CN106732208B - A kind of injection circulation reactor and application method - Google Patents
A kind of injection circulation reactor and application method Download PDFInfo
- Publication number
- CN106732208B CN106732208B CN201611043568.7A CN201611043568A CN106732208B CN 106732208 B CN106732208 B CN 106732208B CN 201611043568 A CN201611043568 A CN 201611043568A CN 106732208 B CN106732208 B CN 106732208B
- Authority
- CN
- China
- Prior art keywords
- reactor
- liquid
- catalyst
- reactor shell
- injection circulation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 diffuser (7), diffuser (7) is located in reactor shell (1), there are bottom filters (2) in reactor shell (1) lower part, bottom filters (2) are in disk form, its diameter is identical as the internal diameter of reactor shell (1), the surrounding of bottom filters (2) with the inner wall of reactor shell 1 is closed is 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), 1 bottom end of reactor shell has instead Object is answered to export (30).The present invention has can successive reaction, catalyst and the segregative advantage of product.
Description
Technical field
The invention belongs to the injection circulation reactors and its use of a kind of reactor more particularly to gas-liquid-solid reaction
Method.
Background technique
Chemical reactor is the core of chemical engineering process, is engineering design and industrial key, due to variousization
The condition and characteristic difference, each reaction process for learning reaction require matched reactor.It the exploitation of reactor and sets
Meter selection should determine most with the viewpoint of system engineering according to reaction process and the feature of catalyst according to technique actual conditions
Good reactor parameter.Therefore, the exploitation of the reactor to match with reaction process is one of the key link of new process development.
Mature fischer-tropsch synthesis process mainly has iron-based slurry bed process and cobalt-based fixed-bed process at present, the reaction used
Device mainly has bubble slurry bed reactor and tubulation fixed bed reactors.It is easy to put although cobalt-based tubulation fixed bed reactors have
Big advantage, but since Fischer-Tropsch synthesis thermal discharge is big, cause reaction tube diameter smaller for control bed temperature, the sky of gas
Speed is lower, and reactor production capacity is low, and catalyst is easy carbon deposit and results in blockage.Structure is complicated for fixed bed reactors simultaneously, behaviour
Make and maintenance is also very difficult, therefore there are larger difficulties for 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 easier and flexibly, reaction heat is easy diffusion, reactor heat exchange efficiency
Height, operating flexibility is big, and catalyst reaction is high-efficient, and the production capacity of catalyst is larger, is highly suitable for the extensive life of F- T synthesis
It produces.In the report of many of existing document and patent.As CN99127184.X provides a kind of airwater mist cooling circulation
Reactor；CN03151109.0 provides a kind of airwater mist cooling slurry bed system industrial reactor of continuous operation；
CN200710037008.5 provides the slurry reactor device and its application of a kind of band interior circulation and external heat-exchanging；
CN101396647A discloses the airwater mist cooling suspended-bed reactor for Fiscber-Tropscb synthesis, provides reactor configuration
It is led with the filtration system of the layout of size design, gas distributor and heat exchanger and design, wax and catalyst, inside reactor
Flow the mist cancellation element of device and reactor head.
But paste state bed reactor provided above is primarily present uneven, distributor blocking of back-mixing, catalyst distribution etc.
Problem.Distributor is in reactor bottom, is easily accessible liquid and solid catalyst, causes outlet unstable, and gas is unevenly distributed,
Distributor needs often maintenance.In addition it is easy the small solid catalyst particle of absorption on bubble to be lost with tail gas, vapor condensation
Also it is inevitably mixed into solid catalyst particle in liquid, influences product quality.Therefore, for slurry bed ft synthetic reactor, how
Particle suspension, solid mass transfer, heat transfer and the reaction uniformly between mixing and three-phase of liquid strengthened in entire reactor are still it
One of core technology.
Injection circulation reactor has that airwater mist cooling good mixing effect, multiphase mass transfer performance are good, heat transfer efficiency is high, work
Make the advantages that volume is big, operating flexibility is high, structure of reactor is simple, catalyst performance can be given full play to, is that a kind of performance is excellent
Different paste state bed reactor, is widely used in chemical field.CN 103030622B provides a kind of injection circulation reactor and is used for
The method of catalyst preparation, the solid catalyst particle used recycle in reactor, and not only the requirement to pump is high, but also
The pipelines such as heat exchanging device cause to wash away；Catalyst serious wear in cyclic process simultaneously causes subsequent product to separate difficult.
