CN110523350A - The method of paste state bed reactor and F- T synthesis - Google Patents
The method of paste state bed reactor and F- T synthesis Download PDFInfo
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- CN110523350A CN110523350A CN201810510409.6A CN201810510409A CN110523350A CN 110523350 A CN110523350 A CN 110523350A CN 201810510409 A CN201810510409 A CN 201810510409A CN 110523350 A CN110523350 A CN 110523350A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
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- General Chemical & Material Sciences (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The present invention relates to hydro carbons to synthesize field, specifically provide a kind of paste state bed reactor and Fischer-Tropsch synthesis method, the reactor includes: the reactor inlet section being arranged from bottom to top, gas distributor, the gentle solid-liquor separation section of conversion zone, the solid-liquid separator with the liquid product stream outlet of reactor is internally provided in the conversion zone, multiple slurries diversion components are set in the side wall of the conversion zone, the slurries diversion component is used to the reaction paste of the wall region of conversion zone forcing back-mixing to the axial region of conversion zone along the slurries diversion component.Compared with prior art, reactor of the invention is applied to gas-liquid-solid phase reaction, can be obviously improved the performance of catalyst, and the attrition of catalyst is obviously reduced.
Description
Technical field
The present invention relates to hydro carbons to synthesize field, more particularly to a kind of paste state bed reactor and a kind of side of F- T synthesis
Method.
Background technique
As oil price is constantly soaring in recent years, people increasingly pay attention to the technology of development and production substitution oil product, pass through
Coal, natural gas or other materials produce synthesis gas, and the requirement further according to fischer-tropsch synthetic catalyst to synthesis gas is become by water-gas
It changes and synthesis gas is handled with purified synthesis gas technique, hydro carbons is produced by F- T synthesis using synthesis gas after processing as raw material,
Then by-product oxygenatedchemicals simultaneously is processed using mature Petroleum Processing Technology, produces the environmental-friendly of high quality
Oil product.Fischer-Tropsch synthetic technology is developed, is had very important significance to the production technology of development substitution oil product.
Fischer-Tropsch synthesis device is the core reaction device of F- T synthesis technology, and being widely used both at home and abroad at present being capable of voluminous hydrocarbon
The three phase slurry bed reactor of product.Paste state bed reactor is uniformly easily-controllable with temperature, gas velocity opereating specification is wide, product Alpha
The advantages that value is high, catalyst can replace online.
CN1233451C discloses a kind of gas-liquid-solid three-phase slurry bed system industrial reactor that can be operated continuously, the reactor
Inlet gas distributed elements including the progress even gas distribution being made of inlet gas distributor pipe, one or more layers carries out bed
Heating/cooling heat exchanger tube component, one or more layers liquid-solid separator component that can be cleaned automatically remove liquid foam and solid folder
The outlet dedusting demister component of band.
CN101391198B discloses a kind of slurry bed system synthesis reactor, the reactor include conversion zone, reactor inlet,
Reactor outlet and the extension diameter section that slurry bed system top is arranged in, the extension diameter section includes settling section, washing section and foam removal section.
CN1233451C proposes the gas-liquid-solid three-phase slurry bed system industrial reactor of continuous operation, it is believed that can go out in reactor
Liquid foam and solid entrainment are removed at mouthful, while temperature and Liquid level are good.F- T synthesis paste state bed reactor requires catalyst
Granularity between 20-100 microns, otherwise catalyst and product can not form slurries phase, but this also bring by catalyst with
The problem of Fischer-Tropsch synthetic (including the liquid and gas product under reaction condition) separation.
In particular with the progress of reaction, catalyst abrasion is more and more severe, and average diameter of particles is smaller and smaller, gas-solid point
From being increasingly difficult to, solid entrainment is serious, influences subsequent operation.
Summary of the invention
The slurry bed system of the mass-and heat-transfer inside gas-liquid-solid slurry phase reactor can be improved the object of the present invention is to provide one kind
Reactor and a kind of mass-and heat-transfer that can improve gas-liquid-solid promote the performance of catalyst and the Fischer-Tropsch for the abrasion for reducing catalyst
Synthetic method.
