CN110102227A - Biomass pyrolysis liquid fluidized bed reactor and its application - Google Patents
Biomass pyrolysis liquid fluidized bed reactor and its application Download PDFInfo
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- CN110102227A CN110102227A CN201910342938.4A CN201910342938A CN110102227A CN 110102227 A CN110102227 A CN 110102227A CN 201910342938 A CN201910342938 A CN 201910342938A CN 110102227 A CN110102227 A CN 110102227A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1872—Details of the fluidised bed reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
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- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses a kind of biomass pyrolysis liquid fluidized bed reactor and its applications.The reactor specifically includes that the cylinder-shaped pressure-bearing shell perpendicular to ground, the fluid distributor for being set to pressure-bearing shell bottom, the coaxial feed nozzle being set on fluid distributor and the three phase separator for being set to pressure-bearing shell top；Three phase separator consolidates the coaxial arrangement from top to bottom from outside to inside of cyclone separator and back taper baffle at equipped with a gas-liquid product mix outlet at the top of pressure-bearing shell by inner wall, the liquid on pressure-bearing shell top.Biomass pyrolysis liquid under the reactor is participated in for catalyst is to have the advantages that operating flexibility is big, catalyst inventory is high, space reactor utilization rate is high, reactor manufacturing cost is low in the hydrogenation deoxidation technical process of feedstock oil.
Description
Technical field
The present invention relates to a kind of fluidized bed reactor, in particular relate to a kind of biomass pyrolysis liquid fluidized bed reactor and its
Using.
Background technique
Existing Biomass-pyrolysis can be by low-grade biomass energy (such as stalk, timber, crop waste
Object) it is converted into the biomass thermal pyrolytic behavior of liquid.But biomass thermal pyrolytic behavior produced is highly corrosive, oxygen content is high,
Unstable, the characteristics of calorific value is lower, easy coking, can not achieve the purpose that substituting petroleum uses.Chinese invention patent
CN101831328 B discloses a kind of preparation method of green fuel oil, biomass pyrolysis liquid can be passed through a series of plus hydrogen
Deoxidation, the operation being hydrocracked obtain the green fuel oil of gasoline and diesel oil etc..Due to the easy coking of biomass pyrolysis liquid and biology
The volatile activity of matter pyrolytic behavior hydrogenation catalyst, traditional fixed bed and moving bed can not be applicable in since bed is easy to block.Cause
This, Chinese invention patent CN101831328 B, which is disclosed, can be used boiling for the hydrogenation deoxidation process of biomass pyrolysis liquid
Bed reactor.
For the boiling bed hydrogenation deoxidization technique process of biomass pyrolysis liquid, Chinese invention patent CN 103920430A is public
The fluidized bed reactor of a kind of pair of biomass coke tar (i.e. biomass pyrolysis liquid) hydrogenation deoxidation has been opened, it is easy for biomass pyrolysis liquid
Biomass char oil-in is set to the side wall of the reactor shell by the characteristic of coking, while being arranged in biomass char oil-in
Cooling water jacket is used for the cooling of biomass char oil-in；And to the catalyst separation problem of fluidized bed reactor outlet, it uses
The means that gas-liquid separator is arranged outside control catalyst bed expansion height and reactor realize three phase separation.Due to biomass
The molten Hydrogen Energy power of pyrolytic behavior is poor, performance of dissolving each other with the recycle oil in reactor is poor, leads to the biomass pyrolysis liquid into reactor
It is unable to rapid dispersion and catalytic hydrogenation reaction occurs, caused by easily causing reactor inlet local biologic matter pyrolytic behavior excessive concentration
Reactor inlet coking problem.Meanwhile using control catalyst bed expansion height, the separation hand of gravity settling separation catalyst
Section, due to the limitation of separating property, it has to which the space for sacrificing more inside reactors is used for the sedimentation of catalyst；More very
It is to cause system process too long using gas-liquid separation outside device and high-tension apparatus increase.Therefore, for biomass pyrolysis liquid
During boiling bed hydrogenation technique, it is badly in need of a kind of suitable boiling bed hydrogenation reactor technology.
Currently, the shape that industrialized boiling bed hydrogenation reactor technology can be fluidized according to catalyst in reactor both at home and abroad
State is divided into two kinds: (1) expanded bed state, i.e. gap between gas-liquid two-phase catalyst filling particle, so that catalyst bed is swollen
It is swollen to certain altitude, the interface of liquid-solid two-phase can be obviously observed on reaction bed top, with " H-Oil " and " LC-
Fining " technology and its deriving technology are representative；(2) another is catalyst complete mixing flow recurrent state, i.e., in gas-liquid two-phase
Under momentum transmitting, at the top of catalyst granules expansion reaction bed, there is no the interface of apparent liquid-solid two-phase in reaction bed, with
Middle petrochemical industry " STRONG " technology is representative.
To above two different ebullated bed state, so that the separator built in corresponding boiling bed hydrogenation reactor head
Structure is entirely different.Under expanded bed state, control catalyst bed is expanded to certain altitude, in the catalyst bed of expansion
Top is the gas-liquid mixture without solid；In fact, required for the top of the fluidized bed reactor of this expanded bed state
What is solved is the separation of gas-liquid two-phase.Under complete mixing flow state, the expansion height of catalyst bed is not controlled, catalyst can flow
Change to the charge level height of reactor, entire reaction bed is all gas-liquid-solid three-phase mixture, therefore required for reactor head
What is solved is the separation of gas-liquid-solid three-phase.
The boiling bed hydrogenation reactor technology of expanded bed state, either " H-Oil ", " LC-Fining " technology and its spread out
Raw technology, development are from United States Patent (USP) USRE.25, and 770；The subsequent United States Patent (USP) US 3,197 for improving patent such as HRI company,
The beauty of 4,971,678, the Acomo company of United States Patent (USP) US4,886,644 and US of 288 and US, 4,221,653, Texaco company
State patent US 4,911,893 and US 4,950,459A, the United States Patent (USP) US 7,449,155 of Shell company.United States Patent (USP)
USRE.25,770 and its above-mentioned subsequent improvement patent, the fluidized state of the reaction bed in disclosure is expanded bed shape
State, the technical solution for reactor head separation are by control loop oil stream amount, in active control fluidized bed reactor
Catalyst bed expansion height, in catalyst bed expansion height, the above are the decanting zones of catalyst granules to obtain without solid
The gas-liquid two-phase of particle realizes reaction in reactor head using circulation cup or the circulation cup equipped with gas-liquid cyclone separator
Gas-liquid separation, the clear liquid-phase product of extraction at the top of device is as recycle oil or product.Since the separation for catalyst is equal
It is realized by gravitational settling, therefore the operation of the selection and reactor for catalyst system has specific requirement: (1) is catalyzed
Agent size is larger, has preferable settling property, and such as United States Patent (USP) USRE.25,770 specifications the 1st arrange suggests in the 66th row
Catalyst size be " at least about 1/32 inch (i.e. 0.8mm) of average diameter, most common range be 1/16~1/4 inch (i.e.