103977746 A of CN has invented a kind of circulation flow reactor for synthesis gas conversion, although solving returning for paste state bed reactor
The disadvantages of mixed, but the separation of its catalyst and product is difficult, the solid-liquid separator of setting is easy to block, and causes operation tired
It is difficult.
Summary of the invention:
It can successive reaction, catalyst and the segregative injection circulation of product in view of the above-mentioned problems, the present invention provides one kind
Reactor and application method.
The present invention is to reinforce the mass transfer and heat-transfer effect of airwater mist cooling in the way of injection circulation, and utilize liquid
Product solves the blockage problem of filter to filter continuous wash, ensure 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
Diffuser, diffuser are located in reactor cylinder body, have bottom filters in reactor shell lower part, bottom filters are in disk
Shape, diameter is identical as the internal diameter of reactor shell, the surrounding of the bottom filters and inner wall of reactor shell is closed is 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
There is reactant exit in bottom end.
Roof shooter as described above includes that cylinder, circulating liquid entrance and nozzle, cylinder are made of inner barrel and outer barrel,
The top of inner cylinder is circulating liquid entrance, and inner cylinder lower end is connect with nozzle, and nozzle is located in outer cylinder, the lower end of outer cylinder and injector
Outlet connection, outer cylinder have unstripped gas entrance, and unstripped gas entrance is located on nozzle.
7 length of diffuser is the 1/2-4/5, the preferably 2/3- of reactor shell height of 1 height of reactor shell
4/5。
Base injcction device as described above is hollow disk, there is 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 the 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, leads to
Pipeline is crossed to be connected with force (forcing) pump.
In injection circulation reactor provided by the invention, to the materials of bottom filters, there is no limit can be used sintering
Wire mesh 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
The type of catalyst granules, the scale of reactor and the reaction type that is carried out and change.
In injection circulation reactor provided by the invention, the base injcction device is located in the bottom filters
The heart is connected by pipeline with external pressurisation pump, and the base injcction device is hollow disc-shape, utilizes the liquid ejected at a high speed
Body material purges the solid catalyst particle of bottom filters adsorption, reduces solid catalyst and filters in bottom
Absorption on device prevents the blocking of bottom filters.
The present invention provides a kind of methods 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, gas is cut into tiny gas
Bubble, forms uniformly mixed gas-liquid two-phase in diffuser, circulation in being formed is ejected into reactor cylinder body, with the intracorporal slurry of cylinder
Liquid catalyst reacts；
(2) unconverted unstripped gas and the low boiling point gaseous products of generation are by top filter, by a small amount of solid of entrainment
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；Uncooled Gaseous materials emptying is sent to other aftertreatment technologies；
(3) liquid material in reactor shell 1 passes through filter, separates with solid catalyst, the liquid without catalyst
State material is exchanged heat in heat exchanger by circulating pump, and a part of liquid material is recycled to roof shooter, into reactor shell,
Liquid material described in another part enters in filter, the trace solid catalyst granules of liquid material entrainment is separated, separation
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.
The liquid material may include liquid product and the slurry medium for reaction.
In injection circulation reactor provided by the invention, the fluid pressure of base injcction device will be entered by the force (forcing) pump
It is increased to, preferably 0.2-0.3MPa 0.1-0.5MPa higher than the pressure in reactor cylinder body.Injection circulation provided by the invention is anti-
It answers in device, the flow rate of liquid by the roof shooter is 1-12m/s, preferably 5-10m/s.
Circulation flow reactor provided by the invention reinforces 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 may be implemented, improve alternate mass transfer and heat transfer coefficient, mention
High catalytic reaction activity；Setting bottom filters ensure that catalyst does not enter reaction pipeline and the pump housing, alleviate catalyst mill
Damage and catalyst wash away equipment, while reducing the seal request of circulating pump；It is arranged using above bottom filters
The mode of injector, continuously cleans filter, essentially eliminates the blocking of bottom filters, guarantees the long period of device
Operation；Reactor and its application method of the invention is suitable for gas-liquid-solid reaction and needs to isolate liquid from slurries
The chemical reaction process of product, such as Fischer-Tropsch synthesis, methanol-fueled CLC, using the hydrocarbon oil hydrogenation of suspension bed or paste state bed reactor
And certain embodiments.