The present inventor thinks that the fluid motion inside slurry bed system is more multiple by the F- T synthesis research of many years
Miscellaneous, the physico-chemical properties performance such as the performance of catalyst and abrasion is not only controlled with the temperature of paste state bed reactor, gas distributor etc.
Component is related, also related in the heat and mass and fluid motion speed of inside reactor with slurries.
Therefore when design paste state bed reactor, need to consider improvement gas-liquid-solid slurry phase reactor inside mass-and heat-transfer,
And influence of the rate of fluid to catalyst abrasion.When specifically applying to Fischer-Tropsch synthesis, Fischer-Tropsch synthesis is one
Whether the strong exothermal reaction of gas-liquid-solid three-phase, the distribution of Fischer-Tropsch synthetic and the property of catalyst and the temperature of inside reactor
Uniformly, the concentration distribution of catalyst, gas holdup distribution and fluid flow rate have very big relationship.
Background technique provided by the invention be related to it is above-mentioned in the prior art, the design of Fischer-Tropsch synthesis device mainly collects
In in common inner member, such as gas distributor, heat exchanger and the gas-liquid separator of tower top etc., it is less to consider how to adjust
Control the hydrodynamics of inside reactor.And the present inventor thinks, in the design of Fischer-Tropsch synthesis device, reinforces
Mass transfer inside paste state bed reactor, being evenly distributed for heat transfer, and pressure gas holdup, serum density etc. are conducive to improve indirectly
The service performance of catalyst and the abrasion for reducing catalyst.
The object of the present invention is to provide a kind of novel slurry bed ft synthetic reactors and technique, can not only improve anti-
Device internal mass transfer is answered to conduct heat, additionally it is possible to which the slurries back-mixing rate for reducing inside reactor reduces the rate of depreciation of catalyst, in turn
Improve catalyst performance.
To realize foregoing purpose, according to the first aspect of the invention, the present invention provides a kind of paste state bed reactors, this is anti-
Answering device includes: the reactor inlet section being arranged from bottom to top, gas distributor, the gentle solid-liquor separation section of conversion zone, wherein in institute
It states conversion zone and is internally provided with solid-liquid separator with the liquid product stream outlet of reactor, in the side wall of the conversion zone
Multiple slurries diversion components are set, and the slurries diversion component is used for the reaction paste of the wall region of conversion zone along described
Slurries diversion component forces back-mixing to the axial region of conversion zone.
According to the second aspect of the invention, the present invention provides a kind of methods of F- T synthesis, and this method is in institute of the present invention
It is carried out in the reactor stated, wherein this method comprises: synthesis gas enters from reactor inlet section, be distributed by gas distributor
Enter conversion zone after uniformly and contacts progress Fischer-Tropsch synthesis with catalysts and solvents；Wherein, the wall region of conversion zone is anti-
Slurry is answered to force back-mixing to the axial region of conversion zone along the slurries diversion component；Reaction paste passes through the degassing liquid collecting
Back-mixing is forced after diversion component removing gas in conversion zone, tail gas, which enters gas-liquid-solid segregation section, to carry out de- liquid and take off admittedly, then
Discharge；Liquid material is discharged after solid-liquid separator separates solid from the product liquid outflux of reactor.
Compared with prior art, reactor of the invention is applied to gas-liquid-solid phase reaction, can be obviously improved catalyst
Performance, and the attrition of catalyst is obviously reduced, thus it is speculated that is thus further demonstrated since mass-and heat-transfer is strengthened
The conception that the present inventor proposes in research.
Detailed description of the invention
Fig. 1 is the cross-sectional view of paste state bed reactor of the invention；
Fig. 2 is the cross-sectional view of slurries diversion component according to a preferred embodiment of the present invention；
Fig. 3 is the cross-sectional view of degassing liquid collecting diversion component according to a preferred embodiment of the present invention；
Fig. 4 is the top view of degassing liquid collecting diversion component according to a preferred embodiment of the present invention.