1.6mm~6.35mm) "；Commercial plant is mostly diameter 1mm, the bar rope shape catalyst granules of length 2mm；(2) active control is catalyzed
Agent bed expansion height, such as United States Patent (USP) USRE.25,770 specification the 10th arranges in the claim 11 of the 18th row and discloses " institute
It states static bed and is expanded to few 10%, and be no more than 50%；So that the catalyst granules can be in bed upon inflation freely
Movement, and catalyst is not taken out of from catalyst bed "；United States Patent (USP) USRE.25,770 subsequent improvement patented technology, although urging
The expansion rate of agent bed can be improved, but must still control the expansion height of catalyst bed, be no more than 100%,
Reserve the space of catalyst sedimentation.Design involved in the isolation technics scheme of the fluidized bed reactor of above-mentioned expanded bed state is wanted
It asks, so that there are following technology limitations for external boiling bed hydrogenation reactor technology: (1) catalyst size is big, increases
Catalyst resistance to mass tranfer is big；(2) catalyst inventory is lower (be usually no more than reactor volume 50%), reduces reactor
Processing capacity；(3) sedimentation separation space is big, and it is low to reduce space reactor utilization rate；(4) the separation residence time is long, increases
Liquid-phase product stops the risk for causing secondary thermal cracking coking for a long time under non-catalytic hydroconversion condition.Therefore in processing oil product day
Under the current conditions of beneficial heaviness, in poor quality and the intensive unit scale benefit of more pursuit, the ebullated bed of expanded bed state is anti-
The technical limitation of device is answered to become increasingly conspicuous.In particular for the boiling bed hydrogenation deoxidation for the biomass pyrolysis liquid for being easy to coking, by
It is long in the separation residence time, reactor coking is easily caused, device can not long-term operation.
The boiling bed hydrogenation reactor technology of complete mixing flow state, the country are represented using middle petrochemical industry " STRONG " technology as representative
Property patent be Chinese invention patent CN1448212A.The isolation technics scheme of its reactor head are as follows: be arranged in reactor head
There is the three phase separator of three layers or multilayer concentric tube-in-tube structure form, realizes that catalyst is trapped in instead by the method that baffling settles
It answers in device, the purpose of reaction gas and liquid removal reactor.Since two concentric inner barrel and outer barrels are mounted on reactor enclosure
At the top of body, activity space of the catalyst in reactor is increased, so that there is reactor catalyst inventory height, reactor to utilize
The high advantage of rate.Then on the basis of Chinese invention patent CN1448212A, Chinese invention patent CN101376092 is disclosed
In the three phase separator lower end of concentric tube-in-tube structure form, setting cross sectional shape is trapezoidal or bowed guide frame, middle promulgated by the State Council
Bright patent CN101721961A discloses the increase diamond shape deflection cone internals below the three phase separator of concentric tube-in-tube structure form,
Chinese invention patent CN101618305 discloses a kind of in reactor head setting changeover portion and expanding reach, Chinese invention patent
CN101721960A is that inverted-cone shape and lower part are positive and set taper by the way that concentric inner barrel and outer barrel is designed as top, Lai Youhua
The separation condition of gravitational settling；Above-mentioned these sustained improvements to Chinese invention patent CN1448212A, still do not get rid of
The technical thought of state patent of invention CN1448212A, be all by inner cylinder implement gas abjection, then using inner barrel and outer barrel it
Between annular space channel and outer cylinder and reactor shell between annular space channel to dehydrogenation catalyst slurry implement gravitational settling from
And realize the separation of catalyst and oil product.Therefore, the cross-sectional area design in these annular space channels must satisfy in annular space channel
Liquid linear velocity is less than the sinking speed of catalyst granules, can be only achieved the effect of gravitational settling.From the operation of catalyst fluidization
Condition considers, it is desirable that the liquid linear velocity on the cross section of reactor has to be larger than the sinking speed of particle.It is described concentric
Inner barrel and outer barrel is installed in reactor inner top, and the annular space aisle spare formed with reactor shell three is also centainly less than
The cross-sectional area of reactor；Therefore, even if the catalyst pulp into annular space channel has contained seldom or without gas, ring
Liquid linear velocity in gap channel still can keep higher speed.Even if using the mistake of Chinese invention patent CN101618305
The design for crossing section and expanding reach, as Chinese invention patent CN101618305 claim 1 disclosure " expanding reach it is straight
Diameter is 1.2~2 times of reactor direct tube section ", i.e., using the expanding reach design of 2 times of direct tube section diameters, baffling sedimentation obtained
Area of section be 1.5 times of direct tube section, that is, the liquid phase linear velocity in expanding reach is reduced to direct tube section liquid linear speed
The 66% of degree, only relies on gravitational settling, and the separating property of three phase separator is limited.Separator is also resulted in this way
Operating flexibility it is smaller, and the separating property of separator also determines the operation domain range of fluidized bed reactor, i.e. ebullated bed is anti-
Answer the operating flexibility of device also smaller.It is especially worth noting that, in order to balance complete mixing flow state and sedimentation separation, generally in this way
Boiling bed hydrogenation reactor generally use the lesser catalyst of the size (embodiment 1 of such as Chinese invention patent CN1448212A
Described in use 0.1~0.2 millimeter of microspherical catalyst) and lesser operation gas-liquid it is fast.The lesser catalyst granules tool of size
There is preferable fluidizing performance, often only just realizes that complete mixing flow operates under the action of feedstock oil；But the lesser catalyst of size
Interference (or free) sinking speed of particle is also smaller；Need to control the linear velocity of liquid in reactor in lower level,
Be able to satisfy in three phase separator for baffling sedimentation annular space in liquid linear velocity be less than catalyst granules interference (or from
By) sinking speed, realize separation；Therefore, this boiling bed hydrogenation reactor is often not provided with additional recycle oil；If using
Recycle oil technique, then the working ability of reactor will decline to a great extent.But biomass pyrolysis liquid is due to easy coking, molten Hydrogen Energy power
The characteristic of difference, hydrogenation process could be completed by needing to be diluted it using the recycle oil of large scale, this is that this ebullated bed is anti-
Answer device that can not operate.
101376092 B of Chinese invention patent CN 10172196 B and CN is also to continue Chinese invention patent
The baffling of CN1448212A settles thinking；107297186 B of Chinese invention patent CN is related to a kind of three phase separator structure,
It will be by the object in baffling sedimentation type three phase separator on the basis of 101376092 B of Chinese invention patent CN 10172196B and CN
Flow separation flow direction is changed to three-phase logistics and rises degassing from the outermost layer channel of baffling sedimentation type three phase separator, after degassing
The middle layer that two-phase logistics is deflected into baffling sedimentation type three phase separator carries out the gravitational settling under bubble-free disturbed condition, most
Clear liquid phase stream enters the central core discharge reactor of baffling sedimentation type three phase separator afterwards；In Chinese invention patent CN
As it can be seen that the oxidation for being directed to 0.7~0.8mm using the three phase separator in the patent in the comparative example of 107297186 B
Al catalysts, under the conditions of identical operating gas velocity and liquid speed, the drag-out of catalyst is compared with CN 10172196 B and CN
101376092 B raising merely reduces 0.2~0.4 μ g/g, and separating effect is slightly good, but operating flexibility range is almost the same.In
108144555 A of state patent of invention CN is related to a kind of three phase separator, in the technical foundation of 107297186 B of CN, anti-
It answers device outlet to be provided with suction tube, cooperates the eddy flow guide plate being arranged in the central core of baffling decanter type three phase separator, play
Vacuum flashing and the effect for preventing liquid from being carried secretly by gas.
