CN106732208A - A kind of injection circulation reactor and application method - Google Patents
A kind of injection circulation reactor and application method Download PDFInfo
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- CN106732208A CN106732208A CN201611043568.7A CN201611043568A CN106732208A CN 106732208 A CN106732208 A CN 106732208A CN 201611043568 A CN201611043568 A CN 201611043568A CN 106732208 A CN106732208 A CN 106732208A
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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
- B01J8/224—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 the particles being subject to a circulatory movement
- B01J8/226—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 the particles being subject to a circulatory movement internally, i.e. the particles rotate within the vessel
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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
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/006—Separating solid material from the gas/liquid stream by filtration
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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
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
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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
- B01J8/1809—Controlling processes
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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
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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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/342—Apparatus, reactors with moving solid catalysts
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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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00823—Mixing elements
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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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00893—Feeding means for the reactants
- B01J2208/00902—Nozzle-type feeding elements
Abstract
A kind of injection circulation reactor includes reactor shell (1),Roof shooter (20),Top filter (18),Base injcction device (19),There are roof shooter (20) and top filter (18) in reactor shell (1) top,Roof shooter (20) lower end connects anemostat (7),Anemostat (7) is in reactor shell (1),There are bottom filters (2) in reactor shell (1) bottom,Bottom filters (2) are in disk form,Its diameter is identical with the internal diameter of reactor shell (1),The surrounding of bottom filters (2) is closed with the inwall of reactor shell 1 to be connected,In bottom filters (2), centre bit is equipped with base injcction device (19),Base injcction device (19) is embedded in the surface of bottom filters (2),The bottom of reactor shell 1 has reactant to export (30).The present invention has can successive reaction, catalyst and the segregative advantage of product.
Description
Technical field
The invention belongs to a kind of reactor, more particularly to gas-liquid-solid reaction injection circulation reactor and its use
Method.
Background technology
Chemical reactor is the core of chemical engineering process, is engineering design and industrial key, due to variousization
The condition for learning reaction is different with characteristic, and each reaction process is required for matched reactor.The exploitation of reactor and set
Meter selection should be according to technique actual conditions, with the viewpoint of system engineering, according to course of reaction and the feature of catalyst, it is determined that most
Good reactor parameter.Therefore, the exploitation of the reactor for matching with reaction process is one of key link of new process development.
Ripe fischer-tropsch synthesis process mainly has iron-based slurry bed process and cobalt-based fixed-bed process, the reaction for using at present
Device mainly has bubble slurry bed reactor and tubulation fixed bed reactors.Although cobalt-based tubulation fixed bed reactors have easily putting
Big advantage, but because Fischer-Tropsch synthesis thermal discharge is big, for control bed temperature causes reaction tube diameter smaller, the sky of gas
Speed is relatively low, and reactor production capacity is low, and the easy carbon deposit of catalyst results in blockage.Fixed bed reactors complex structure, grasps simultaneously
Make and repair also very difficult, therefore there is larger difficulty in the large-scale production of cobalt-based fixed bed F- T synthesis.And bubble slurry
Slurry is close Isothermal Condition in bed reactor, and temperature control is more prone to and flexibly, reaction heat easily spreads, reactor heat exchange efficiency
Height, operating flexibility is big, and catalyst reaction efficiency high, the production capacity of catalyst is larger, is highly suitable for the extensive life of F- T synthesis
Produce.There is the report of many in existing document and patent.As CN99127184.X is circulated there is provided a kind of airwater mist cooling
Reactor；CN03151109.0 provides a kind of airwater mist cooling slurry bed system industrial reactor of continuous operation；
CN200710037008.5 provides a kind of slurry reactor device with interior circulation and external heat-exchanging and its application；
CN101396647A discloses the airwater mist cooling suspended-bed reactor for Fiscber-Tropscb synthesis, and it provides reactor configuration
Filtration system, inside reactor with the layout of size design, gas distributor and heat exchanger and design, wax and catalyst are led
The mist cancellation element of stream device and reactor head.
But, paste state bed reactor provided above is primarily present back-mixing, catalyst distribution are uneven, distributor is blocked etc.
Problem.Distributor is in reactor bottom, is easily accessible liquid and solid catalyst, causes outlet unstable, gas skewness,
Distributor needs often maintenance.Small solid catalyst particle is easily adsorbed on other bubble to be lost in tail gas, vapor condensation
Also solid catalyst particle is mixed into liquid unavoidably, product quality is influenceed.Therefore, for slurry bed ft synthetic reactor, how
Strengthen that particle in whole reactor suspends, liquid mass transfer admittedly uniformly between mixing and three-phase, heat transfer and reaction are still it
One of core technology.