Description of symbols
1 reactor inlet section；2 gas distributors；
3 conversion zones；4 gas-liquid-solid segregation sections；
5 tail gas；6 degassing liquid collecting diversion components；
7 solid-liquid separators；8 choana sections
9 water conservancy diversion pipeline sections；The deflector hole of 10 choana sections
Deflector hole on 11 slurries diversion component, 12 rectangular slab
D1 taper round mouth diameter；The diameter of the straight round tube of D2 water conservancy diversion
Water conservancy diversion bore dia on the diameter D4 rectangular slab of the deflector hole of D3 choana section
The length of S axial region L rectangular slab
The width of W rectangular slab
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In the present invention, in the case where being not specifically noted, the noun of locality used such as " upper and lower, left and right " is typically referred to
Accordingly refer to upper and lower, left and right shown in the drawings；" inside and outside " refers to relative to the inside and outside of each component or component itself profile.
Method provided by the present invention is further described with reference to the accompanying drawing, but the present invention not therefore and by
To any restrictions.In order to protrude process thought of the invention, many necessary equipment when industrial application are omitted in figure, such as pump,
Valve and the heat exchange equipment of inside reactor etc..Since above equipment is the conventional arrangement of this field, the present invention is herein
Without detailed description.
As before, as Figure 1-Figure 4, the present invention provides a kind of paste state bed reactor, which includes: from bottom to top
Reactor inlet section 1, gas distributor 2, the gentle solid-liquor separation section 4 of conversion zone 3 of setting, wherein inside the conversion zone 3
It is provided with the solid-liquid separator 7 with the liquid product stream outlet of reactor, multiple slurries are set in the side wall of the conversion zone 3
Liquid diversion component 11, the slurries diversion component 11 are used for the reaction paste of the wall region of conversion zone 3 along the slurries
Diversion component 11 forces back-mixing to the axial region S of conversion zone 3.
The axial region refers to the region near radially extending using the axis of conversion zone as center line, such as horizontal
Region apart from the 0-3/4 that the axis is conversion zone radius, the region S as shown in Figure 1.
According to the present invention, by the way that the slurries diversion component is arranged, so that reactor of the invention is used for gas-liquid-solid three-phase
When reaction, it can be obviously improved the performance of catalyst, and the attrition of catalyst is obviously reduced, thus it is speculated that be due to of the invention
The reason of inside reactor mass-and heat-transfer is strengthened is caused.
Slurries diversion component provided by the invention, by the slurries water conservancy diversion in reactor wall region to reactor central region, instead
Answer the slurries gas holdup at wall region low, density is big, and reactor central region slurries gas holdup is high, and density is low, therefore starches
After liquid diversion component water conservancy diversion slurries, the air pocket inside slurries can be destroyed, the gap of gas holdup is reduced, thus reduced slurries and cut
To opposite rate, the abrasion of catalyst is reduced.
, according to the invention it is preferred to the slurries diversion component 11 is arranged in the sidewall slope of the conversion zone 3, it is preferably described
Inclination angle is 15-60 °.Thus, it is possible to greatly reinforce the effect of slurries diversion component, when being specifically applied to reaction, can obviously change
The performance of kind catalyst, and the attrition of catalyst is obviously reduced.
Wherein, the inclination angle refers to the angle of slurries diversion component and horizontal plane.
Wherein, the slurries diversion component 11 can be tilted or be tilted down upwards.
According to the present invention, depending on the length of the slurries diversion component can be according to the specific size of reactor, for existing
Some paste state bed reactors, the length of the preferably described slurries diversion component are 0.3-3m, preferably 0.5-2m.
According to the present invention, as long as the slurries diversion component 11 can be realized the above-mentioned function of the present invention, to its shape
Shape and material etc. are without particular/special requirement, as long as not influencing reaction.A preferred embodiment of the invention, the slurries
Diversion component 11 includes rectangular slab and the multiple deflector holes 12 being arranged on the rectangular slab.
A preferred embodiment of the invention, the length and width ratio of the preferably described rectangular slab is L/W=2-10, more excellent
Select L/W=3-8；Wherein L refers to the length of rectangular slab, and W refers to the width of rectangular slab.Thus, it is possible to greatly reinforce slurries to lead
The effect of stream unit can be obviously improved the performance of catalyst, and the attrition of catalyst is obvious when being specifically applied to reaction
Reduce.