Compare fluidized bed reactor technology both domestic and external, it can be seen that domestic " STRONG " technology is that the ebullated bed of representative is anti-
The use for answering device to operate by small particle catalyst and complete mixing flow, overcoming foreign countries with " H-Oil " and " LC-Fining " technology is
The technology limitation of the fluidized bed reactor of " expanded bed " state represented, that is, realize: (1) reactor uses the catalyst of small particle
Particle, reactor resistance to mass tranfer are small；(2) reactor bed is gas-liquid-solid three-phase, and catalyst inventory is high, space reactor utilizes
Rate is high.But for the three phase separation at the top of fluidized bed reactor, technical solution both domestic and external is by gravitational settling
Mode is implemented, and liquid phase is under non-catalytic hydroconversion condition after the big, separation that causes that three phase separating efficiency is low, three phase separator takes up space
The common problem of residence time length.The common problem of domestic and international fluidized bed reactor, so that existing boiling bed hydrogenation is anti-at present
Device technology is answered not to be available in the hydrogenation deoxidation process of the biomass pyrolysis liquid for easy coking.
In petroleum catalytic cracking field, the catalytic cracking of the gas-particle two-phase reaction of 20~100 μm of molecular sieve catalysts is used
In reactor, often reactor is built-in with single-stage or multistage gas-solid cyclone separator, constitutes the outlet gas-solid seperator of reactor
Structure, to carry out the operation of Removal of catalyst particle, such as 101935043 B of Chinese invention CN to outlet gas-phase product, still
Gas-solid cyclone separator used often has very long underflow pipe structure or flutter valve structure, may not apply to gas-liquid-solid completely
Gas-liquid-solid three-phase separates in the fluidized bed reactor of phase reaction.Also technical staff attempts in ebullating bed reactor using level-one
Or multistage cyclone separator separating catalyst, in 103769014 A of Chinese invention CN 103773490 A and CN, reactor head
The reactant collected after cyclone separator isolates most catalyst granules, but it is useless both to have cannot achieve three phase separation
It cannot achieve the limited removing of catalyst again, it is necessary to which reactor outlet is provided with the multistage baffle that is provided with of special designing
It is further separated in high-pressure separator, catalyst is continuously carried out reactor and accumulates in high-pressure separator, causes device
It is unable to operate normally.105363392 B of Chinese invention patent CN is to be provided with point ebullated bed of chamber decanter type three phase separator anti-
The surge tank that spinning liquid structure is provided with after the liquid outlet of device is answered, to due to dividing chamber decanter type three phase separator separating capacity not
Catalyst entrainment implements secondary solid-liquor separation caused by foot, but the circulation of circulation type fluidized bed reactor must be cooperated to aspirate
It is just able to satisfy application under the collective effect of effect and the effect of longer liquid leg, therefore such rotary filter press structure can be only installed at
Outside reactor.The U.S. US 3,668,116 of Esso company can only also be provided with liquid outside slurry bed system (ebullated bed) reactor device
Phase cyclone separator, the entrance of the cyclone separator are submerged in the charge level of reactor or less, more than catalyst bed expansion height
Position；Gaseous products in reactor directly have the top discharge of reactor to go to recycle hydrogen system, and liquid-phase product is by outer
The liquid phase of the separation for the liquid phase cyclone separator set, acquisition goes to high-pressure separator.Eddy flow knot is also explored by HRI and Texaco company
Structure replaces the funnel in circulation cup structure in the circulation cup structure of the fluidized bed reactor of expanded bed type using cyclone structure
Shape structure, if United States Patent (USP) US 4,354,852 is related to a kind of fluidized bed reactor, using single cylindrical gas-liquid cyclonic separation
Device replaces funnel shaped circulation cup structure, the gas-liquid separation process strengthened by centrifugal force.Cyclone separator it is multiple tangential
Entrance is located at the upper edge of freeboard region, i.e. supernatant liquid and gas phase enters whirlwind by the tangential inlet of cyclone separator jointly
Separator.In cyclone separator, the resulting liquid phase of centrifugal force separate is directly gone to circulation by cyclone underflow mouth and is pumped into
Mouthful；And purified gas phase is expelled directly out reactor by the overflow port of cyclone separator as the gaseous products of reactor.The U.S.
Patent US 4,810,359 is related to a kind of fluidized bed reactor, also replaces circulation cup structure, cyclonic separation using cyclone separator
Device entrance is located at catalyst expansion height or more, is deaerated using cyclone separator to recycle oil, optimizes circulating pump
Entrance condition.
In conclusion the hydrogenation deoxidation process of the biomass pyrolysis liquid for easy coking, it would be highly desirable to which developing one kind can mix entirely
Stream operation realizes that three phase separation, three phase separation be space-minimized, the maximized fluidized bed reactor of reaction compartment in reactor.
Summary of the invention
In order to overcome, easy coking of the existing technology, three phase separation space is big, operating flexibility is small and reactor utilization rate
Low technical problem, the present invention provides a kind of biomass pyrolysis liquid fluidized bed reactors.
Biomass pyrolysis liquid fluidized bed reactor provided by the invention specifically includes that the cylinder-shaped pressure-bearing perpendicular to ground
Shell, the fluid distributor for being set to pressure-bearing shell bottom, coaxial feed nozzle and the setting being set on fluid distributor
Three phase separator in pressure-bearing shell top；Three phase separator by inner wall, the liquid on pressure-bearing shell top consolidate cyclone separator and
The coaxial arrangement from top to bottom from outside to inside of back taper baffle is at pressure-bearing shell top is equipped with a gas-liquid product mix and goes out
Mouthful.
The liquid consolidate cyclone separator from top to bottom successively by gas-liquid mix outlet pipe, overflow pipe, shell of column, impeller guide structure,
Cone section, downspout and non-return cone are coaxially disposed；Overflow pipe is placed on gas-liquid and mixes outlet pipe periphery, and shell of column is placed on overflow pipe periphery；
Shell of column, cone section and downspout are from top to bottom sequentially connected, and impeller guide structure is set on shell of column inner wall, and non-return cone is set to downspout
Lower section.
The gas-liquid is mixed outlet pipe lower end and is suspended in overflow pipe, and upper end consolidates the gas-liquid mixed phase outlet of cyclone separator as liquid
It is connected with the gas-liquid product mix outlet at the top of pressure-bearing shell.
The expanding circle in the top that the pressure-bearing shell is isometrical cylindrical vessel or upper diameter is 1~2 times of lower diameter
Drum ladle.
The shell of column is cylindrical tube, and the cone section is inverted conical shape cylinder.
The back taper baffle is the baffle of single layer, two or more layers covering.
The impeller guide structure is made of or the multiple swirl vanes being set on shell of column inner wall by processing on shell of column inner wall
The helical duct, two helical ducts or multiple helical ducts in internal screw thread shape out is constituted.
The axis of the cyclone separator is overlapped with the axis of pressure-bearing shell, and shell of column diameter is the 10 of pressure-bearing shell diameter
~90%, shell of column height is the 2.5~10% of pressure-bearing shell tangent line height.
The axis of the cone section is overlapped with the axis of shell of column, and the angle in cone section bus same level face is 20~80 °, preferably 20
~60 °, or further preferably 20~40 °.
The non-return cone is spindle-type α-Fe2O3, and top cone angle is 15~150 °, and lower part cone angle is greater than top cone angle.