Injection circulation reactor has that airwater mist cooling good mixing effect, multiphase mass transfer performance are good, efficiency is high for heat transfer, work
Make the advantages of volume is big, operating flexibility is high, structure of reactor is simple, catalyst performance can be given full play to, be that a kind of performance is excellent
Different paste state bed reactor, is widely used in chemical field.CN 103030622B are used for there is provided a kind of injection circulation reactor
The method of catalyst preparation, in reactor interior circulation, not only the requirement to pump is high for the solid catalyst particle for using, and
The pipelines such as heat exchanging device cause to wash away；Catalyst serious wear in cyclic process, causes follow-up product to separate difficult simultaneously.
The A of CN 103977746 have invented a kind of circulation flow reactor for synthesis gas conversion, although solve returning for paste state bed reactor
Mixed the shortcomings of, but its catalyst separates difficulty with product, and its solid-liquid separator for setting is easy to block, and causes operation tired
It is difficult.
The content of the invention：
Regarding to the issue above, can successive reaction, catalyst and the segregative injection circulation of product the invention provides one kind
Reactor and application method.
The present invention is to strengthen the mass transfer and heat-transfer effect of airwater mist cooling using the mode for spraying circulation, and utilizes liquid
Product solves the blockage problem of filter to filter continuous wash, it is ensured that the continuous-stable extraction of product liquid.
A kind of injection circulation reactor of the invention, it includes reactor shell, roof shooter, top filter, bottom
Portion's injector, it is characterised in that there are roof shooter and top filter, the connection of roof shooter lower end in reactor shell top
Anemostat, anemostat is located in reactor cylinder body, has bottom filters in reactor shell bottom, and bottom filters are in disk
Shape, its diameter is identical with the internal diameter of reactor shell, and the surrounding of bottom filters is closed with the inwall of reactor shell to be connected,
Bottom filters centre bit is equipped with base injcction device, and base injcction device is embedded in the surface of bottom filters, reactor shell 1
Bottom has reactant to export.
Roof shooter as described above includes cylinder, circulating liquid entrance and nozzle, and cylinder is made up of inner cylinder and outer barrel,
The top of inner cylinder is circulating liquid entrance, and inner cylinder lower end is connected with nozzle, nozzle in outer barrel, the lower end of outer barrel and injector
Outlet connection, outer barrel has unstripped gas entrance, and unstripped gas entrance is located on nozzle.
The length of the anemostat 7 is the 1/2-4/5, the preferably 2/3- of reactor shell height of the height of reactor shell 1
4/5。
Base injcction device as described above is hollow disk, has liquid spray orifice on the side wall of disk, under liquid spray orifice
Edge is equal with the upper surface of bottom filters, and liquid is sprayed by the liquid spray orifice on described side wall.Each liquid spray orifice hole
Diameter between 1-5mm, the pitch of holes of each liquid spray orifice is 1-5mm.There is liquid inlet 31 below base injcction device, lead to
Pipeline is crossed to be connected with force (forcing) pump.
In the injection circulation reactor that the present invention is provided, the material to bottom filters is not limited, it is possible to use sintering
Woven wire micropore filter material, sintering metal powder micropore filter material, metal micro-holes membrane material, sintered metal fiber micropore
Material, micropore ceramics material, ceramic membrane materials or other types of filtering material.The pore diameter range of screen pipe can be by specifically making
With the species of catalyst granules, the scale of reactor and the reaction type that is carried out and change.
In the injection circulation reactor that the present invention is provided, described base injcction device is located in described bottom filters
The heart, is connected by pipeline with external pressurisation pump, and the base injcction device is hollow disc-shape, the liquid ejected using high speed
Body material, the solid catalyst particle to bottom filters adsorption is purged, and is reduced solid catalyst and is filtered in bottom
Absorption on device, prevents the blocking of bottom filters.