A preferred embodiment of the invention, the diameter D4 of the preferably described deflector hole 12 are 0.01-0.2m.Thus
The effect that slurries diversion component can be greatly reinforced can be obviously improved the performance of catalyst, and urge when being specifically applied to reaction
The attrition of agent is obviously reduced.
According to the present invention, the number of the deflector hole is determined according to the size of slurries diversion component, according to the present invention one
Kind preferred embodiment, the number of the preferably described deflector hole 12 are 2-16, more preferably 4-10.Thus, it is possible to greatly reinforce
The effect of slurries diversion component can be obviously improved the performance of catalyst, and the abrasion of catalyst disappears when being specifically applied to reaction
Consumption is obviously reduced.
A preferred embodiment of the invention, the length of rectangular slab are 0.3-3m, more preferably 0.5-2m.Thus
The effect that slurries diversion component can be greatly reinforced can be obviously improved the performance of catalyst, and urge when being specifically applied to reaction
The attrition of agent is obviously reduced.
A preferred embodiment of the invention, the slurries diversion component 11 along the conversion zone 3 side wall
Radially uniform distribution, quantity 2Q, Q=1-10, preferably 2-8.Thus, it is possible to greatly reinforce the effect of slurries diversion component,
When being specifically applied to reaction, it can be obviously improved the performance of catalyst, and the attrition of catalyst is obviously reduced.
A preferred embodiment of the invention, the slurries diversion component 11 is on the side wall of the conversion zone 3
Under be divided into 2-10 layers of distribution, preferably 2-6 layers.Thus, it is possible to greatly reinforce the effect of slurries diversion component, it is specifically applied to react
When, it can be obviously improved the performance of catalyst, and the attrition of catalyst is obviously reduced.
, according to the invention it is preferred to be internally provided with multiple degassing liquid collecting diversion components 6, the degassing in the conversion zone 3
Liquid collecting diversion component 6 includes the choana section 8 being connected to from top to bottom and water conservancy diversion pipeline section 9.
In the present invention, the set-up mode of the degassing liquid collecting diversion component is without particular/special requirement, such as can pass through welding
Mode is welded on inside conversion zone.
According to the present invention, by the way that the degassing liquid collecting diversion component is arranged, so that reactor of the invention is used for gas-liquid-solid
When phase reaction, it can be obviously improved the performance of catalyst, and the attrition of catalyst is obviously reduced, thus it is speculated that be due to this hair
The reason of bright inside reactor mass-and heat-transfer is strengthened is caused.
Reactor according to the present invention, when being used for gas-liquid-solid phase reaction, degassing liquid collecting diversion component deaerates slurries
Afterwards, since density increases, water conservancy diversion to diversion pipe lower part forces back-mixing, mass transfer enhancement heat transfer.
, according to the invention it is preferred to the maximum of the maximum cross section area of the choana section 8 and the water conservancy diversion pipeline section 9
The ratio of cross-sectional area is 9-100.Within the scope of the ratio of above-mentioned cross-sectional area, degassing liquid collecting diversion component can be greatly reinforced
Effect, be specifically applied to reaction when, the performance of catalyst can be obviously improved, and the attrition of catalyst is obviously reduced.
, according to the invention it is preferred to which the axis of the choana section 8 and the angle of bus are 15 ° -70 °, more preferably
21°-60°.Thus, it is possible to maximize the effect for playing degassing liquid collecting diversion component.
According to the present invention, as long as described guarantee that the degassing liquid collecting diversion component has choana section, to tool
The funnel-form form of body is cone without particular/special requirement, a preferred embodiment of the invention, the choana section 8
Shape.
According to the present invention, the setting form of the water conservancy diversion pipeline section can be diversified, can be reducer pipe, or same
Diameter pipe can be rectangular tube, or round tube.
A preferred embodiment of the invention, the water conservancy diversion pipeline section 9 are the straight round tube of water conservancy diversion.
A kind of more preferable embodiment according to the present invention, the diameter D2 of the taper round mouth diameter D1 and the straight round tube of water conservancy diversion
Ratio be 3-10.
According to the present invention, it is the endurance for reducing the degassing liquid collecting diversion component, its service life is improved, preferably in institute
State the circumferential setting deflector hole 10 of choana section 8.