The bottom of the pressure-bearing shell is provided with the mixed phase entrance or two for recycle oil and hydrogen mixed feeding
A or multiple entrances respectively individually fed for recycle oil and hydrogen, the top position in pressure-bearing shell bottom is equipped with for being catalyzed
The catalyst outlet of agent discharge；The catalyst that one is added for catalyst is additionally provided at the top of the pressure-bearing shell to be added
Mouthful.
The structure of the fluid distributor can selected from Johnson screen mesh type distributor or bubblecaps or
Multi-nozzle distributor structure.
The coaxial feed nozzle is set to the side of the pressure-bearing shell, by an outer tube being arranged concentrically and one
Pipe is constituted, and an annular space is formed between inner and outer tubes, and inner tube is used for the charging of feedstock oil, and the annular space between outer tube and inner tube is used for
The charging of hydrogen supply agent；Coaxial feed nozzle sprays mouth down, and axis same level face angle is 0~45 °, and ejiction opening is located at fluid
More than the upper surface of distributor 200~1000mm.
The present invention also provides a kind of applications of biomass pyrolysis liquid fluidized bed reactor, it is characterised in that the reactor
Biomass pyrolysis liquid under participating in for catalyst is in the hydrogenation deoxidation technical process of feedstock oil, and the biology pyrolytic behavior is each
Kind biomass is by fast pyrolysis, at a slow speed thermal cracking, hydrogenation liquefaction, gasification or the charing obtained liquid of thermal cracking processes.
The operation temperature of the hydrogenation deoxidation technical process is 250~500 DEG C, and operating pressure is 4~20Mpa, reaction weight
When air speed be 0.1~4h-1。
The static bed height of catalyst loaded in the biomass pyrolysis liquid fluidized bed reactor accounts for the fluid distrbution
To 10~85% of the height between the lower end surface of the downspout, catalyst granules is expanded to described after fluidizing for the upper surface of device
Liquid level in biomass pyrolysis liquid fluidized bed reactor.
The particle of the catalyst is to have supported in the periodic table of elements from IIIB race to Group IIB transition metal element and it
Between the silica of alloy that is formed or porous carbon or make carrier metal oxide spheric granules, particle diameter
For 0.2~2mm.
Alternatively, the particle of the catalyst is to have supported in the periodic table of elements from IIIB race to Group IIB transition metal member
Element and the silica of alloy formed between them or porous carbon or make carrier metal oxide bar rope shape particle,
Particle diameter is 0.2~2mm, and draw ratio is 1~10.
Further, a part of conduct of the liquid-phase product after the biomass pyrolysis liquid fluidized bed reactor hydrogenation deoxidation
Recycle oil is entered after heating by biomass pyrolysis liquid fluidized bed reactor bottom with high pressure hydrogen Hybrid Heating or individually；Into
The recycle oil and hydrogen entered in reactor flows up after the fluid distributor is uniformly distributed, reaches static catalyst bed
Fluidized state；Feedstock oil and hydrogen supply agent enter the biomass pyrolysis liquid fluidized bed reactor by the coaxial feed nozzle；Quilt
Recycle oil and the catalyst bed of hydrogen fluidisation are mixed with feedstock oil and hydrogen supply agent, formed containing hydrogen, recycle oil, feedstock oil,
The gas-liquid-solid three-phase mixture of hydrogen supply agent, catalyst granules occurs to react the hydrogenation deoxidation of feedstock oil；The gas-liquid-solid three-phase is mixed
Object is closed after three phase separator separation, gas phase and liquid-phase product are mixed by the gas-liquid product that the top of pressure-bearing shell is arranged
Close outlet discharge.
Further, the weight percent of the total amount and feedstock oil of the recycle oil and hydrogen supply agent is 0.5~10.
Further, the mode that two-stage fluidized bed reactor is used in series, the liquid phase of first order fluidized bed reactor can be used
Product goes to second level fluidized bed reactor and continues to add hydrogen.
Further, the mode that two-stage fluidized bed reactor is used in series, the liquid phase of first order fluidized bed reactor can be used
Product goes to second level fluidized bed reactor after heating stove heating and continues to add hydrogen.
During cyclonic separation, the centrifugal force that centrifugal force field applies the dispersed phase in continuous fluid is far longer than dispersed phase
Suffered gravity；Dispersed phase only needs radially to migrate in cyclone separator to cyclone separator side wall simultaneously,
Therefore separating rate, separation accuracy, the separative efficiency of cyclone separator are significantly larger than gravitational settling means, and the volume of equipment
Far smaller than gravitational settling equipment.Inventor is studied for a long period of time based on recycling ebullated bed and cyclone separator to complete mixing flow, in conjunction with
Cyclone separators are coupled by the two characteristic with complete mixing flow circulation ebullated bed.Utilize the same liquid phase of gas phase, the density variation of solid phase
It is larger, fast eliminating at the top of ebullated bed can be recycled in complete mixing flow, form liquid-solid two-phase mixture, consolidate cyclonic separation in conjunction with liquid
Device implements solid-liquor separation, just can be quickly obtained clean liquid-phase product and simultaneously retain catalyst in the reactor.In ebullated bed
There are a macroscopic views to circulate for liquid phase and solid phase in reactor, i.e., is the speed risen from fluidized bed reactor center, anti-
The side wall for answering device is the speed declined.It is arranged on the central axes of reactor by cyclone separator, is retained from cyclone separator
The catalyst to get off is just mixed with rising logistics in reactor, in the conversion zone of Returning reactor so that urging in reactor
Agent concentration is more uniform.
The present invention has the advantages that
(1) three phase separator is designed based on the gradient combination of inertial separation, cyclone de-solid, and operating flexibility is big and separation accuracy
Height, so that the fluidized bed reactor of complete mixing flow operation is corresponding with operating flexibility is big, catalyst inventory is high, space reactor is sharp
With the advantage that rate is high, reactor manufacturing cost is low.
(2) three phase separator makes full use of the fireballing advantage of cyclonic separation, so that the separation of gas-liquid-solid three-phase mixture
Residence time substantially shortens, and avoids long-time stop of the liquid phase under non-catalytic hydroconversion condition and causes reactor coking.
(3) three phase separator is built in the fluidized bed reactor of complete mixing flow operation, and reactor later separation process is substantially
Shorten, device high-tension apparatus is reduced, and device intrinsic safety is increased.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of fluidized bed reactor of the invention；
Fig. 2 is a kind of structural schematic diagram of coaxial feed nozzle of the invention；
Fig. 3 is a kind of structural schematic diagram of three phase separator of the invention；
Fig. 4 is another structural schematic diagram of fluidized bed reactor of the invention；
Fig. 5 is the process flow diagram using the cold work die of fluidized bed reactor of the invention；
Fig. 6 is the process flow signal using the 200L/h stalk pyrolytic behavior hydrogenation deoxidation of fluidized bed reactor of the invention
Figure；
Fig. 7 is the process flow signal using the 100L/h sawdust pyrolytic behavior hydrogenation deoxidation of fluidized bed reactor of the invention
Figure.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing.