The invention provides a kind of method using circulation flow reactor of the invention, the described method comprises the following steps：
(1) unstripped gas is introduced in roof shooter, is sprayed by the high speed of circulating liquid, and gas is cut into tiny gas
Bubble, forms well mixed gas-liquid two-phase in anemostat, circulation in being formed is ejected into reactor cylinder body, with the slurry in cylinder
Liquid catalyst reacts；
(2) unconverted unstripped gas and the low boiling gaseous products of generation are a small amount of solid by what is carried secretly by top filter
Body catalyst particle filtering, the Gaseous materials isolated are condensed by condenser, the liquid product that condenses out and uncooled
Gaseous materials are separated by gas-liquid separator, and the liquid material of condensation is pumped into or without heat exchanger by pressurization
Base injcction device, for cleaning filter surfaces；Other aftertreatment technologys are delivered in uncooled Gaseous materials emptying；
(3) liquid material in reactor shell 1 is separated by filter with solid catalyst, the liquid without catalyst
State material exchanges heat by circulating pump in heat exchanger, and a part of liquid material is recycled to roof shooter, into reactor shell,
Liquid material described in another part enters in filter, and the trace solid catalyst granules that liquid material is carried secretly is separated, and separates
Liquid material afterwards is produced as liquid product, and the liquid material after the concentration containing a small amount of catalyst is recycled to roof shooter,
Into reactor shell.
Described liquid material may include liquid product and the slurry medium for reacting.
In the injection circulation reactor that the present invention is provided, the fluid pressure of base injcction device will be entered by the force (forcing) pump
Bring up to than the pressure 0.1-0.5MPa high, preferably 0.2-0.3MPa in reactor cylinder body.The injection circulation that the present invention is provided is anti-
Answer in device, be 1-12m/s, preferably 5-10m/s by the flow rate of liquid of the roof shooter.
The circulation flow reactor that the present invention is provided strengthens the mass transfer and heat-transfer effect of airwater mist cooling by the way of injection,
Being sufficiently mixed for solid catalyst particle, liquid form product and unstripped gas can be realized, alternate mass transfer and heat transfer coefficient is improved, carried
Catalytic reaction activity high；Bottom filters are set and ensure that catalyst does not enter reaction pipeline and the pump housing, alleviate catalyst mill
Damage and catalyst washes away to equipment, while reducing the seal request of circulating pump；Set using above bottom filters
The mode of injector, continuously cleans to filter, essentially eliminates the blocking of bottom filters, it is ensured that the long period of device
Operation；Reactor of the invention and its application process are suitable for gas-liquid-solid reaction and needs isolate liquid from slurries
The chemical reaction process of product, such as Fischer-Tropsch synthesis, methanol-fueled CLC, the hydrocarbon oil hydrogenation using suspension bed or paste state bed reactor
And certain embodiments.
The method that the present invention is provided can be used for F- T synthesis production liquid hydrocarbon or paraffin, and wherein raw material is synthesis gas,
Operating condition in reactor shell 1 is：Temperature be 160-300 DEG C, preferably 180-250 DEG C, absolute pressure be 1.0-5.5MPa,
It is preferred that 1.5-3.5MPa, the air speed of unstripped gas is 500-5000h-1, preferably 1000-3000h-1。
Used catalyst can be urged for precipitated iron catalyst, molten iron when the method that the present invention is provided is used for fischer-tropsch synthesis process
Agent or cobalt-base catalyst, the particle size range of catalyst is 1-300 μm, and preferred scope is 5-100 μm.
Brief description of the drawings
Fig. 1 is flow chart of the present invention using injection circulation reactor；
Fig. 2 is injection circulation reactor structural representation of the present invention；
Fig. 3 is base injcction device structural representation of the present invention；
Fig. 4 is bottom filters of the present invention and base injcction device structural representation；
Fig. 5 is roof shooter structural representation of the present invention.
As shown in the figure：1. reactor shell, 2. bottom filters, 3. circulating pump, 4. heat exchanger, 5. force (forcing) pump, 6. filters
Device, 7. anemostat, 8. gas-liquid separator, 9. unstripped gas, the 10. liquid material without catalyst, 11. circulation liquid materials, 12.
Liquid material after concentration, 13. enter roof shooters liquid material, 14. Gaseous materials, 15. liquid products, 16. without
Filter liquid state material, liquid material, 18. top filters, 19. base injcction devices, 20. roof shooters, 21. after 17. condensations
Liquid spray orifice, 22. condensers, 23. tail gas, 24. injector inner cylinders, 25. injector outer barrels, 26. circulating liquid entrances, 27. is former
Material gas entrance, 28. nozzles, the outlet of 29. roof shooters, the outlet of 30. reactants, 31. base injcction device liquid inlets.
Specific embodiment
The tool that the injection circulation reactor of present invention offer is used in Fischer-Tropsch synthesis is illustrated below in conjunction with the accompanying drawings
Body embodiment, but the present invention not therefore and be restricted.