According to the present invention, the diameter of the deflector hole can be configured according to the size of choana section, needle
To the present invention, the diameter D3 of the preferably described deflector hole 10 is 0.01-0.1m.
A preferred embodiment of the invention is evenly arranged with n in the circumferential direction of the choana section 8 and leads
Discharge orifice, n are 2-16, preferably 4-10.
According to the present invention, the degassing liquid collecting diversion component size setting can be carried out according to the size of paste state bed reactor
Selection, according to the present invention, when conventional paste state bed reactor applied to the prior art, the height of the degassing liquid collecting diversion component 6
Degree can be set to 1-5m, preferably 1.5-4m.
The height ratio of a preferred embodiment of the invention, the water conservancy diversion pipeline section 9 and choana section 8 is 1-
10:1, more preferably 1-6:1.
According to a kind of preferred embodiment of invention, the degassing liquid collecting diversion component 2-100.
A preferred embodiment of the invention, the degassing liquid collecting diversion component 6 divide M layers to set in conversion zone 3
It sets, M 2-10, more preferably 2-6.
A preferred embodiment of the invention, the degassing liquid collecting diversion component 6 of every layer of setting are 2N, N 1-
10, preferably 2-8.
A preferred embodiment of the invention, the slurries diversion component 11 is on the side wall of the conversion zone 3
Lower leaf distribution, preferably 2-10 layers of distribution, more preferable 2-6 layers of distribution；The degassing liquid collecting diversion component (6) is in conversion zone (3)
Inside divide M layers of setting, M 2-10, more preferably 2-6.
A preferred embodiment of the invention, the more preferable slurries diversion component layer are led with the degassing liquid collecting
Stream unit layer along conversion zone 3 axially staggered distribution.
According to the present invention, unrestricted whether the degassing liquid collecting diversion component number of every layer of setting is identical, preferably every layer sets
The degassing liquid collecting diversion component set is identical, in the specific implementation process, can slightly adjust according to the actual situation, such as due to anti-
Answer the number that can be set in the case where causing spatial dimension not allow when other inner members are set in device different.
The degassing liquid collecting diversion component is set in the manner described above, the work of degassing liquid collecting diversion component can be greatly reinforced
With the performance of catalyst can be obviously improved, and the attrition of catalyst is obvious when being specifically applied to gas-liquid-solid phase reaction
Reduce.
When being used for Fischer-Tropsch synthesis, since F- T synthesis is exothermic reaction, reactor preferably of the invention further includes
For the heat exchanger components of heat exchange, thus heat of reaction can be tieed up by taking heat out of reactor after heat exchanger components exchange heat
Temperature of reactor is held to stablize.
The heat exchanger components are, for example, heat exchanging pipe, therefore heat can pass through the latent of the high-temperature water flowed in heat exchanging pipe
Heat takes heat out of reactor, and temperature of reactor is maintained to stablize.
The set-up mode of the heat exchanger components can be configured according to the conventional arrangement mode of this field, and the present invention is to this
Without particular/special requirement.
According to the present invention, the gas-liquid-solid segregation section at the top of paste state bed reactor provided by the invention can be using this field
The design in paste state bed reactor known, such as can be arranged in the form of being provided in CN101391198B.
According to the present invention, the reactor inlet section, gas distributor, conversion zone, solid-liquid separator setting can be by
It is configured according to the conventional method of this field, this is not described in detail here by the present invention.
The present invention provides a kind of method of F- T synthesis, this method carries out in reactor of the present invention, wherein
This method comprises: synthesis gas enters from reactor inlet section 1, enters conversion zone 3 after gas distributor 2 is evenly distributed and urge
Agent and solvent contact carry out Fischer-Tropsch synthesis, wherein the reaction paste of the wall region of conversion zone 3 is led along the slurries
Stream unit 11 forces back-mixing to the axial region S of conversion zone 3；Reaction paste removes gas by the degassing liquid collecting diversion component 6
Back-mixing is forced after body in conversion zone 3, tail gas, which enters gas-liquid-solid segregation section 4, to carry out de- liquid and take off admittedly, is then discharged out；Liquid material
It is discharged after solid-liquid separator 7 separates solid from the product liquid outflux of reactor.