Method provided by the invention 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 are as follows: temperature is 160-300 DEG C, preferably 180-250 DEG C, absolute pressure 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 urge when method provided by the invention is used for fischer-tropsch synthesis process for precipitated iron catalyst, molten iron
Agent or cobalt-base catalyst, the particle size range of catalyst are 1-300 μm, and preferred scope is 5-100 μm.
Detailed description of the invention
Fig. 1 is the flow chart that the present invention uses injection circulation reactor；
Fig. 2 is injection circulation reactor structural schematic diagram of the present invention；
Fig. 3 is base injcction device structural schematic diagram of the present invention；
Fig. 4 is bottom filters of the present invention and base injcction device structural schematic diagram；
Fig. 5 is roof shooter structural schematic diagram of the present invention.
It is as shown in the figure: 1. reactor shells, 2. bottom filters, 3. circulating pumps, 4. heat exchangers, 5. force (forcing) pumps, 6. filterings
Device, 7. diffusers, 8. gas-liquid separators, 9. unstripped gas, 10. liquid materials 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 after 17. condensations, 18. top filters, 19. base injcction devices, 20. roof shooters, 21.
Liquid spray orifice, 22. condensers, 23. tail gas, 24. injector inner cylinders, 25. injector outer cylinders, 26. circulating liquid entrances, 27. is former
Expect gas entrance, 28. nozzles, the outlet of 29. roof shooters, 30. reactant exits, 31. base injcction device liquid inlets.
Specific embodiment
Injection circulation reactor provided by the invention is illustrated with reference to the accompanying drawing for the tool in Fischer-Tropsch synthesis
Body embodiment, but therefore the present invention is not restricted.
As seen from Figure 1, the reactor include two parts, i.e., the part in reactor shell 1 and reactor shell with
Outer part.It include roof shooter 20, diffuser 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, which can be, any is dispersed in liquid by solid catalyst particles
The slurries formed in state substance.The injection circulation reactor includes at least part slurry that can be used in reactor shell 1
State material is drawn and the external circulating device of reactor shell 1 is returned at least part 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 to be 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
It sets the Gaseous materials after it will react and draws condensation, and be recycled back to base injcction device 19.Gaseous materials after the reaction can
Including the gaseous products obtained after reaction and the unstripped gas not converted completely in reaction, the unstripped gas may include participating in reaction
Unstripped gas and be not involved in the inert gas of reaction.
Using well known to a person skilled in the art the pipelines, valve, control device etc. by automation control or manual control
Transfer unit send unstripped gas 9 needed for reaction process to roof shooter 20.According to specific process requirement, these conveyings
Component can also include optional pump, pressurizing device, decompressor, heating device, cooling device, detection device etc..Conveying
Unstripped gas 9 may include any gas needed for reaction process, such as reactant, inert dilution gas, be used to so that reactant
System inactivates and stops the gas etc. of reaction.These unstripped gas can be mixed mutually first, be then re-fed into roof shooter 20,
Or plurality of raw materials gas can be conveyed to roof shooter 20 simultaneously according to required ratio by more parallel pipelines.
The roof shooter 20 can be arbitrary injector, and Fig. 4 shows the venturi spray that can be used as injector
Emitter structural schematic diagram.The venturi-type eductors be open downwards, opening near bore be first gradually reduced then again by
Flaring is big, and the variation of such 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 introduced 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
Equal solid matters are suspended in be formed in the substances such as the solvent, product, by-product of liquid.The height of the gas-liquid interface of the slurries
Higher than the lower position of the roof shooter diffuser 7, so that the latter is respectively positioned under gas-liquid interface.