As seen from Figure 1, the reactor include two parts, i.e. reactor shell 1 in part and reactor shell with
Outer part.Include roof shooter 20, anemostat 7, bottom filters 2 and base injcction device 19 in the reactor shell 1.
The reactor shell 1 can contain serum materials, and the serum materials can any be dispersed in liquid by solid catalyst particles
The slurries formed in state material.The injection circulation reactor includes can be used at least a portion slurry by reactor shell 1
State material is drawn and the external circulating device of reactor shell 1 is returned at least a portion outer circulation；The external circulating device mainly includes
Bottom external circulating device and top external circulating device.In normal working conditions, the bottom external circulating device is used for being free of
The liquid material of catalyst granules is drawn from reactor and outer circulation returns to the roof shooter 20；The top outer circulation dress
Put for reacted Gaseous materials are drawn into condensation, and loop back base injcction device 19.The reacted Gaseous materials can
Including the gaseous products obtained after reaction and the unstripped gas not converted completely in reaction, the unstripped gas may include to participate in reaction
Unstripped gas and be not involved in reaction inert gas.
Using well known to a person skilled in the art by Automated condtrol or manually operated pipeline, valve, control device etc.
Transfer unit, roof shooter 20 is delivered to by the unstripped gas 9 needed for reaction process.According to specific technique needs, these conveyings
Part can also be including optional pump, pressue device, decompressor, heater, cooling device, detection means etc..Conveying
Unstripped gas 9 can include reaction process needed for any gas, for example reactant, inert dilution gas, for cause reactant
System inactivates and stops gas of reaction etc..These unstripped gas can be mixed mutually first, be then re-fed into roof shooter 20,
Or can simultaneously convey plurality of raw materials gas to roof shooter 20 according to required ratio by many parallel pipelines.
The roof shooter 20 can be arbitrary injector, and Fig. 4 shows can be sprayed as the venturi of injector
Emitter structural representation.The venturi-type eductors opening downwards, its opening near bore be first gradually reduced then again by
Flaring is big, and the change of this kind of bore can make correspondingly to increase by the pressure and flow velocity of the liquid of the Venturi tube, and
Side forms negative pressuren zone, gas material is incorporated into nozzle, so that Gaseous materials and liquid material are in the down-comer of center
It is sufficiently mixed.
In a state of use, slurries are accommodate in the reactor shell 1, the slurries can be corresponding catalyst
It is suspended in what is formed in the materials such as the solvent of liquid, product, accessory substance Deng solid matter.The height of the gas-liquid interface of the slurries
Higher than the lower position of the roof shooter anemostat 7 so that the latter is respectively positioned under gas-liquid interface.
Bottom external circulating device and top external circulating device are additionally provided with the outside of the reactor shell 1.The bottom
Portion's external circulating device includes circulating pump 3, heat exchanger 4 and filter 6, can only include circulating pump 3 and heat exchanger 4, is produced in liquid
Thing continuously in the case of extraction, is optionally added into filter 6.Lead to by liquid material 10 of the internal ramp 2 without catalyst
Cross circulation and be pumped into heat exchanger 4, roof shooter 20 is transported to by the part or all of liquid material after heat exchanger, follow
In loopback reactor cylinder 1；It is micro solid by what is contained in liquid material or a portion liquid material is by filter 6
Body catalyst is filtered, and reaction system is removed as liquid product 15；And filter after concentrated liquid material 12 with it is filtered
Liquid material 16 returns to roof shooter 20 together, so as to complete the bottom outer loop process of slurries.In this bottom outer circulation
In device, the device such as the circulating pump and heat exchanger can be any suitable means well known in the art, but at one preferably
Implementation method in, the circulating pump is preferably unshrouded impeller circulating pump.
Described liquid material in the external circulating device cyclic process of bottom, by the heat exchanger 4 exchange heat after, liquid
The temperature of material is general lower than the temperature of entrance, but outlet temperature will will ensure liquid on the fusing point of liquid material
The mobility of material, in one preferred embodiment, described liquid material compares entrance by the temperature after heat exchanger 4
Temperature it is low 10-30 DEG C, it is preferred low 10-20 DEG C.
The top external circulating device includes top filter 18, condenser 22, gas-liquid separator 8 and force (forcing) pump 5.Gaseous state
After material leaves reactor shell 1, a small amount of solid catalyst particle by removing entrainment after top filter 18, in condenser
Condensed in 22, condensed liquid material and gas are sufficiently separated in gas-liquid separator 8, isolated liquid object
Material by or without heat exchanger 4, as outer circulation liquid material by force (forcing) pump 5, base injcction device 19 is sent back to, into anti-
Answer in device cylinder 1.The Gaseous materials isolated are as exhaust emissions or deliver to other aftertreatment technologys.