As shown in Figure 1, biomass pyrolysis liquid fluidized bed reactor includes: perpendicular to the pressure-bearing shell 1 on ground, gas-liquid fluid
Distributor 2, coaxial feed nozzle 3 and three phase separator 4；The bottom of the pressure-bearing shell 1 be provided with one for recycle oil and
The mixed phase entrance 5 of hydrogen mixed feeding and one are provided with a gas-liquid for the catalyst outlet 6 of catalyst discharge, top
Mouth 8 is added in product mix outlet 7 and a catalyst being added for catalyst；The fluid distributor 2 is set to pressure-bearing shell
The lower part of body 1, for the recycle oil and hydrogen that are entered by the mixed phase entrance to be uniformly distributed in reactor cross-section and
Catalyst granules required for carrying is reacted；Pressure-bearing shell 1 of the coaxial feed nozzle 3 of eddy flow bed course in fluidized bed reactor
Installation site be higher than fluid distributor 2 upper surface；In preferred scheme, coaxial feed nozzle 3 is in fluidized bed reactor
Entrance on pressure-bearing shell is higher than 200~1000mm of upper surface of gas-liquid distributor；The ejiction opening position of the coaxial feed nozzle 3
More than the upper surface of the fluid distributor；The three phase separator 4 is set to the top of pressure-bearing shell.
The coaxial feed nozzle 3 is as shown in Fig. 2, include an outer tube 9 being arranged concentrically and inner tube 10, a biomass
Pyrolytic behavior (feedstock oil) entrance 11 and hydrogen supply agent entrance 12 are constituted；Said inner tube 10 is used for the charging of feedstock oil, 9 He of outer tube
The annular space formed between inner tube 10 is used for the charging of hydrogen supply agent.
The three phase separator 4 is as shown in figure 3, by cyclone separator 14, back taper baffle 13 and with the cyclonic separation
The inner wall that device is in the pressure-bearing shell 1 of same level height is constituted；The cyclone separators are by shell of column 15, cone section 16, rotation
It flows guide ring 17, downspout 18, non-return cone 19, overflow pipe 20 and gas-liquid and mixes the composition of outlet pipe 21；
A kind of preferred biomass pyrolysis liquid fluidized bed reactor of the present invention of Fig. 1, Fig. 2 and Fig. 3 description, can be according to it
Its inner space is divided into three functional spaces by operating function, comprising:
(1) fluid distrbution space: the space in the pressure-bearing shell 1 below of the lower end surface of fluid distributor 2 is used for recycle oil
Mixing with hydrogen and uniformly distributed；
(2) reactive agent space: more than the upper surface of fluid distributor 2 until the small end of the cone section 16 of cyclone separator 14
Level height between pressure-bearing shell 1 in space (not comprising space occupied by downspout 18), for providing gas-liquid-solid
The place of the generation hydrogenation reaction of three-phase mixture；
(3) three phase separation space: more than the level height of the small end of the cone section 16 of cyclone separator 14 until pressure-bearing shell 1
The space at top, it is therein for implementing " inertia point to the gas-liquid-solid three-phase mixture moved upwards by " reactive agent space "
From ", " cyclone de-solid ", " eddy flow degassing ", obtain clarification liquid-phase product and gaseous products.
A kind of operation of preferred biomass pyrolysis liquid fluidized bed reactor of the present invention described in Fig. 1, Fig. 2 and Fig. 3
Process is as follows: recycle oil and hydrogen enter fluidized bed reactor by the mixed phase entrance of 1 bottom of pressure-bearing shell of fluidized bed reactor；
It is sufficiently mixed in " fluid distrbution space " interior recycle oil and hydrogen, and the fluid distributor 2 by pressure-bearing shell lower part is arranged in
Be evenly distributed with so that the two-phase mixture of recycle oil and hydrogen is uniformly upwardly into " reactive agent on the cross section of pressure-bearing shell 1
Space ".Other than the uniform fluid distribution effect of two-phase mixture of the fluid distributor 2 in addition to realizing recycle oil and hydrogen, carrying is also acted as
The effect of catalyst granules；The structure of the fluid distributor 2 can be selected from Johnson screen mesh type distributor, bubble-cap type point
Cloth device, multi-nozzle distributor structure.The two-phase mixture of recycle oil and hydrogen passes through fluid distributor 2 in " reactive agent space "
The pore channel of the catalyst bed of upper carrying moves upwards, and acts in the momentum transmitting of recycle oil and hydrogen two-phase mixture
Under, the catalyst granules accumulated on fluid distributor 2 is fluidized and is in free movement state.Biomass pyrolysis liquid and hydrogen supply agent
Ebullated bed is introduced by the annular space that the inner tube 10 and outer tube 9 of the coaxial feed nozzle 3 on the side wall of fluidized bed reactor are formed respectively
Reactor；Hydrogen supply agent plays heat-insulated effect during biomass pyrolysis liquid is fed, and biomass pyrolysis liquid is avoided to connect
Before catalyst, hydrogen in touching reactor, reach 90 DEG C or more；Meanwhile hydrogen supply agent enters ebullated bed in biomass pyrolysis liquid
Play the role of dissolving hydrogen after reactor, biomass pyrolysis liquid is promoted to dissolve each other with recycle oil, so that biomass pyrolysis liquid is anti-
It answers in device and quickly spreads and participate in hydrogenation reaction, avoid the localized rich due to biomass pyrolysis liquid in reactor inlet and spend
It is high and not up to reaction condition and the problem of pyrolysis coking occurs.Biomass pyrolysis liquid and hydrogen supply agent enter ebullated bed together
After reactor, flow direction perpendicular to fluidized bed reactor axis, therewith with along the upward recycle oil of fluidized bed reactor axis,
Hydrogen, catalyst contact mixing, it is mixed to form biomass pyrolysis liquid, hydrogen supply agent, recycle oil, hydrogen, the gas-liquid-solid three-phase of catalyst
Object is closed, and hydrogenation deoxidation reaction occurs in " the reactive agent space " of reactor.Under the guiding role of non-return cone 19, reacting
The gas-liquid-solid three-phase mixture moved upwards in " the reactive agent space " of device around downspout catalyst outlet continue to
On be moved into " inertial separation space ", until " inertial separation " (or referred to as momentum separate) occurs after striking cone section 16,
Here it is " first order separation " that the gas-liquid-solid three-phase mixture after 4 pairs of the three phase separator reactions is implemented.Inertial separation
In the process, minute bubbles stick together, gather simultaneously, become air pocket and quickly upward in " inertial separation space ", arrival reactor
In charge level position, and deviate from charge level position enter reactor head " gas-phase space " continue sedimentation separation, finally obtain gas
Phase product is stored in " gas-phase space "；And catalyst solid particle bores section 16 striking inertia baffle 13 as rigid body particle
It rebounds afterwards, the direction of motion becomes moving downward (direction of momentum from becoming downward upwards) from moving upwards；Due to catalysis
The momentum of agent particle is greater than gas and liquid (density that the density of catalyst granules is greater than gas and liquid), in collision process,
In addition to the loss of mechanical energy, the momentum of the rebound of acquisition is also larger, promotes catalyst granules along wall of reactor descending motion.
The three-phase mixture entrance that most gas and partial catalyst granules are stripped of in " inertial separation " procedure is retouched
The liquid stated consolidates cyclone separator 14, implements cyclonic separation.Isolated catalyst granules warp in cyclonic separation separation process
The concentration for crossing cone section 16, by the discharge of downspout 18, " the reactive agent region " of Returning reactor；The clarification that cyclonic separation obtains
Liquid via the gaseous products in overflow pipe 16, with " gas-phase space " simultaneously pass through gas-liquid mix outlet pipe 21 gas-liquid mixed phase outlet and
Gas-liquid product mix outlet discharge reactor at the top of pressure-bearing shell, gas-liquid mix the lower end surface of outlet pipe 21 with the material in overflow pipe 16
Face is located at sustained height.