Bottom external circulating device and top external circulating device are additionally provided in 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, produce in liquid
In the case that object continuously produces, it is optionally added into filter 6.Liquid material 10 by internal ramp 2 without catalyst is logical
It crosses circulating pump and is transported to heat exchanger 4, liquid material is transported to roof shooter 20 some or all of after heat exchanger, follows
In loopback reactor cylinder 1；Or a portion liquid material passes through filter 6, it is micro solid by what is contained in liquid material
Body catalyst filtering removes reaction system as liquid product 15；And filtered concentrated liquid material 12 with it is filtered
Liquid material 16 returns to roof shooter 20 together, to complete the bottom outer loop process of slurries.In this bottom outer circulation
In device, the devices such as the circulating pump and heat exchanger can be any suitable means well known in the art, but preferably at one
Embodiment in, the circulating pump is preferably unshrouded impeller circulating pump.
The liquid material is in the external circulating device cyclic process of bottom, after the heat exchanger 4 heat exchange, liquid
The temperature of material is generally lower than the temperature of entrance, but outlet temperature will will guarantee liquid on the fusing point of liquid material
The mobility of material, in one preferred embodiment, the liquid material compare entrance by the temperature after heat exchanger 4
Temperature it is 10-30 DEG C low, 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 of entrainment is removed after top filter 18, in condenser
It is condensed in 22, condensed liquid material and gas are adequately separated in gas-liquid separator 8, isolated liquid object
Material by or without heat exchanger 4, pass through force (forcing) pump 5 as outer circulation liquid material, send base injcction device 19 back to, into anti-
It answers in device cylinder 1.The Gaseous materials isolated are as exhaust emissions or send to other aftertreatment technologies.
By using injection circulation reactor of the invention, provide a kind of with the mixing of increase airwater mist cooling and increasing
Strong mass transfer, heat transfer slurry reactor method.Specifically, the method can follow the steps below: firstly, by raw material
Gas 9 is sent to roof shooter 20, and unstripped gas is sufficiently mixed with recycle stock in down-comer 7, and mixed material is ejected into instead
It answers in cylinder 1, drives catalyst slurry to form interior circulation in the reaction tube, reach well-mixed purpose, and complete anti-
It answers.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 top external circulating device is sent into, and the top external circulating device is 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, is recycled back within reactor shell 1, for cleaning bottom filters 2；It is unreacted
Gaseous materials are as exhaust emissions or send to other aftertreatment technologies.
Therefore, the present invention is sprayed using slurries by raw material autogenous cutting by the way that roof shooter is arranged at the top of circulation flow reactor
It is cut into small bubble, reaches the well-mixed purpose of gas-liquid, by the guiding role of down-comer, so that mixed gas-liquid object
Material contacts with catalyst slurry in reactor cylinder body and forms interior circulation.Meanwhile by top external circulating device and bottom outside
Circulator, so that at least part slurry material and Gaseous materials are returned in reactor cylinder body by external circulating device, it is right
Gas reaction material and catalyst granules in slurries play stirring, suspension effect.Above two effect combines, and enhances institute
State the particle suspension in circulation flow reactor, liquid mixes admittedly and conducts heat and mass transfer.
The reaction that this method progress can be used 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 carrying out Fischer-Tropsch synthesis 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, generate hydrocarbon product and few
The by-products such as water, the carbon dioxide of amount.In the case, the top external circulating device removes in slurries in outer loop process
Hydrocarbon product separation is then returned to base injcction device by gaseous matter.And the liquid in the external circulating device of bottom is mainly high boiling
The heavier hydrocarbon components of point remove reaction heat by bottom external circulating device, while utilizing the filtering system of bottom external circulating device
System, the heavy hydrocarbon continuous-stable of generation can be produced.
The following examples further explain method provided by the invention, 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 20 lower end of roof shooter in 1 top of reactor shell
Diffuser 7, diffuser 7 are located in reactor shell 1, have bottom filters 2 in 1 lower part of reactor shell, bottom filters 2 are in
Disc, diameter is identical as the internal diameter of reactor shell 1, and the surrounding of bottom filters 2 and the inner wall of reactor shell 1 are closed
Be connected, be equipped with base injcction device 19 in 2 centre bit of bottom filters, base injcction device 19 be embedded in bottom filters 2 just on
Side, there is reactant exit 30 in 1 bottom end of reactor shell.