By using injection circulation reactor of the invention, there is provided one kind has to be increased airwater mist cooling mixing and increase
Strong mass transfer, the slurry reactor method of heat transfer.Specifically, methods described can be followed the steps below：First, by raw material
Gas 9 delivers to roof shooter 20, and unstripped gas is sufficiently mixed with recycle stock in down-comer 7, and mixed material is ejected into instead
Answer in cylinder 1, drive catalyst slurry to form interior circulation in described reaction tube, reach well-mixed purpose, and complete anti-
Should.Unreacted Gaseous materials and the volatile products of generation are lifted off reactor shell 1 entrainment of a small amount of slurries, from top
Filter 18 is drawn, and feeding top external circulating device, the top external circulating device as described above, is condensed by condenser 22,
Liquids and gases are separated using gas-liquid separator 8, the liquid material isolated passes through or without heat exchanger 4, by pressurizeing
Pump 5 is pressed and delivered to base injcction device 19, loops back within reactor shell 1, for cleaning bottom filters 2；It is unreacted
Gaseous materials are as exhaust emissions or deliver to other aftertreatment technologys.
Therefore, the present invention is sprayed raw material autogenous cutting by setting roof shooter at the top of circulation flow reactor using slurries
Small bubble is cut into, the well-mixed purpose of gas-liquid is reached, by the guide effect of down-comer so that mixed gas-liquid thing
Material is contacted with catalyst slurry in reactor cylinder body and forms interior circulation.Meanwhile, by top external circulating device and bottom outside
EGR so that at least a portion slurry material and Gaseous materials are returned in reactor cylinder body by external circulating device, right
Gas reaction material and catalyst granules in slurries play stirring, suspension effect.Above two effect is combined, and enhances institute
The suspension of the particle in circulation flow reactor, liquid is stated to mix admittedly and conduct heat and mass transfer.
The reaction that can be carried out using the method is selected from Fischer-Tropsch synthesis, DCL/Direct coal liquefaction reaction, synthesis gas synthesis two
The reaction of methyl ether and the reaction of synthesis gas synthesizing methanol, preferably fischer-tropsch reaction.
When Fischer-Tropsch synthesis are carried out using reactor of the invention, the slurries are that solid catalyst is suspended in
The slurries formed in hydrocarbon ils, unstripped gas CO and H2Mixed gas reacted in the slurries, generation hydrocarbon product and few
The accessory substances such as water, the carbon dioxide of amount.In the case, during the top external circulating device removes slurries in outer loop process
Gaseous matter, hydrocarbon product is separated and is then returned to base injcction device.And the liquid in the external circulating device of bottom is mainly height boiling
The heavier hydrocarbon components of point, by bottom external circulating device, remove reaction heat, while using the filtering system of bottom external circulating device
System, the heavy hydrocarbon continuous-stable extraction that will can be generated.
The following examples are further illustrated to the method that the present invention is provided, but therefore do not limit this hair
It is bright.
Embodiment 1
A kind of circulation flow reactor, including reactor shell 1, roof shooter 20, top filter 18, base injcction device
19, it is characterised in that there are roof shooter 20 and top filter 18, the connection of the lower end of roof shooter 20 in the top of reactor shell 1
Anemostat 7, anemostat 7 is located in reactor shell 1, has bottom filters 2 in the bottom of reactor shell 1, and bottom filters 2 are in
Disc, its diameter is identical with the internal diameter of reactor shell 1, and the surrounding of bottom filters 2 is closed with the inwall of reactor shell 1
It is connected, base injcction device 19 is equipped with the centre bit of bottom filters 2, base injcction device 19 is embedded in just going up for bottom filters 2
Side, the bottom of reactor shell 1 has reactant to export 30.
Roof shooter 20 as described above includes cylinder, circulating liquid entrance 26 and nozzle 28, and cylinder is by the He of inner cylinder 24
Outer barrel 25 is constituted, and the top of inner cylinder 24 is circulating liquid entrance 26, and the lower end of inner cylinder 24 is connected with nozzle 28, and nozzle 28 is located at outer barrel
In 25, the lower end of outer barrel 25 is connected with injector outlet 29, and outer barrel 25 has unstripped gas entrance 27, and unstripped gas entrance 27 is located at nozzle
On 28.