According to the method for the present invention, happens is that gas-liquid-solid phase reaction, internal liquid flow pattern in paste state bed reactor
Belong to heterogeneous flow pattern, the gas holdup of reactor axially and radially, catalyst concn is all very different.All things considered, reaction
Bubble is big at device center, and gas holdup is high, and catalyst concn is low；Region bubble is small at wall of reactor, and gas holdup is low, and catalyst is dense
Degree is high；Thus it forms central area gas-liquid inside Fischer-Tropsch synthesis device to flow up, the part that wall nearby flows downward is followed
Ring back-mixing state.
The inventors of the present invention discovered through researches that liquid dispersion is very acute when the gas holdup difference in different zones is too big
Strong, tangentially opposite rate maximum can achieve 20-30m/s to slurries, and catalyst abrasion is caused to aggravate.
According to the method for the present invention, the slurries diversion component and degassing liquid collecting diversion component, can destroy inside slurries
Air pocket, reduce the gap of gas holdup, thus reduce the tangential opposite rate of slurries.It is possible thereby to further increase catalyst
Performance reduces the abrasion of catalyst.
A preferred embodiment of the invention, wherein the speed that preferably synthetic gas enters from reactor inlet section 1
For 5-40cm/s；The speed of tail gas discharge is 8-25cm/s.
According to the present invention, the Fischer-Tropsch synthesis condition can be the conventional selection of this field, and the present invention is unknown herein
Thin description.
According to the present invention, gas-liquid-solid three-phase generates hydro carbons and produces inside paste state bed reactor after Fischer-Tropsch synthesis
Product.Liquid product carries out subsequent processing by discharge after being distributed in the liquid-solid separator filtering of inside reactor, and tail gas passes through anti-
Enter follow-up equipment after answering the gas-liquid-solid segregation section at the top of device to remove catalyst and liquid to be handled.
According to the present invention, the solvent can be the conventional selection of this field, for example, liquid wax and/or heavy diesel fuel.
A preferred embodiment of the invention, as shown in Figure 1, synthesis gas (carbon monoxide and hydrogen) is from slurry bed system
The reactor inlet section 1 of reactor bottom enters, and conversion zone 3 is entered after gas is evenly distributed after gas distributor 2.Instead
It answers and is previously charged into liquid wax and fischer-tropsch catalysts inside device.Gas-liquid-solid three-phase after Fischer-Tropsch synthesis, is given birth in inside reactor
At hydrocarbon products.By being discharged after being distributed in the filtering of solid-liquid separator 7 of inside reactor, tail gas 5 passes through liquid hydrocarbon product
The gas-liquid-solid segregation section 4 of reactor head enters subsequent processing after isolating catalyst and liquid wax.
The gas-liquid-solid slurries of the wall region of conversion zone 3 are along the slurries diversion component 11 to the axial area of conversion zone 3
Domain S forces back-mixing；The gas-liquid-solid slurries of inside reactor deaerate on degassing 6 top of liquid collecting diversion component, from degassing liquid collecting water conservancy diversion
The water conservancy diversion pipeline section 9 and deflector hole 10 of component 6 are discharged, and achieve the purpose that increase mass-and heat-transfer.