Roof shooter 20 as described above includes cylinder, circulating liquid entrance 26 and nozzle 28, and cylinder is by 24 He of inner cylinder
Outer cylinder 25 forms, and the top of inner cylinder 24 is circulating liquid entrance 26, and 24 lower end of inner cylinder is connect with nozzle 28, and nozzle 28 is located at outer cylinder
In 25, the lower end of outer cylinder 25 is connect with injector outlet 29, and outer cylinder 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, has 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, high 2m, roof shooter 20 is using Venturi nozzle, the spray
7 length of emitter diffuser is 1.3m；Bottom filters 2 are the disk of diameter 0.5m, and the filter used is sintered porous metal
Net, is located at 1 bottom 1/6 of reactor shell by 1 μm of average pore size；Base injcction device 19 is embedded in the centre bit of bottom filters 2
It sets, the liquid spray orifice of diameter 1.5mm, pitch of holes 2mm is dispersed on the side wall of base injcction device 19.
The present embodiment is with H2The synthesis gas that/CO molar ratio is 2 is unstripped gas, and F- T synthesis produces liquid hydrocarbon, using cobalt-based
Catalyst, wherein the mass fraction of cobalt is 20wt%, Kong Rongwei 0.40m3/ g, specific surface area 260m2/ g, heap density are 1.0g/
cm3, 50-100 μm of particle size range.
It the described method comprises the following steps:
(1) unstripped gas 9 is introduced in roof shooter 20, is sprayed, gas is cut into tiny by the high speed of circulating liquid
Bubble, form uniformly mixed gas-liquid two-phase in diffuser 7, circulation in being formed be ejected into reactor shell 1, with cylinder
Interior slurry catalyst reacts；
(2) unconverted unstripped gas and the low boiling point gaseous products 14 of generation are by top filter 18, by lacking for entrainment
Solid catalyst particle filtering is measured, 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, and the liquid material of condensation is with or without heat exchanger 4, by adding
Press pump 5 is sent to base injcction device 19, for cleaning 2 surface of filter；The uncooled emptying of Gaseous materials 23 is sent to others
Aftertreatment technology；
(3) liquid material in reactor shell 1 passes through filter 2, separates with solid catalyst, the liquid without catalyst
State material 10 exchanges heat in heat exchanger 4 by circulating pump 3, and a part of liquid material is recycled to roof shooter 20, into reaction
Device cylinder 1, liquid material described in another part enter in filter 6, the trace solid catalyst granules that liquid material is carried secretly
Separation, the liquid material after separation are produced as liquid product 15, and the liquid material 12 after the concentration containing a small amount of catalyst recycles
To roof shooter 20, into reactor shell 1.
The flow control of circulating liquid is in 7m/s, and the product liquid after heat exchanger 4 is than the reaction in reacting cylinder body 1
Temperature is 20 DEG C low.
The operating condition of reaction are as follows: reaction temperature is 210 DEG C, absolute pressure 3.0MPa, and unstripped gas air speed is 2000h-1,
Catalyst useful load is 16% (volumn concentration).It reacts 120 hours in this operating condition, CO conversion ratio reaches in synthesis gas
92.5%.It is fractionated treated product distribution are as follows: methane selectively 5.2%, C5 +Selectivity 91%.
Medium of the condensate liquid as cleaning bottom filters is utilized in circulation flow reactor of the invention, by bottom filters table
The catalyst granules of face deposition washes, and solves the problems, such as plugged filter, ensure that the continuous-stable of product liquid
Extraction, after continuous operation 1000 hours, catalyst content 4 μ g/ of the filter there is no significantly blocking, in liquid product
ml。
Embodiment 2
The diameter 1m of injection circulation reactor, high 4m, injector 20 is using Venturi nozzle, 7 length of injector diffuser
For the 3m of reactor cylinder body length；Bottom filters 2 be diameter 1m disk, the filter used for metal micro-holes membrane material,
1 μm of average pore size, it is located at 1 bottom 1/7 of reactor shell；Base injcction device 19 is embedded in the center of bottom filters 2,
The liquid spray orifice of diameter 2mm, pitch of holes 3mm are dispersed on the side wall of base injcction device 19.