Base injcction device 19 as described above is hollow disk, there is liquid spray orifice 21, liquid spray orifice on the side wall of disk
21 lower edge is equal with the upper surface of bottom filters 2.
The diameter 0.5m of the circulation flow reactor of the present embodiment, 2m high, roof shooter 20 uses Venturi nozzle, the spray
The length of emitter anemostat 7 is 1.3m；Bottom filters 2 are the disk of diameter 0.5m, and the filter for using is sintered porous metal
Net, 1 μm of average pore size, at the bottom 1/6 of reactor shell 1；Base injcction device 19 is embedded in the centre bit of bottom filters 2
Put, the liquid spray orifice of diameter 1.5mm is dispersed with the side wall of base injcction device 19, pitch of holes is 2mm.
The present embodiment is with H2/ CO mol ratios be 2 synthesis gas for unstripped gas, F- T synthesis production liquid hydrocarbon, using cobalt-based
The mass fraction of catalyst, wherein cobalt is 20wt%, and pore volume is 0.40m3/ g, specific surface area 260m2/ g, heap density is 1.0g/
cm3, 50-100 μm of particle size range.
The described method comprises the following steps：
(1) unstripped gas 9 is introduced in roof shooter 20, is sprayed by the high speed of circulating liquid, gas is cut into tiny
Bubble, well mixed gas-liquid two-phase is formed in anemostat 7, circulation in being formed is ejected into reactor shell 1, with cylinder
Interior slurry catalyst reacts；
(2) unconverted unstripped gas and the low boiling gaseous products 14 of generation pass through top filter 18, by lacking for carrying secretly
Amount solid catalyst particle filtering, the Gaseous materials isolated are condensed by condenser 22, the liquid product that condenses out and not
The Gaseous materials of condensation are separated by gas-liquid separator 8, the liquid material of condensation with or without heat exchanger 4, by plus
Press pump 5 is sent to base injcction device 19, for cleaning the surface of filter 2；Uncooled Gaseous materials 23 are vented or deliver to other
Aftertreatment technology；
(3) liquid material in reactor shell 1 is separated by filter 2 with solid catalyst, the liquid without catalyst
State material 10 exchanges heat by circulating pump 3 in heat exchanger 4, and a part of liquid material is recycled to roof shooter 20, into reaction
Device cylinder 1, liquid material described in another part enters in filter 6, the trace solid catalyst granules that liquid material is carried secretly
Separate, the liquid material after separation is produced as liquid product 15, and the liquid material 12 after the concentration containing a small amount of catalyst is circulated
To roof shooter 20, into reactor shell 1.
The flow control of circulating liquid in 7m/s, by the product liquid after heat exchanger 4 than the reaction in reacting cylinder body 1
Temperature is low 20 DEG C.
The operating condition of reaction is：Reaction temperature is 210 DEG C, and absolute pressure is 3.0MPa, and unstripped gas air speed is 2000h-1,
Catalyst useful load is 16% (volumn concentration).React 120 hours in this operating condition, CO conversion ratios reach in synthesis gas
92.5%.Being fractionated into the product slates after treatment is：Methane selectively 5.2%, C5 +Selectivity 91%.
Circulation flow reactor of the invention make use of condensate liquid as the medium of cleaning bottom filters, by bottom filters table
The catalyst granules of face deposition is washed, and efficiently solves the problems, such as plugged filter, it is ensured that the continuous-stable of product liquid
Extraction, after continuously running 1000 hours, there is no obvious blocking, the μ g/ of catalyst content 4 in fluid product in filter
ml。
Embodiment 2
The diameter 1m of injection circulation reactor, 4m high, injector 20 uses Venturi nozzle, the length of injector anemostat 7
It is the 3m of reactor cylinder body length；Bottom filters 2 are the disk of diameter 1m, and the filter for using is metal micro-holes membrane material,
1 μm of average pore size, at the bottom 1/7 of reactor shell 1；Base injcction device 19 is embedded in the center of bottom filters 2,
The liquid spray orifice of diameter 2mm is dispersed with the side wall of base injcction device 19, pitch of holes is 3mm.
By the flow control of circulating liquid in 10m/s, by the product liquid after heat exchanger 4 than in reacting cylinder body 1
Reaction temperature is low by 25.
With H2/ CO mol ratios be 2 synthesis gas for raw material, F- T synthesis production liquid hydrocarbon, using cobalt-based catalyst, wherein cobalt
Mass fraction be 20wt%, pore volume is 0.35m3/ g, specific surface area 260m2/ g, heap density is 1.0g/cm3, particle size range 50-
100μm。
The operating condition of reactor is：Reaction temperature is 210 DEG C, and absolute pressure is 3.0MPa, and unstripped gas air speed is
2000h-1, catalyst useful load is 16% (volumn concentration), and remaining is with embodiment 1.