Another preferred biomass pyrolysis liquid fluidized bed reactor of the invention, as shown in figure 4, pressure-bearing shell can be used
1 is the expanding cylindrical vessel in top that upper diameter is 1~2 times of lower diameter.
Take United States Patent (USP) US 25,770 as the boiling bed hydrogenation reactor technology of technology source, generally requires anti-by controlling
The circulation oil flow rate in device is answered, realizes to the control of the expansion height of catalyst in reactor bed, generally requires catalyst bed
Layer expansion 10%~200% is the particle gravity settling separation slot milling of reactor head；Ebullating bed reactor in the present invention
Device, the expansion height for the catalyst bed being fluidized have reached the charge level position (gas-liquid two-phase i.e. in reactor in reactor
Interface), it is not necessary to control catalyst bed expansion height.
Inside a kind of preferred biomass pyrolysis liquid fluidized bed reactor of the present invention described in Fig. 1, Fig. 2 and Fig. 3
The macroscopic view flowing mark sheet of catalyst granules is existing are as follows: moves upwards from reactor center bottom, " inertial separation is empty described in arrival
Between ", a part of catalyst granules declines along the inner wall of reactor arrives at reactor bottom, close to full response on one scale of shape
Systemic circulation flowing on device, position close to the catalyst granules of reactor side wall in the axial direction；Another part catalyst exists
It is continued up in " inertial separation space ", arrives at the charge level position height (interface of gas-liquid two-phase) in reactor, then lead to
Cross cyclone separator 14 through downspout 18 return " reactive agent space ", formed one up to reactor charge level, down toward non-return cone
19, the systemic circulation flowing positioned at the catalyst granules of reactor center in the axial direction；This is in traditional fluidized bed reactor
Catalyst only has a systemic circulation flowing basis along reactor center rising, on the axial direction of reactor side wall decline
On, the systemic circulation flowing on an axial direction is increased, so that catalyst " axial mixed flow " enhances in fluidized bed reactor.Together
Sample, the present invention in biomass pyrolysis liquid fluidized bed reactor in liquid phase macroscopic view flow characteristics with catalyst granules macroscopic flow
Dynamic feature is almost the same, and difference is that there is also one liquid phases as liquid-phase product extraction reactor.Due to catalyst granules and
The enhancing of " the axial mixed flow " of liquid phase in the reactor, so as to reaction stream (including catalyst, recycle oil, biomass pyrolytic
Liquid, hydrogen supply agent, liquid-phase product, gaseous products) concentration distribution in the reactor is more uniform, reaction depth is more uniform, anti-
Answer temperature more uniform.
Embodiment 1
The biomass pyrolysis liquid fluidized bed reactor of the invention that FIG. 1 to FIG. 3 describes is used for 5000L/h ebullating bed reactor
The process flow diagram of device cold model unit is as shown in Figure 5.
1, process flow
For tap water from sink b, tap water is anti-by ebullated bed after circulating pump c is pressurized and (is higher than reactor pressure)
The mixed phase entrance of the bottom of device a is answered to enter reactor；Air in atmosphere is stored in air accumulator e after air compressor machine d pressurization,
Air is exported by air accumulator e enters reactor by the mixed phase entrance of the bottom of fluidized bed reactor a.In the dynamic of originally water and air
It measures under transmitting effect, the catalyst granules in fluidized bed reactor a reaches fluidized state.In fluidisation in fluidized bed reactor
Three phase separator separation of the gas-liquid-solid three-phase mixture of state Jing Guo reactor head, the gas phase of acquisition is the same as the liquid phase one obtained
Play the gas-liquid products export discharge for mixing outlet pipe by fluidized bed reactor through gas-liquid.The gas-liquid two-phase liquid phase of fluidized bed reactor discharge
It is back in sink b, gas phase emission is into atmosphere.
2, fluidized bed reactor structural dimensions
Fluidized bed reactor structural dimensions are shown in Table 1, and relative dimensions signal and appended drawing reference are shown in Fig. 3.
1 5000L/h fluidized bed reactor cold model unit structure size of table
3, implementation result
The test process of 5000L/h boiling bed hydrogenation cold model unit uses originally water and air and is tested, and tests
As a result such as table 2.In terms of test result, catalyst reaches even fluidizing, and continuous operation 20 hours without failure, 0.5mm catalysis
Agent drag-out is controlled less than 2.5 μ g/g.
2 5000L/h boiling bed hydrogenation cold model unit test result of table
Embodiment 2
The biomass pyrolysis liquid fluidized bed reactor of the invention that FIG. 1 to FIG. 3 describes is used for 200L/h stalk pyrolytic behavior
The process flow diagram of hydrogenation deoxidation device is as shown in Figure 6.
1, process flow
Feedstock oil and hydrogen supply agent enter reactor by the coaxial feed nozzle of the side of fluidized bed reactor a, wherein raw material
Oil is stalk pyrolytic behavior.The control range of the feeding temperature of feedstock oil and hydrogen supply agent is room temperature~45 DEG C, general control hydrogen supply agent
Mass ratio with feedstock oil is 0.25~2:1.The hydrogen supply agent may come from the boiling bed hydrogenation deoxidation product of feedstock oil
The diesel oil obtained by fractionation the perhaps diesel oil or wax oil fraction of wax oil distillate or the high arene content outside device
Oil.From the oil of cold high pressure separator g, mutually outlet g-1, recycle oil are pressurized to 8~20Mpa through circulating pump c and (are higher than recycle oil
Reactor pressure) after, same to hydrogen (including the recycle hydrogen from circulating hydrogen compressor and the new hydrogen from device for producing hydrogen) mixing；
After the heated furnace b of the mixture of recycle oil and hydrogen is heated to 200~450 DEG C, entered by the mixed phase of the bottom of fluidized bed reactor a
Mouth enters reactor.Under the momentum transmitting effect of recycle oil and hydrogen, the catalyst granules in fluidized bed reactor a reaches stream
Change state.Catalytic hydrodeoxygenation reaction occurs in fluidized bed reactor for feedstock oil, and the oxygen atom in feedstock oil is with water (H2O) and
Carbon dioxide (CO2) form removing, it obtains using alkane, aromatic hydrocarbons as the oil product of main component.It completes to add in fluidized bed reactor
Three phase separator separation of the gas-liquid-solid three-phase mixture Jing Guo reactor head after hydrogen deoxygenation, the gaseous products packet of acquisition
It includes dissolution that the components such as reactor remaining hydrogen, carbon dioxide, vapor, the lighter hydrocarbons that reaction generates, which are included, with the liquid-phase product obtained
The alkane and aromatic component of hydrogen mix outlet pipe through gas-liquid together and are discharged by the gas-liquid products export of fluidized bed reactor.Ebullated bed is anti-
The gas-liquid two-phase product for answering device to be discharged goes to high-pressure air cooler by high pressure hot separator d flash liberation, the hot high score gas of acquisition
f；Hot high score gas carries out de- liquid after high-pressure air cooler f is cooled to 40~50 DEG C, into cold high pressure separator g, is free of
The cold high score gas of drop；Cold high score gas passes through the separating-purifying of membrane separator i, obtains the higher circulating hydrogen of hydrogen purity, follows
Ring hydrogen mixes after air compressor machine j pressurization with new hydrogen.The separation of the bottom cold high pressure separator g obtains oil and mutually arranges with water phase, water phase
Device out, for a part of oily phase as recycle oil Returning reactor, another part of oily phase goes to cold low separator h.From heat
High score obtains hot high score oil and goes to thermal low-pressure separators e.It is separated through thermal low-pressure separators e, the hot low point of gas of acquisition is gone to cold low
Separator h is pressed, the heat low oil of acquisition goes to fractionating device.In cold low separator h, the cold low point of gas for separating acquisition is gone to
It torch or is used as fuel gas, the cold low oil of acquisition goes to fractionating device.