By the flow control of circulating liquid in 10m/s, the product liquid after heat exchanger 4 is than in reacting cylinder body 1
Reaction temperature low 25.
With H2The synthesis gas that/CO molar ratio is 2 is raw material, and F- T synthesis produces liquid hydrocarbon, using cobalt-based catalyst, wherein cobalt
Mass fraction be 20wt%, Kong Rongwei 0.35m3/ g, specific surface area 260m2/ g, heap density are 1.0g/cm3, particle size range 50-
100μm。
The operating condition of reactor are as follows: reaction temperature is 210 DEG C, absolute pressure 3.0MPa, and unstripped gas air speed is
2000h-1, catalyst useful load is 16% (volumn concentration), remaining is the same as embodiment 1.
It reacts 120 hours in this operating condition, CO conversion ratio is up to 91.3% in synthesis gas.It is fractionated treated product
Distribution are as follows: methane selectively 6.1%, C5 +Selectivity 90%.
Medium of the condensate liquid as cleaning bottom filters is utilized in circulation flow reactor of the invention, by bottom filters table
The catalyst granules of face deposition washes, and solves the problems, such as plugged filter, ensure that the continuous-stable of product liquid
Extraction, after continuous operation 1000 hours, catalyst content 3.5 μ g/ of the filter there is no significantly blocking, in liquid product
ml。
Embodiment 3
The diameter 1m of injection circulation reactor, high 4m, injector 20 is using Venturi nozzle, 7 length of injector diffuser
It is the 3.5 of reactor cylinder body length；Bottom filters 2 be diameter 1m disk, the filter used for micropore ceramics membrane material,
1 μm of average pore size, it is located at 1 bottom 1/6 of reactor shell；Base injcction device 19 is embedded in the center of bottom filters 2,
The liquid spray orifice of diameter 2mm, pitch of holes 2mm are dispersed on the side wall of base injcction device 19.
The flow control of circulating liquid is in 8m/s, and the product liquid after heat exchanger 4 is than anti-in reactor cylinder body
Answer temperature low 20.
With H2The synthesis gas that/CO molar ratio is 1 is raw material, and F- T synthesis produces liquid hydrocarbon, is catalyzed using quenching skeleton iron
Agent, the mass fraction of iron are 83wt%, specific surface area 51m2/ g, Kong Rongwei 0.11m3/ g, heap density are 1.2g/cm3, partial size
30-50 μm of range.
The operating condition of reactor are as follows: reaction temperature is 260 DEG C, pressure 2.0MPa, and unstripped gas air speed is 2000h-1, urge
Agent useful load is 15% (volumn concentration), remaining is the same as embodiment 1.
It reacts 120 hours in this operating condition, CO conversion ratio is up to 81.5% in synthesis gas.It is fractionated treated product
Being distributed as dry gas is 11.5wt%, liquefied gas 18.2wt%, naphtha 28.6wt%, and diesel oil 32.5wt%, hard wax is
10.8wt%.
Medium of the condensate liquid as cleaning bottom filters is utilized in circulation flow reactor of the invention, by bottom filters table
The catalyst granules of face deposition washes, and solves the problems, such as plugged filter, ensure that the continuous-stable of product liquid
Extraction, after continuous operation 1000 hours, catalyst content 2.0 μ g/ of the filter there is no significantly blocking, in liquid product
ml。
Claims (15)
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 diffuser (7), and diffuser (7) is located in reactor shell (1), in reactor shell (1) lower part
Have bottom filters (2), bottom filters (2) are in disk form, and diameter is identical as the internal diameter of reactor shell (1), bottom mistake
The surrounding of filter (2) with the inner wall of reactor shell (1) is closed is connected, in bottom filters (2), centre bit is equipped with base injcction
Device (19), base injcction device (19) are embedded in the surface of bottom filters (2), and reactor shell (1) bottom end has reactant to go out
Mouth (30), the base injcction device (19) are hollow disk, have 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), there is liquid inlet (31) below base injcction device (19).