Embodiment 1
F- T synthesis paste state bed reactor internal diameter is 5m, total reactor height 45m, upper layer and lower layer peace in paste state bed reactor
Removable gas liquid collecting diversion component, degassing liquid collecting diversion component top is taper, lower part is water conservancy diversion straight tube, the axis of conical section and mother
The angle of line is 30 °, is evenly arranged with 6 deflector holes on each degassing liquid collecting diversion component, degassing liquid collecting diversion component totally 48
It is a, 24 every layer, wherein D1=0.5m, D2=0.15m, D3=0.08m, the water conservancy diversion pipeline section 9 and choana section 8
Height is than being 5:1；The total height of single degassing liquid collecting diversion component is 3m, using entrance as initial position, first layer degassing collection
The setting position of liquid diversion component is at the 23-26m of reactor, and the setting position of second layer degassing liquid collecting diversion component is reaction
At the 30-33m of device；
Slurries diversion component totally 16, divide upper layer and lower layer, 8 every layer, wherein L=1.5m, W=0.5m, inclination angle are
30°；
6 deflector holes, D4=0.1m are set on each slurries diversion component；
Slurries diversion component layer and degassing liquid collecting diversion component layer are staggered；
Reaction condition includes:
Pressure into reactor gas-liquid-solid segregation section tail gas is 2.9Mpa, and the velocity of discharge of tail gas is 15cm/s, synthesis
The flow velocity that gas enters is 20cm/s, and reactor temperature is 250 DEG C.Filling fischer-tropsch synthetic catalyst is iron-based catalysis in slurry bed system
Agent, size distribution are 30-100 μm, 80 microns of average grain diameter；Reaction dissolvent is paraffin, H in fresh synthesis gas2/ CO=1.7 (rubs
Your ratio), after 1000h is operated, the conversion ratio of carbon monoxide is stablized 94%, and methane selectively is stablized 2.8%, titanium dioxide
Carbon selectivity is stablized 17.3%；
After F- T synthesis device operates 1000h, the catalyst in catalyst slurry is taken out.Through detecting, catalyst grain size point
Cloth is 25-90 μm, 70 μm of average grain diameter.
Comparative example 1
Paste state bed reactor internal diameter is 5m, total reactor height 45m, and degassing liquid collecting is not loaded onto paste state bed reactor and is led
Stream unit and slurries diversion component.
Reaction condition includes:
Pressure into reactor gas-liquid-solid segregation section tail gas is 2.9Mpa, and the velocity of discharge of tail gas is 15cm/s, synthesis
The flow velocity that gas enters is 20cm/s, and reactor temperature is 250 DEG C.Filling fischer-tropsch synthetic catalyst is iron-based catalysis in slurry bed system
Agent, size distribution are 30-100 μm, 80 microns of average grain diameter；Reaction dissolvent is paraffin, H in fresh synthesis gas2/ CO=1.7 (rubs
Your ratio), after 1000h is operated, the conversion ratio of carbon monoxide is stablized 91%, and methane selectively is stablized 4.5%, titanium dioxide
Carbon selectivity is stablized 22.1%；After taking out the catalyst in catalyst slurry, measuring catalyst grain size distribution is 15-90 μm,
65 μm of average grain diameter.
Can be seen that the present invention by above-mentioned comparison has raising catalyst performance, reduces the advantage of catalyst abrasion.
Claims (11)
1. a kind of paste state bed reactor, which includes: the reactor inlet section (1) being arranged from bottom to top, gas distributor
(2), the gentle solid-liquor separation section (4) of conversion zone (3), wherein be internally provided in the conversion zone (3) and produced with the liquid of reactor
The solid-liquid separator (7) of stream outlet connection, which is characterized in that multiple slurries water conservancy diversion are set in the side wall of the conversion zone (3)
Component (11), the slurries diversion component (11) are used for the reaction paste of the wall region of conversion zone (3) along the slurries
Diversion component (11) forces back-mixing to the axial region (S) of conversion zone (3).
2. reactor according to claim 1, wherein side of the slurries diversion component (11) in the conversion zone (3)
Wall is obliquely installed, and the preferably described inclination angle is 15-60 °.
3. reactor according to claim 1 or 2, wherein
The slurries diversion component (11) includes rectangular slab and multiple deflector holes (12) for being arranged on the rectangular slab；
It is preferred that the length and width ratio of the rectangular slab is L/W=2-10, more preferable L/W=3-8；
It is preferred that the diameter D4 of the deflector hole (12) is 0.01-0.2m；
It is preferred that the number of the deflector hole (12) is 2-16, more preferably 4-10；
It is preferred that the length of rectangular slab is 0.3-3m, more preferably 0.5-2m.
4. reactor according to claim 3, wherein the slurries diversion component (11) is along the conversion zone (3)
The radially uniform distribution of side wall, quantity 2Q, Q=1-10, preferably 2-8；
The slurries diversion component (11) is divided into 2-10 layers of distribution up and down in the side wall of the conversion zone (3), and preferably 2-6 layers.