React 120 hours in this operating condition, CO conversion ratios are up to 91.3% in synthesis gas.It is fractionated into the product after treatment
It is distributed as：Methane selectively 6.1%, C5 +Selectivity 90%.
Circulation flow reactor of the invention make use of condensate liquid as the medium of cleaning bottom filters, by bottom filters table
The catalyst granules of face deposition is washed, and efficiently solves the problems, such as plugged filter, it is ensured that the continuous-stable of product liquid
Extraction, after continuously running 1000 hours, there is no obvious blocking, the μ g/ of catalyst content 3.5 in fluid product in filter
ml。
Embodiment 3
The diameter 1m of injection circulation reactor, 4m high, injector 20 uses Venturi nozzle, the length of injector anemostat 7
It is the 3.5 of reactor cylinder body length；Bottom filters 2 are the disk of diameter 1m, and the filter for using is micropore ceramics membrane material,
1 μm of average pore size, at the bottom 1/6 of reactor shell 1；Base injcction device 19 is embedded in the center of bottom filters 2,
The liquid spray orifice of diameter 2mm is dispersed with the side wall of base injcction device 19, pitch of holes is 2mm.
The flow control of circulating liquid in 8m/s, by the product liquid after heat exchanger 4 than anti-in reactor cylinder body
Answer temperature low by 20.
With H2/ CO mol ratios be 1 synthesis gas for raw material, F- T synthesis production liquid hydrocarbon is catalyzed using quenching skeleton iron
Agent, the mass fraction of iron is 83wt%, and specific surface area is 51m2/ g, pore volume is 0.11m3/ g, heap density is 1.2g/cm3, particle diameter
30-50 μm of scope.
The operating condition of reactor is：Reaction temperature is 260 DEG C, and pressure is 2.0MPa, and unstripped gas air speed is 2000h-1, urge
Agent useful load is 15% (volumn concentration), and remaining is with embodiment 1.
React 120 hours in this operating condition, CO conversion ratios are up to 81.5% in synthesis gas.It is fractionated into the product after treatment
Dry gas is distributed as 11.5wt%, liquefied gas is 18.2wt%, and naphtha is 28.6wt%, and diesel oil is 32.5wt%, and hard wax is
10.8wt%.
Circulation flow reactor of the invention make use of condensate liquid as the medium of cleaning bottom filters, by bottom filters table
The catalyst granules of face deposition is washed, and efficiently solves the problems, such as plugged filter, it is ensured that the continuous-stable of product liquid
Extraction, after continuously running 1000 hours, there is no obvious blocking, the μ g/ of catalyst content 2.0 in fluid product in filter
ml。
Claims (16)
1. a kind of injection circulation reactor, it includes reactor shell (1), roof shooter (20), top filter (18), bottom
Portion's injector (19), it is characterised in that there are roof shooter (20) and top filter (18), top in reactor shell (1) top
Injector (20) lower end connects anemostat (7), and anemostat (7) is interior positioned at reactor shell (1), in reactor shell (1) bottom
There are bottom filters (2), bottom filters (2) are in disk form, and its diameter is identical with the internal diameter of reactor shell (1), bottom mistake
The surrounding of filter (2) is closed with the inwall of reactor shell 1 to be connected, and in bottom filters (2), centre bit is equipped with base injcction device
(19), base injcction device (19) is embedded in the surface of bottom filters (2), and the bottom of reactor shell 1 has reactant to export
(30)。
2. a kind of injection circulation reactor as claimed in claim 1, it is characterised in that described roof shooter (20) includes
Cylinder, circulating liquid entrance (26) and nozzle (28), cylinder are made up of inner cylinder (24) and outer barrel (25), and the top of inner cylinder (24) is
Circulating liquid entrance (26), inner cylinder (24) lower end is connected with nozzle (28), and nozzle (28) is interior positioned at outer barrel (25), outer barrel (25)
Lower end is connected with injector outlet (29), and outer barrel (25) has unstripped gas entrance (27), and unstripped gas entrance (27) is positioned at nozzle (28)
On.
3. a kind of injection circulation reactor as claimed in claim 1, it is characterised in that anemostat (7) length is reactor
The 1/2-4/5 of the height of cylinder 1.