2. a kind of injection circulation reactor as described in claim 1, it is characterised in that the roof shooter (20) includes
Cylinder, circulating liquid entrance (26) and nozzle (28), cylinder are made of inner cylinder (24) and outer cylinder (25), and the top of inner cylinder (24) is
Circulating liquid entrance (26), inner cylinder (24) lower end are connect with nozzle (28), and nozzle (28) is located in outer cylinder (25), outer cylinder (25)
Lower end is connect with injector outlet (29), and outer cylinder (25) has unstripped gas entrance (27), and unstripped gas entrance (27) is located at nozzle (28)
On.
3. a kind of injection circulation reactor as described in claim 1, it is characterised in that diffuser (7) length is reactor
The 1/2-4/5 of cylinder (1) height.
4. a kind of injection circulation reactor as claimed in claim 3, it is characterised in that diffuser (7) length is reactor
The 2/3-4/5 of cylinder height.
5. a kind of injection circulation reactor as claimed in claim 4, 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.
6. a kind of injection circulation reactor as described 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.
7. a kind of use technique of injection circulation reactor as claimed in any one of claims 1 to 6, it is characterised in that
The following steps are included:
(1) unstripped gas is introduced in roof shooter (20), is sprayed by the high speed of circulating liquid, gas is cut into tiny gas
Bubble forms uniformly mixed gas-liquid two-phase in diffuser (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 point gaseous products of generation are by top filter (18), by a small amount of solid of entrainment
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 bottom filters (2) surface；Uncooled Gaseous materials emptying is sent
To other aftertreatment technologies；
(3) liquid material in reactor shell (1) passes through bottom filters (2), separates with solid catalyst, is free of catalyst
Liquid material by circulating pump (3), heat exchange, a part of liquid material in the heat exchanger (4) are recycled to roof shooter (20),
Into reactor shell (1), liquid material described in another part enters in filter (6), by the micro solid of liquid material entrainment
The separation of body catalyst particle, the liquid material after separation are produced as liquid product, the liquid after the concentration containing a small amount of catalyst
Matter Transfer is to roof shooter (20), into reactor shell (1).
8. a kind of use technique of injection circulation reactor as claimed in claim 7, it is characterised in that the force (forcing) pump (5) will
Into base injcction device (19) fluid pressure be increased to it is 0.1-0.5MPa higher than the pressure in reactor shell (1).
9. a kind of use technique of injection circulation reactor as claimed in claim 8, it is characterised in that the force (forcing) pump 5 will be into
Enter base injcction device (19) fluid pressure be increased to it is 0.2-0.3MPa higher than the pressure in reactor shell (1).
10. a kind of use technique of injection circulation reactor as claimed in claim 7, it is characterised in that the roof shooter
(20) flow rate of liquid is 1-12m/s.
11. a kind of use technique of injection circulation reactor as claimed in claim 10, it is characterised in that the top jet
The flow rate of liquid of device (20) is 5-10m/s.
12. a kind of use technique of injection circulation reactor as claimed in claim 7, it is characterised in that unstripped gas is synthesis
Gas produces liquid hydrocarbon or paraffin for F- T synthesis, the operating condition in reactor shell (1) are as follows: and temperature is 160-300 DEG C,
Absolute pressure is 1.0-5.5MPa, and the air speed of unstripped gas is 500-5000h-1。
13. a kind of use technique of injection circulation reactor as claimed in claim 12, it is characterised in that reactor shell (1)
Interior operating condition are as follows: temperature is 180-250 DEG C, absolute pressure 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.
14. a kind of use technique of injection circulation reactor as claimed in claim 13, it is characterised in that the partial size of catalyst
Range is 1-300 μm.
