomposition gasification of nickel-base catalyst stove
Tar in combustion gas.There is the deficiency that consumption is big, catalytic efficiency is low in coke and dolomite etc..Nickel-base catalyst activity is high, tar
Lytic effect preferably, but the easy coking in its surface and inactivate；Nickel-base catalyst is typically made up of nickel, auxiliary agent and carrier, uses preceding need
By catalyst reduction, elemental nickel is the avtive spot of catalyst.Patent（CN104549450A）Disclosed Ni-MgO/HZSM-5,
Patent（CN102145292A）Disclosed NiO-MgO-CeO2-WO3- olivine, patent（CN101693204B）Disclosed NiO-
La2O3-CeO2-MgO-γAl2O3, patent（CN100404135C）Disclosed monoblock type NiO- γ Al2O3The biomass such as-cordierite
Gasification tar catalytic cracking catalyst, is required for first using H when in use2Reduced.After above-mentioned nickel-base catalyst carbon distribution inactivation,
It is complex process, costly by except carbon, two step regenerative processes of reduction, should in industry using nickel-base catalyst pyrolysis fuel oil
By the serious restriction of cost in.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, being reformed based on chemical chain it is an object of the invention to provide one kind, it is biological to remove
The device and method of matter gasification tar, it is intended to solve existing tar removing sulfuldioxide in the presence of easy carbon distribution, need prereduction and regeneration tired
Difficult problem.
Technical scheme is as follows：
It is a kind of based on chemical chain reform removing biomass gasification tar device, wherein, including be sequentially connected for biology
The thick combustion gas of matter gasification separate the first cyclone separator, the preheating for being preheated to the thick combustion gas of gasification of biomass of dedusting
Device, for the thick combustion gas of gasification of biomass after preheating and the carrier of oxygen are carried out the reforming reactor of reforming reaction with for that will reform
The reacted carrier of oxygen carries out the air burning reactor of combustion reaction, the air burning reactor and reforming reaction with air
The second cyclone separator for the carrier of oxygen after oxidized separate dedusting is connected between device, the reforming reactor is also
It is connected with the 3rd cyclone separator for reacted combustion gas separate dedusting.
A kind of method that biomass gasification tar is removed using device as described above, wherein, comprise the following steps：
After the thick combustion gas of step A, gasification of biomass separates dedusting and preheater preheating through the first cyclone separator, into reforming reaction
Reforming reaction is carried out in device with the carrier of oxygen, after reacted combustion gas separates dedusting through the 3rd cyclone separator, clean fuel gas is obtained；
Carrier of oxygen air inlet combustion reactor after step B, reforming reaction, combustion reaction, the carrier of oxygen are carried out with air
After being oxidized, recycled into the reforming reactor after then separating dedusting through the second cyclone separator.
Described method, wherein, the oxygen denuded air that combustion reaction is produced in the air burning reactor is through the second whirlwind
Separator enters the preheater thick combustion gas of preheating after separating dedusting.
Described method, wherein, in the step A, tar content and oxygen in the reforming reactor in the thick combustion gas
The Lattice Oxygen mass ratio of carrier is 1:0.5-5.
Described method, wherein, in the step B, the burned surplus coefficient of air is in the air burning reactor
0.5-1.5。
Described method, wherein, in the step A, the operation temperature of the reforming reactor is 550-950 DEG C, operates
Pressure is 0.1MPa.
Described method, wherein, the operation temperature of the air burning reactor is 850-1050 DEG C, operating pressure is
0.1MPa。
Described method, wherein, the active component of the carrier of oxygen is Fe oxides, Cu oxides, Ni oxides, Ce oxygen
One or more in compound, Mn oxides, Ca oxides, the inert component of the carrier of oxygen is Al2O3, in MgO, ZrO one
Plant or various.
Described method, wherein, the content of the active component is 30-80wt%, and the content of the inert component is 20-
70wt%。
Described method, wherein, the particle size range of the carrier of oxygen is 0.1-5mm.