2, fluidized bed reactor structural dimensions
Fluidized bed reactor structural dimensions are shown in Table 3, and relative dimensions signal and appended drawing reference are shown in Fig. 3.
3 200L/h stalk pyrolytic behavior hydrogenation deoxidation device fluidized bed reactor structure size of table
3, implementation result
The test process of 200L/h stalk pyrolytic behavior hydrogenation deoxidation device uses stalk pyrolytic behavior and is tested, and tests
As a result such as subordinate list 4.In terms of test result, catalyst reaches even fluidizing, does not occur reactor coking within continuous operation 2000 hours,
0.5mm catalyst taking-out amount is controlled less than 2.5 μ g/g.
4 200L/h stalk pyrolytic behavior hydrogenation deoxidation device experiment result of table
Embodiment 3
The biomass pyrolysis liquid fluidized bed reactor of the invention that FIG. 1 to FIG. 3 describes is used for 100L/h sawdust pyrolytic behavior
The process flow diagram of hydrogenation deoxidation device is as shown in Figure 7.
1, process flow
Feedstock oil and hydrogen supply agent enter reactor by the coaxial feed nozzle of the side of I a of fluidized bed reactor, wherein raw material
Oil is stalk pyrolytic behavior.The control range of the feeding temperature of feedstock oil and hydrogen supply agent is room temperature~45 DEG C, general control hydrogen supply agent
Mass ratio with feedstock oil is 0.25~2:1.The hydrogen supply agent may come from the boiling bed hydrogenation deoxidation product of feedstock oil
The diesel oil obtained by fractionation the perhaps diesel oil or wax oil fraction of wax oil distillate or the high arene content outside device
Oil.From the oil of cold high pressure separator i, mutually outlet i-1, recycle oil are pressurized to 8~20Mpa through circulating pump e and (are higher than recycle oil
Reactor pressure) after, same to hydrogen (including the recycle hydrogen from circulating hydrogen compressor and the new hydrogen from device for producing hydrogen) mixing；
After heated I c of furnace of the mixture of recycle oil and hydrogen is heated to 200~450 DEG C, by the mixed phase of the bottom of I a of fluidized bed reactor
Entrance enters reactor.Under the momentum transmitting effect of recycle oil and hydrogen, the catalyst granules in I a of fluidized bed reactor reaches
To fluidized state.Catalytic hydrodeoxygenation reaction occurs in fluidized bed reactor for feedstock oil, and the oxygen atom in feedstock oil is with water
(H2) and carbon dioxide (CO O2) form removing, it obtains using alkane, aromatic hydrocarbons as the oil product of main component.In fluidized bed reactor
Three phase separator separation of the gas-liquid-solid three-phase mixture Jing Guo reactor head after completing hydrogenation deoxidation reaction, the gas phase of acquisition
Product includes reactor remaining hydrogen, reacts the components such as carbon dioxide, vapor, the lighter hydrocarbons generated with the liquid-phase product packet obtained
The alkane and aromatic component for including dissolution hydrogen mix outlet pipe through gas-liquid together and are discharged by the gas-liquid products export of fluidized bed reactor.Boiling
The liquid phase product mixture of I a of reactor discharge is risen after II d of heating furnace is heated to 200~450 DEG C, it is anti-by ebullated bed
The mixed phase entrance of the bottom of II b of device is answered to enter reactor.Recycle oil mutually exports i-1, circulation from the oil of cold high pressure separator i
Oil is after circulating pump e is pressurized to 8~20Mpa (being higher than reactor pressure), and same hydrogen is (including following from circulating hydrogen compressor
Ring hydrogen and new hydrogen from device for producing hydrogen) mixing；Heated I c of furnace of the mixture of recycle oil and hydrogen is heated to 200~450 DEG C
Afterwards, reactor is entered by the mixed phase entrance of the bottom of II b of fluidized bed reactor.It is acted in the momentum transmitting of recycle oil and hydrogen
Under, the catalyst granules in II b of fluidized bed reactor reaches fluidized state.It is mixed that preliminary liquid phase is obtained from I a of fluidized bed reactor
The oxygen atom in the raw catalytic hydrodeoxygenation reaction of II b of fluidized bed reactor relaying supervention, product of product is closed with water (H2O) and
Carbon dioxide (CO2) form removing, it obtains using alkane, aromatic hydrocarbons as the oil product of main component.It is completed in II b of fluidized bed reactor
Three phase separator separation of the gas-liquid-solid three-phase mixture Jing Guo reactor head after hydrogenation deoxidation reaction, the gaseous products of acquisition
The components such as carbon dioxide, vapor, the lighter hydrocarbons generated including reactor remaining hydrogen, reaction include molten with the liquid-phase product obtained
The alkane and aromatic component for solving hydrogen mix outlet pipe through gas-liquid together and are discharged by the gas-liquid products export of II b of fluidized bed reactor.Boiling
A gas-liquid two-phase product for reactor discharge is risen by high pressure hot separator f flash liberation, the hot high score gas of acquisition goes to high pressure
Air cooler h；Hot high score gas carries out de- liquid after high-pressure air cooler h is cooled to 40~50 DEG C, into cold high pressure separator i, obtains
Obtain the cold high score gas without drop；Cold high score gas passes through the separating-purifying of membrane separator k, obtains the higher recycle hydrogen of hydrogen purity
Gas, circulating hydrogen mix after air compressor machine l pressurization with new hydrogen.The separation of the bottom cold high pressure separator i obtains oil phase and water phase, water
Phase discharger, for a part of oily phase as recycle oil Returning reactor, another part of oily phase goes to cold low separator j.
Hot high score oil, which is obtained, from hot high score f goes to thermal low-pressure separators g.It is separated through thermal low-pressure separators g, the hot low point of gas of acquisition is gone to
The heat low oil of cold low separator j, acquisition go to fractionating device.In cold low separator j, the cold low point of gas of acquisition is separated
It goes to torch or is used as fuel gas, the cold low oil of acquisition goes to fractionating device.
2, fluidized bed reactor structural dimensions
Fluidized bed reactor structural dimensions are shown in Table 5, and relative dimensions signal and appended drawing reference are shown in Fig. 3.
5 100L/h sawdust pyrolytic behavior hydrogenation deoxidation device of table
3, implementation result
The test process of 100L/h sawdust pyrolytic behavior hydrogenation deoxidation device uses sawdust pyrolytic behavior and is tested, and tests
As a result such as table 6.In terms of test result, catalyst reaches even fluidizing, does not occur reactor coking within continuous operation 2500 hours,
0.6mm catalyst taking-out amount is controlled less than 1.5 μ g/g.