4. a kind of injection circulation reactor as claimed in claim 3, it is characterised in that anemostat (7) length is reactor
The 2/3-4/5 of cylinder height.
5. a kind of injection circulation reactor as claimed in claim 1, it is characterised in that during described base injcction device (19) is
Empty disk, there is liquid spray orifice (21), the lower edge of liquid spray orifice (21) and the upper table of bottom filters (2) on the side wall of disk
Face is equal, there is liquid inlet (31) below base injcction device (19).
6. a kind of injection circulation reactor as claimed in claim 5, it is characterised in that the diameter in each liquid spray orifice (21) hole
Between 1-5mm, the pitch of holes of each liquid spray orifice (21) is 1-5mm.
7. a kind of injection circulation reactor as claimed in claim 1, it is characterised in that bottom filters (2) use sintering metal
Silk screen micropore filter material, sintering metal powder micropore filter material, metal micro-holes membrane material, sintered metal fiber micropore material
Material, micropore ceramics material or ceramic membrane materials.
8. the use technique of a kind of injection circulation reactor as described in claim any one of 1-7, it is characterised in that
Comprise the following steps：
(1) unstripped gas is introduced in roof shooter (20), is sprayed by the high speed of circulating liquid, and gas is cut into tiny gas
Bubble, forms well mixed gas-liquid two-phase in anemostat (7), circulation in being formed is ejected into reactor shell 1, in cylinder
Slurry catalyst react；
(2) unconverted unstripped gas and the low boiling gaseous products of generation are a small amount of solid by what is carried secretly by top filter (18)
Body catalyst particle filtering, the Gaseous materials isolated are condensed by condenser (22), the liquid product that condenses out and not cold
Solidifying Gaseous materials are separated by gas-liquid separator (8), the liquid material of condensation with or without heat exchanger (4), by
Force (forcing) pump 5 is sent to base injcction device (19), for cleaning filter (2) surface；Uncooled Gaseous materials emptying delivers to it
Its aftertreatment technology；
(3) liquid material in reactor shell (1) is separated, the liquid without catalyst by filter (2) with solid catalyst
State material heat exchange in heat exchanger (4) by circulating pump (3), a part of liquid material is recycled to roof shooter (20), enters
Reactor shell (1), liquid material described in another part enters in filter (6), and the trace solid that liquid material is carried secretly is urged
Catalyst particles are separated, and the liquid material after separation is produced as liquid product, the liquid material after the concentration containing a small amount of catalyst
Roof shooter (20) is recycled to, into reactor shell (1).
9. the use technique of a kind of injection circulation reactor as claimed in claim 8, it is characterised in that the force (forcing) pump (5) will
Fluid pressure into base injcction device (19) is brought up to than the pressure 0.1-0.5MPa high in reactor shell (1).
10. the use technique of a kind of injection circulation reactor as claimed in claim 9, it is characterised in that the force (forcing) pump 5 will
Fluid pressure into base injcction device (19) is brought up to than the pressure 0.2-0.3MPa high in reactor shell (1).
A kind of use technique of 11. injection circulation reactors as claimed in claim 8, it is characterised in that the roof shooter
(20) flow rate of liquid is 1-12m/s.
A kind of use technique of 12. injection circulation reactors as claimed in claim 11, it is characterised in that the top jet
The flow rate of liquid of device (20) is 5-10m/s.
The use technique of 13. a kind of injection circulation reactors as claimed in claim 8, it is characterised in that unstripped gas is synthesis
Gas, liquid hydrocarbon or paraffin are produced for F- T synthesis, and the operating condition in reactor shell 1 is：Temperature is 160-300 DEG C, absolutely
It is 1.0-5.5MPa to pressure, the air speed of unstripped gas is 500-5000h-1。
The use technique of 14. a kind of injection circulation reactors as claimed in claim 13, it is characterised in that in reactor shell 1
Operating condition be：Temperature is 180-250 DEG C, and absolute pressure is 1.5-3.5MPa, and the air speed of unstripped gas is 1000-3000h-1,
Catalyst is precipitated iron catalyst, fused iron catalyst or cobalt-base catalyst.
A kind of use technique of 15. injection circulation reactors as claimed in claim 14, it is characterised in that the particle diameter of catalyst
Scope is 1-300 μm.
A kind of use technique of 16. injection circulation reactors as claimed in claim 14, it is characterised in that the particle diameter of catalyst
Scope is 5-100 μm.
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| WO2022082622A1 (en) * | 2020-10-21 | 2022-04-28 | 南京延长反应技术研究院有限公司 | Hydrogenation micro-interface system |
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