Beneficial effect：Tar macromolecule fraction is oxidized to CO, H by the present invention at high temperature using the Lattice Oxygen of the carrier of oxygen2
Removed Deng small-molecule substance, while can partly retain and utilize the energy of tar again, the tar of combustion gas after being removed through the present apparatus
Content is less than 1g/Nm3, tar removal efficiency is more than 90%；In addition, the cycle set of the carrier of oxygen is transmitted oxygen, heat-carrying and is catalyzed in one,
The oxidation reaction heat and thick combustion gas sensible heat of the carrier of oxygen can be made full use of；Additionally, the carrier of oxygen is by reforming reactor and sky
Circular regeneration simply, is beneficial to maintenance with possible carbon distribution, carrier of oxygen regeneration and elimination carbon distribution is eliminated between gas combustion reactor
The continuous operation of system.
Brief description of the drawings
Fig. 1 is a kind of schematic device of removing biomass gasification tar of being reformed based on chemical chain of the invention.
Specific embodiment
The present invention provides a kind of device and method of removing biomass gasification tar of being reformed based on chemical chain, to make the present invention
Purpose, technical scheme and effect it is clearer, clear and definite, the present invention is described in more detail below.It should be appreciated that this place
The specific embodiment of description is only used to explain the present invention, is not intended to limit the present invention.
With reference to shown in Fig. 1, a kind of schematic device of removing biomass gasification tar of being reformed based on chemical chain of the invention,
As illustrated, including being sequentially connected for carrying out separating the first cyclone separator of dedusting to the thick combustion gas of gasification of biomass, using
In the preheater preheated to the thick combustion gas of gasification of biomass, for the thick combustion gas of gasification of biomass after preheating and the carrier of oxygen to be entered
The reforming reactor of row reforming reaction and the air burning for the carrier of oxygen after reforming reaction and air to be carried out combustion reaction
Reactor, the air burning reactor be connected between reforming reactor for separate removing to the carrier of oxygen after oxidized
Second cyclone separator of dirt, the reforming reactor is also associated with for carrying out separating dedusting to reacted combustion gas of reforming
3rd cyclone separator.
Based on said apparatus, the present invention provides a kind of method that biomass gasification tar is removed using device as described above,
Wherein, comprise the following steps：
After the thick combustion gas of step A, gasification of biomass separates dedusting and preheater preheating through the first cyclone separator, into reforming reaction
Reforming reaction is carried out with the carrier of oxygen in device, after the combustion gas after reforming reaction separates dedusting through the 3rd cyclone separator, obtains clean
Combustion gas；
Carrier of oxygen air inlet combustion reactor after step B, reforming reaction, combustion reaction, the carrier of oxygen are carried out with air
After being oxidized, recycled into the reforming reactor after then separating dedusting through the second cyclone separator.
With reference to shown in Fig. 1, the method to above-mentioned removing biomass gasification tar of the invention is described in detail below.
In step A, the thick combustion gas for containing tar from biomass gasification system separates dedusting by the first cyclone separator,
Again with the high-temperature tail gas from air burning reactor（Oxygen deprivation tail gas）After preheater preheating, into equipped with metal oxide
（The carrier of oxygen）Reforming reactor, there is partial oxidation with the Lattice Oxygen of the high temperature carrier of oxygen in macromolecular tar material in thick combustion gas
CO, H after reaction conversion2Deng small-molecule substance, the carrier of oxygen is reduced, and reacted combustion gas is separated by the 3rd cyclone separator and removed
After dirt, clean fuel gas are obtained.The present invention using the carrier of oxygen Lattice Oxygen the tar fraction in biomass rough gas be oxidized to CO,
H2Removed Deng small-molecule substance, while can partly retain and utilize the energy of tar again.
In step A, tar content is with the Lattice Oxygen mass ratio of the carrier of oxygen in the reforming reactor in the thick combustion gas
1:0.5-5, it is preferable that mass ratio is 1:1-3, such as mass ratio are 1:1、1:2 or 1:3
In step A, the operation temperature of the reforming reactor is 550-950 DEG C, operating pressure is 0.1MPa.It is of the present invention heavy
Temperature institute's calorific requirement of whole reactor is carried by the sensible heat of thick combustion gas and the high temperature carrier of oxygen, air burning reactor high temperature tail gas sensible heat
For.