5. reactor according to claim 1 or 2, wherein be internally provided with multiple degassing liquid collectings in the conversion zone (3)
Diversion component (6), degassing liquid collecting diversion component (6) includes the choana section (8) being connected to from top to bottom and diversion pipe
Section (9)；
It is preferred that the maximum cross section area of the maximum cross section area of the choana section (8) and the water conservancy diversion pipeline section (9)
Ratio be 9-100；
It is preferred that the axis of the choana section (8) and the angle of bus are 15 ° -70 °, preferably 21 ° -60 °；
The more preferable choana section (8) is taper, and the water conservancy diversion pipeline section (9) is the straight round tube of water conservancy diversion, the taper round mouth
The ratio of the diameter D2 of diameter D1 and the straight round tube of water conservancy diversion is 3-10.
6. reactor according to claim 5, wherein in the circumferential setting deflector hole of the choana section (8)
(10), the diameter D3 of the preferably described deflector hole (10) is 0.01-0.1m；
It is preferred that the circumferential direction in the choana section (8) is evenly arranged with n deflector hole, n is 2-16, preferably 4-10
It is a.
7. reactor according to claim 5 or 6, wherein the height of degassing liquid collecting diversion component (6) is 1-5m,
Preferably 1.5-4m；The height ratio of the more preferable water conservancy diversion pipeline section (9) and choana section (8) is 1-10:1, preferably 1-
6:1。
8. reactor according to claim 5 or 6, wherein the degassing liquid collecting diversion component (6) is in conversion zone (3)
Divide M layers of setting, M 2-10, more preferably 2-6；
It is preferred that the degassing liquid collecting diversion component (6) of every layer of setting is 2N, N 1-10, preferably 2-8.
9. reactor according to claim 8, wherein side of the slurries diversion component (11) in the conversion zone (3)
Wall is divided into 2-10 layers of distribution up and down；The more preferable slurries diversion component layer and the degassing liquid collecting diversion component layer are along reacting
The axially staggered distribution of section (3).
10. a kind of method of F- T synthesis, which is characterized in that reaction of this method described in any one of claim 1-9
It is carried out in device, wherein this method comprises: synthesis gas enters from reactor inlet section (1), be distributed by gas distributor (2) equal
Enter conversion zone (3) after even and contacts progress Fischer-Tropsch synthesis with catalysts and solvents；
Wherein, the reaction paste of the wall region of conversion zone (3) is along the slurries diversion component (11) to the axis of conversion zone (3)
Back-mixing is forced to region (S)；Reaction paste is after the degassing liquid collecting diversion component (6) removes gas in conversion zone (3)
Force back-mixing；
Tail gas, which enters gas-liquid-solid segregation section (4), to carry out de- liquid and takes off admittedly, is then discharged out；Liquid material passes through solid-liquid separator (7)
It is discharged after separating solid from the product liquid outflux of reactor.
11. according to the method described in claim 10, wherein, the speed that synthesis gas enters from reactor inlet section (1) is 5-
40cm/s；The speed of tail gas discharge is 8-25cm/s.
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| US20090159537A1 (en) * | 2007-12-19 | 2009-06-25 | Chevron U.S.A. Inc. | Reactor having a downcomer producing improved gas-liquid separation and method of use |
| CN202478905U (en) * | 2012-02-03 | 2012-10-10 | 中国石油化工股份有限公司 | Slurry bubble column reactor |
| CN103769008A (en) * | 2014-02-12 | 2014-05-07 | 中国科学院上海高等研究院 | Inner circulation flow reactor of slurry reactor |
| CN207371506U (en) * | 2017-09-30 | 2018-05-18 | 中国海洋石油集团有限公司 | A kind of Airlift circulating reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090159537A1 (en) * | 2007-12-19 | 2009-06-25 | Chevron U.S.A. Inc. | Reactor having a downcomer producing improved gas-liquid separation and method of use |
| CN202478905U (en) * | 2012-02-03 | 2012-10-10 | 中国石油化工股份有限公司 | Slurry bubble column reactor |
| CN103769008A (en) * | 2014-02-12 | 2014-05-07 | 中国科学院上海高等研究院 | Inner circulation flow reactor of slurry reactor |
| CN207371506U (en) * | 2017-09-30 | 2018-05-18 | 中国海洋石油集团有限公司 | A kind of Airlift circulating reactor |
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Application publication date: 20191203 |