6 100L/h sawdust pyrolytic behavior hydrogenation deoxidation device experiment result of table
It is incorporated herein by reference in all documents of present invention topic note, it is independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (24)
1. a kind of biomass pyrolysis liquid fluidized bed reactor, characterized by comprising: perpendicular to ground cylinder-shaped pressure-bearing shell,
It is set to the fluid distributor of pressure-bearing shell bottom, the coaxial feed nozzle that is set on fluid distributor and is set to pressure-bearing
The three phase separator of upper part of the housing；Three phase separator consolidates cyclone separator and back taper by inner wall, the liquid on pressure-bearing shell top
Baffle is coaxially disposed from top to bottom from outside to inside, and a gas-liquid product mix outlet is equipped at the top of pressure-bearing shell.
2. reactor according to claim 1, it is characterised in that: the liquid consolidates cyclone separator from top to bottom successively by gas
Liquid mixes outlet pipe, overflow pipe, shell of column, impeller guide structure, cone section, downspout and non-return cone and is coaxially disposed；Overflow pipe is placed on
Gas-liquid mixes outlet pipe periphery, and shell of column is placed on overflow pipe periphery；Shell of column, cone section and downspout are from top to bottom sequentially connected, impeller guide
Structure is set on shell of column inner wall, and non-return cone is set to below downspout.
3. reactor according to claim 2, it is characterised in that: the gas-liquid is mixed outlet pipe lower end and is suspended in overflow pipe,
Upper end is connected as the gas-liquid mixed phase outlet that liquid consolidates cyclone separator with the gas-liquid product mix outlet at the top of pressure-bearing shell.
4. reactor according to claim 1, it is characterised in that: the pressure-bearing shell is isometrical cylindrical vessel or top
Diameter is the expanding cylindrical vessel in 1~2 times of lower diameter of top.
5. reactor according to claim 2, it is characterised in that: the shell of column is cylindrical tube, and the cone section is to fall
Divergent-cone wall.
6. reactor according to claim 1, it is characterised in that: the back taper baffle is single layer, two or more layers are covered
The baffle of lid.
7. reactor according to claim 2, it is characterised in that: the impeller guide structure is by being set on shell of column inner wall
Multiple swirl vanes compositions or by processed on shell of column inner wall in a helical duct of internal screw thread shape, two helical ducts or
Multiple helical ducts are constituted.
8. reactor according to claim 2, it is characterised in that: the shell of column diameter be pressure-bearing shell diameter 10~
90%, shell of column height is the 2.5~10% of pressure-bearing shell tangent line height.
9. reactor according to claim 2, it is characterised in that: the angle in the bus same level face of the cone section is 20~
80°。
10. reactor according to claim 9, it is characterised in that: the angle in the bus same level face of the cone section is 20
~60 °.
11. reactor according to claim 10, it is characterised in that: the angle in the bus same level face of the cone section is 20
~40 °.
12. reactor according to claim 2, it is characterised in that: the non-return cone is spindle-type α-Fe2O3, and top cone angle is
15~150 °, lower part cone angle is greater than top cone angle.
13. reactor according to claim 1, it is characterised in that: the bottom of the pressure-bearing shell is provided with one and is used for
The mixed phase entrance of recycle oil and hydrogen mixed feeding two or more enters for what recycle oil and hydrogen were respectively individually fed
Mouthful, the top position in pressure-bearing shell bottom is equipped with the catalyst outlet for catalyst discharge；The top of the pressure-bearing shell
It is additionally provided with the catalyst that one is added for catalyst and mouth is added.
14. reactor according to claim 1, it is characterised in that: the fluid distributor is Johnson screen mesh type point
Cloth device or bubblecaps or multi-nozzle distributor.
15. reactor according to claim 1, it is characterised in that: the coaxial feed nozzle is set to the pressure-bearing shell
The side of body is made of the outer tube and an inner tube being arranged concentrically, forms an annular space between inner and outer tubes, coaxial to feed
Nozzle sprays mouth down, and axis same level face angle is 0~45 °, and ejiction opening is located at the upper surface of fluid distributor or more 200
~1000mm.
16. a kind of application of biomass pyrolysis liquid fluidized bed reactor described in claim 1, it is characterised in that the reactor
Biomass pyrolysis liquid under participating in for catalyst is in the hydrogenation deoxidation technical process of feedstock oil, and the biology pyrolytic behavior is each
Kind biomass is by fast pyrolysis, at a slow speed thermal cracking, hydrogenation liquefaction, gasification or the charing obtained liquid of thermal cracking processes.
17. application according to claim 16, it is characterised in that: the operation temperature of the hydrogenation deoxidation technical process is
250~500 DEG C, operating pressure is 4~20Mpa, and reaction weight (hourly) space velocity (WHSV) is 0.1~4h-1。
18. application according to claim 16, it is characterised in that: loaded in the biomass pyrolysis liquid fluidized bed reactor
The static bed height of catalyst account for the upper surface of the fluid distributor to the height between the lower end surface of the downspout
10~85%, catalyst granules is expanded to the liquid level in the biomass pyrolysis liquid fluidized bed reactor after fluidizing.
19. application according to claim 16, it is characterised in that: the particle of the catalyst is to have supported period of element
The silica of the alloy formed from IIIB race to Group IIB transition metal element and them in table or porous carbon carry
The spheric granules of the metal oxide of body, particle diameter are 0.2~2mm.
20. application according to claim 16, it is characterised in that: the particle of the catalyst is to have supported period of element
The silica of the alloy formed from IIIB race to Group IIB transition metal element and them in table or porous carbon carry
The bar rope shape particle of the metal oxide of body, particle diameter are 0.2~2mm, and draw ratio is 1~10.
21. application according to claim 16, it is characterised in that: add hydrogen through the biomass pyrolysis liquid fluidized bed reactor
A part of liquid-phase product after deoxidation is as recycle oil with high pressure hydrogen Hybrid Heating or individually after heating by the biomass
Pyrolytic behavior fluidized bed reactor bottom enters；Into in reactor recycle oil and hydrogen after the fluid distributor is uniformly distributed
It flows up, static catalyst bed is made to reach fluidized state；Feedstock oil and hydrogen supply agent enter institute by the coaxial feed nozzle
State biomass pyrolysis liquid fluidized bed reactor；It is mixed by the catalyst bed that recycle oil and hydrogen fluidize with feedstock oil and hydrogen supply agent
Close, formed containing hydrogen, recycle oil, feedstock oil, hydrogen supply agent, catalyst granules gas-liquid-solid three-phase mixture, occur to raw material
The hydrogenation deoxidation reaction of oil；The gas-liquid-solid three-phase mixture is after three phase separator separation, and gas phase and liquid-phase product are by holding
A gas-liquid product mix of case top setting is pressed to export discharge.
22. application according to claim 21, it is characterised in that: the total amount and feedstock oil of the recycle oil and hydrogen supply agent
Weight percent is 0.5~10.
23. any application in 6~21 according to claim 1, it is characterised in that: in the hydrogenation deoxidation technical process
In, in such a way that two-stage fluidized bed reactor is used in series, the liquid-phase product of first order fluidized bed reactor goes to the second level
Fluidized bed reactor continues plus hydrogen.
24. any application in 6~21 according to claim 1, it is characterised in that: in the hydrogenation deoxidation technical process
In, in such a way that two-stage fluidized bed reactor is used in series, the liquid-phase product of first order fluidized bed reactor passes through heating furnace
Second level fluidized bed reactor is gone to after heating to continue to add hydrogen.
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