In step B, the carrier of oxygen being reduced after reforming reaction（Its surface may have part carbon distribution）Air inlet burning is anti-
Device is answered, combustion reaction occurs with air, the carrier of oxygen regains Lattice Oxygen, surface after being wholly or largely oxidized
It is CO that carbon distribution is fully oxidized2And eliminate, the heat of the carrier of oxygen burned generation simultaneously, the high temperature carrier of oxygen enters after oxidation
Reforming reactor is recycled.
In step B, the burned surplus coefficient of air is 0.5-1.5 in the air burning reactor, and the air burning is superfluous
Coefficient refers to the ratio of amount of actual air for combustion and the theoretical air requirement of reduction-state carrier of oxygen complete oxidation.
The operation temperature of the air burning reactor is 850-1050 DEG C, operating pressure is 0.1MPa.It is of the present invention
Air burning temperature of reactor institute's calorific requirement is provided by the oxidation reaction heat of oxygen in the reduction-state carrier of oxygen and air.
Two steps of above-mentioned steps A and step B form a cyclic process.
Tar fraction in biomass rough gas is oxidized to CO, H by the present invention using the Lattice Oxygen of the carrier of oxygen2Etc. small molecule
Material and remove, while can partly retain and utilize the energy of tar again.The method to the advance reduction of the carrier of oxygen, and need not pass through
Carrier of oxygen Lattice Oxygen continuously can be regenerated and eliminated by circulation of the carrier of oxygen between reforming reactor and air burning reactor
Carbon distribution.
Specifically, the high-temperature tail gas that combustion reaction is produced in air burning reactor of the present invention（Oxygen denuded air）By
Second cyclone separator enters the preheater thick combustion gas of preheating after separating dedusting, to reclaim heat.Part oxygen deprivation after heat recovery
Air can air inlet combustion reactor as needed, to adjust air burning coefficient of excess.
Specifically, the active component of the carrier of oxygen of the present invention can be Fe oxides, Cu oxides, Ni oxides, Ce
One or more in oxide, Mn oxides, Ca oxides etc., the inert component of the carrier of oxygen can be Al2O3、MgO、
One or more in ZrO etc..The present invention, as the carrier of oxygen, reduces operating cost using non-noble metal oxide.Preferably,
The content of the active component is 30-80wt%, and the content of the inert component is 20-70wt%.The particle diameter model of the carrier of oxygen
It is 0.1-5mm to enclose, and preferred particle size range is 0.15-2mm, and such as particle diameter is 0.18mm.
Compared with prior art, the invention has the advantages that：
（1）Tar macromolecule fraction is oxidized to CO, H at high temperature using the Lattice Oxygen of the carrier of oxygen2Taken off Deng small-molecule substance
Remove, while can partly retain and utilize the energy of tar again；
（2）Cycle set transmission oxygen, the heat-carrying of the carrier of oxygen and it is catalyzed in one, makes full use of the oxidation reaction heat of the carrier of oxygen and thick
Combustion gas sensible heat；
（3）The carrier of oxygen is by the circular regeneration between reforming reactor and air burning reactor and eliminates possible carbon distribution, oxygen
Carrier regeneration and elimination carbon distribution are simple, beneficial to the continuous operation of the system of maintenance；
（4）Using non-noble metal oxide as the carrier of oxygen, operating cost is reduced.
Below by embodiment, the present invention is described in detail.
Embodiment 1
It is illustrated as a example by removing the biomass downdraft thick gas tar oil of fixed bed air gasification.
From the thick Nm of combustion gas 10.0 of biomass downdraft fixed bed gasification3/ h, tar content is 2.35g/Nm3, temperature is
450 DEG C, enter reforming reactor after the first cyclone separator separates dedusting, preheater preheating and come from the second cyclonic separation
The high temperature carrier of oxygen of device（CuO-NiO/Al2O3, 6kg/h）Reaction, the carrier of oxygen is reduced, and the tar macromolecular in thick combustion gas is by portion
Oxidation, catalytic reforming is divided to be CO and H2Removing is converted Deng small-molecule substance, is obtained after the 3rd cyclone separator separates dedusting
The tar content for obtaining combustion gas is 0.07g/Nm3, the removal efficiency of tar is 97% in thick combustion gas；
The carrier of oxygen of reduction-state（Surface may have carbon distribution）Air inlet combustion reactor, controls the air of carrier of oxygen combustion reaction
Coefficient of excess is 0.95, and the reduction-state carrier of oxygen regains Lattice Oxygen by air complete oxidation, and area carbon is oxidized to CO2
And eliminate, the carrier of oxygen is recycled after separating dedusting through the second cyclone separator into reforming reactor after oxidation.
The reforming reactor temperature is 850 DEG C, pressure 0.1Mpa, and air burning temperature of reactor is 900 DEG C, pressure
0.1Mpa；The carrier of oxygen active component is CuO, NiO, and inert component is Al2O3, three's mass ratio is 2:2:1, the carrier of oxygen
0.15 ~ 0.84mm of particle size range.
The result of implementation of this method such as table 1 below：
Table 1, result of implementation
Embodiment 2
Removing biomass downdraft is fixed bed oxygen-enriched in this way（50v% oxygen）Gasify and be illustrated as a example by thick gas tar oil.
From biomass fixed-bed oxygen-enriched（50v% oxygen）Gasify the Nm of thick combustion gas 10.03/ h, tar content is 1.02g/
Nm3, temperature is 480 DEG C, enter after the first cyclone separator separates dedusting, preheater preheating reforming reactor with from the
The high temperature carrier of oxygen of two cyclone separators（Mn2O3-NiO/Al2O3, 5kg/h）Reaction, the carrier of oxygen is reduced, Jiao in thick combustion gas
Oily macromolecular is partially oxidized, catalytic reforming is CO and H2Removing is converted Deng small-molecule substance, by the 3rd cyclone separator
The tar content for obtaining combustion gas afterwards is 0.05g/Nm3, the removal efficiency of tar is 95% in thick combustion gas；
The carrier of oxygen of reduction-state（Surface may have carbon distribution）Air inlet combustion reactor, controls the air of carrier of oxygen combustion reaction
Coefficient of excess is 0.8, and the reduction-state carrier of oxygen regains Lattice Oxygen by air complete oxidation, and area carbon is oxidized to CO2
And eliminate, the carrier of oxygen is recycled after separating dedusting through the second cyclone separator into reforming reactor after oxidation.
The reforming reactor temperature is 900 DEG C, pressure 0.1Mpa, and combustion reactor temperature is 1000 DEG C, pressure
0.1Mpa；The carrier of oxygen active component is Mn2O3, NiO, inert component is Al2O3, three's mass ratio is 4:5:1, oxygen is carried
0.35 ~ 1.40mm of body particle size range.
The result of implementation of this method such as table 2 below：
Table 2, result of implementation
Embodiment 3
Remove in this way and be illustrated as a example by the thick gas tar oil of biomass fluid bed air gasification.
From the biomass fluid bed thick Nm of combustion gas 5.0 of gasification3/ h, tar content is 11.72g/Nm3, temperature is 520 DEG C,
Enter reforming reactor and the height from the second cyclone separator after the first cyclone separator separates dedusting, preheater preheating
The warm carrier of oxygen（Fe2O3-NiO/Al2O3, 5.4kg/h）Reaction, the carrier of oxygen is reduced, and the tar macromolecular in thick combustion gas is by part
Oxidation, catalytic reforming are CO and H2Removing is converted Deng small-molecule substance, is obtained after the 3rd cyclone separator separates dedusting
The tar content of combustion gas is 0.92g/Nm3, the removal efficiency of tar is 92% in thick combustion gas；
The carrier of oxygen of reduction-state（Surface may have carbon distribution）Air inlet combustion reactor, controls the air of carrier of oxygen combustion reaction
Coefficient of excess is 0.85, and the reduction-state carrier of oxygen regains Lattice Oxygen by air complete oxidation, and area carbon is oxidized to CO2
And eliminate, the carrier of oxygen is recycled after separating dedusting through the second cyclone separator into reforming reactor after oxidation.
The reforming reactor temperature is 880 DEG C, pressure 0.1Mpa, and combustion reactor temperature is 950 DEG C, pressure
0.1Mpa；The carrier of oxygen active component is Fe2O3, NiO, inert component is Al2O3, three's mass ratio is 4.5:4.5:1,
0.25 ~ 1.19mm of carrier of oxygen particle size range.
The result of implementation of this method such as table 3 below：
Table 3, result of implementation
In sum, the invention provides a kind of device and method of removing biomass gasification tar of being reformed based on chemical chain, this
Inventive method can without the circulation to the advance reduction of the carrier of oxygen, and by the carrier of oxygen between reforming reactor and combustion reactor
So that continuously carrier of oxygen Lattice Oxygen to be regenerated and carbon distribution is eliminated.In addition, the thick combustion gas of high temperature of fuel gas of gasifying furnace outlet can directly enter
Enter reforming reactor, while the sensible heat carried using the thick combustion gas of high temperature and the carrier of oxygen, there is provided the high temperature needed for partial oxidation reaction
Environment, improves efficiency of energy utilization.Additionally, the tar fraction in biomass rough gas is oxidized to using the Lattice Oxygen of the carrier of oxygen
CO、H2Removed Deng small-molecule substance, the energy of tar can be made full use of.The tar content of combustion gas is low after being removed through this method
In 1g/Nm3, tar removal efficiency is more than 90%.The inventive method is a kind of new method of efficient removal biomass gasification tar.
It should be appreciated that application of the invention is not limited to above-mentioned citing, and for those of ordinary skills, can
To be improved according to the above description or converted, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Shield scope.
Claims (10)
1. a kind of reformation based on chemical chain removes the device of biomass gasification tar, it is characterised in that including the use being sequentially connected
In the first cyclone separator, pre- for being carried out to the thick combustion gas of gasification of biomass for the thick combustion gas of gasification of biomass separate dedusting
The preheater of heat, the reforming reactor for the thick combustion gas of gasification of biomass after preheating and the carrier of oxygen to be carried out reforming reaction and use
The carrier of oxygen after by reforming reaction carries out the air burning reactor of combustion reaction with air, the air burning reactor with
The second cyclone separator for the carrier of oxygen after oxidized separate dedusting, the reformation are connected between reforming reactor
Reactor is also associated with the 3rd cyclone separator for reacted combustion gas separate dedusting.
2. the method that a kind of utilization device as claimed in claim 1 removes biomass gasification tar, it is characterised in that including as follows
Step：
After the thick combustion gas of step A, gasification of biomass separates dedusting and preheater preheating through the first cyclone separator, into reforming reaction
Reforming reaction is carried out in device with the carrier of oxygen, after reacted combustion gas separates dedusting through the 3rd cyclone separator, clean fuel gas is obtained；
Carrier of oxygen air inlet combustion reactor after step B, reforming reaction, combustion reaction, the carrier of oxygen are carried out with air
After being oxidized, recycled into the reforming reactor after then separating dedusting through the second cyclone separator.
3. the method according to claim 2, it is characterised in that combustion reaction is produced in the air burning reactor
Oxygen denuded air enters preheater and preheats thick combustion gas after separating dedusting through the second cyclone separator.
4. method according to claim 2, it is characterised in that in the step A, tar content and institute in the thick combustion gas
The Lattice Oxygen mass ratio for stating the carrier of oxygen in reforming reactor is 1:0.5-5.
5. the method according to claim 2, it is characterised in that in the step B, the air burning reactor is hollow
Gas burning coefficient of excess is 0.5-1.5.
6. method according to claim 2, it is characterised in that in the step A, the operation temperature of the reforming reactor
For 550-950 DEG C, operating pressure are 0.1MPa.
7. method according to claim 2, it is characterised in that the operation temperature of the air burning reactor is 850-
1050 DEG C, operating pressure be 0.1MPa.
8. method according to claim 2, it is characterised in that the active component of the carrier of oxygen is Fe oxides, Cu oxygen
One or more in compound, Ni oxides, Ce oxides, Mn oxides, Ca oxides, the inert component of the carrier of oxygen is
Al2O3, one or more in MgO, ZrO.
9. method according to claim 8, it is characterised in that the content of the active component is 30-80wt%, described lazy
Property component content be 20-70wt%.
10. the method according to claim 2, it is characterised in that the particle size range of the carrier of oxygen is 0.1-5mm.
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