15. a kind of use technique of injection circulation reactor as claimed in claim 13, it is characterised in that the partial size of catalyst
Range is 5-100 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611043568.7A CN106732208B (en) | 2016-11-24 | 2016-11-24 | A kind of injection circulation reactor and application method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611043568.7A CN106732208B (en) | 2016-11-24 | 2016-11-24 | A kind of injection circulation reactor and application method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106732208A CN106732208A (en) | 2017-05-31 |
| CN106732208B true CN106732208B (en) | 2019-06-25 |
Family
ID=58974790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611043568.7A Active CN106732208B (en) | 2016-11-24 | 2016-11-24 | A kind of injection circulation reactor and application method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106732208B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110538616B (en) * | 2019-09-18 | 2022-05-03 | 中国石油化工股份有限公司 | Device and method for producing low-viscosity methyl silicone oil |
| CN112340915A (en) * | 2020-10-21 | 2021-02-09 | 南京延长反应技术研究院有限公司 | Wet-type oxidation micro-interface system |
| CN112342055B (en) * | 2020-10-21 | 2023-03-24 | 南京延长反应技术研究院有限公司 | Hydrogenation strengthening micro-interface system |
| CN112322347B (en) * | 2020-10-21 | 2023-03-24 | 南京延长反应技术研究院有限公司 | Hydrogenation micro-interface system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203196620U (en) * | 2013-04-24 | 2013-09-18 | 成都天成碳一化工有限公司 | Reactor for producing methyl formate through carbonylation |
| CN103977746A (en) * | 2013-02-08 | 2014-08-13 | 上海碧科清洁能源技术有限公司 | Slurry bed reactor and method for using thereof |
| CN105218803A (en) * | 2015-09-01 | 2016-01-06 | 南京大学 | A kind of device and method of serialization synthesis poly (propylene carbonate) polyvalent alcohol |
| CN105903425A (en) * | 2016-04-21 | 2016-08-31 | 南京大学 | Jet reactor |
-
2016
- 2016-11-24 CN CN201611043568.7A patent/CN106732208B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977746A (en) * | 2013-02-08 | 2014-08-13 | 上海碧科清洁能源技术有限公司 | Slurry bed reactor and method for using thereof |
| CN203196620U (en) * | 2013-04-24 | 2013-09-18 | 成都天成碳一化工有限公司 | Reactor for producing methyl formate through carbonylation |
| CN105218803A (en) * | 2015-09-01 | 2016-01-06 | 南京大学 | A kind of device and method of serialization synthesis poly (propylene carbonate) polyvalent alcohol |
| CN105903425A (en) * | 2016-04-21 | 2016-08-31 | 南京大学 | Jet reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106732208A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106732208B (en) | A kind of injection circulation reactor and application method | |
| CN102137715A (en) | Parallelized jet loop reactors | |
| CN106629622B (en) | A kind of method for hydrogenation and hydrogenation apparatus of hydrogeneous anthraquinone working solution | |
| CN109985572A (en) | A kind of hydroenhancement mixing serialization hydrogenation reaction device and process | |
| CN102416307B (en) | A kind of internal-circulation type paste state bed reactor and application thereof | |
| CN101293195A (en) | Stirring/flow-guiding multi-phase reactor | |
| CN109847658A (en) | Paste state bed reactor and reaction method | |
| CN109701456A (en) | A kind of novel radial reactor | |
| CN206616014U (en) | A kind of hydrogenation apparatus of hydrogeneous anthraquinone working solution | |
| CN106540637B (en) | A kind of circulation flow reactor and application method | |
| CN100420731C (en) | Coal hydrogenation reaction device and its industrial application | |
| CN103962068A (en) | Slurry bed reactor | |
| CN204656509U (en) | Airlift circulating reactor | |
| CN108295859B (en) | Preparation method and application of Ni-based catalyst microspheres | |
| CN101275080B (en) | Fischer-Tropsch synthesis process based on fixed bed reactor | |
| CN104549065A (en) | Slurry-bed circulation flow reactor and application and method for producing hydrogen peroxide | |
| CN203699908U (en) | Anthraquinone process hydrogen peroxide production device | |
| CN204342435U (en) | The hydrogenation fluidized-bed reactor of anthraquinone legal system hydrogen peroxide | |
| CN108440281A (en) | Chemical reaction equipment and its application | |
| CN104549058A (en) | Slurry bed reactor catalyst filtering application system device | |
| CN104628524B (en) | A kind of slurry bed reactor catalyst filtration technique for applying | |
| WO2014121720A1 (en) | A slurry-bed reactor and a method for conduction slurry-bed reaction using the slurry-bed reactor | |
| CN210434485U (en) | Slurry bed reactor and reaction system for Fischer-Tropsch synthesis | |
| CN104341259A (en) | Synthetic gas catalytic methanation method and device | |
| CN107185476A (en) | A kind of multistage, multi-functional injection reactor assembly and its operating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |