CN101314120A - Slurry bed reactor and uses thereof - Google Patents
Slurry bed reactor and uses thereof Download PDFInfo
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- CN101314120A CN101314120A CNA2007100998484A CN200710099848A CN101314120A CN 101314120 A CN101314120 A CN 101314120A CN A2007100998484 A CNA2007100998484 A CN A2007100998484A CN 200710099848 A CN200710099848 A CN 200710099848A CN 101314120 A CN101314120 A CN 101314120A
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Abstract
The invention provides a slurry-bed loop reactor, comprising an ascending pipe and at least one downtake pipe 3, wherein, the ascending pipe consists of a reaction zone 1 and a settlement zone 2 with an expanded pipe diameter; an exhaust port 13 is arranged on the top of the settlement zone 2; the inside of each downtake pipe 3 is divided into a filtrate zone 5 and a slurry zone 6 by a filter medium 4, wherein, the filtrate zone 5 is communicated with a liquid discharge port 10; two ends of the slurry zone 6 are communicated with two ends of the ascending pipe 1, so the settlement zone 2 is separated into a steady flow zone 19 and a turbulent flow zone 20, wherein, the upper part of the steady flow zone 19 is communicated with the downtake pipe 3 through a pipeline 16; and the bottom of the steady zone 19 is directly communicated with the reaction zone 1 through an open pore 18 or through a draft tube 17. The slurry-bed loop reactor provided by the invention can realize continuous high-efficiency separation of solid catalyst particles, a liquid product and reacting gas, realize continuous discharging of a gas phase, a liquid phase and a solid phase, reduce turbulence of rising slurry from the reaction zone to settling particles in the settlement zone by separating the settlement zone into the turbulent flow zone and the steady flow zone, improve the separation efficiency of the settlement zone, and reduce the filtering load of the downtake pipe, thereby improving the treating capacity and the separation efficiency of the whole reactor, and prolonging the backsurge period.
Description
Technical field
The present invention relates to equipment and method that solia particle is separated from liquid, more particularly, relate to a kind of equipment and application process thereof that slurry bed circulatory flow reactor liquid and solid particle separate continuously that be used for.
Background technology
Paste state bed reactor is a kind of gas-liquid commonly used (slurry) haptoreaction equipment, has high liquid storage amount.For the very big catalytic reaction process of reaction heat, use paste state bed reactor can remove reaction heat effectively, the isothermal operation of realization response device guarantees the normal operation of reactor, has therefore obtained extensive use in current chemical process.And slurry bed circulatory flow reactor is a kind of efficient heterophase reactor that grows up on the basis of slurry attitude bed bubbling reactor.Slurry bed circulatory flow reactor can also make its inner fluid do well-regulated circulating, thereby strengthen mixing, diffusion, heat transfer and mass transfer between the reactant except the whole advantages that have slurry attitude bed bubbling reactor and had.
In paste state bed reactor,, generally adopt tens microns even more fine grain catalyst, but also brought product to separate this difficult problem with catalyst granules thereupon in order to eliminate diffusion influence.How effectively to realize liquid-solid separation, become the key technology in using slurry attitude bed course of reaction.
The liquid-solid separation of paste state bed reactor catalyst slurry is generally carried out outside reactor, and the slurries that contain catalyst must use specific pump to carry, and the catalyst of separating still need send back in the reactor with the slurries form.This process is easy to cause the breakage of catalyst granules, thereby the long-time continuous operation of reactor is brought problem.
USP 6068760, WO 02/097007A2 all disclose and have adopted sedimentation techniques to realize the method for liquid-solid separation in paste state bed reactor, reacted slurries are drawn reactor, behind a sedimentation pipe, slurries enter settling tank and carry out sedimentation, supernatant liquor is discharged as product, and the thick slurry Returning reactor circulation of a large amount of catalyst granules is contained in lower floor.
The disclosed separation method of EP 1405664A1 is that reacted slurries are directly introduced settling tank, sedimentation is provided with baffle plate in irritating, and height of baffle plate is higher than liquid level in the settling tank, therefore after slurry stream is crossed the slit of baffle plate and tank base, clear liquid slowly rises and flows out above settling tank, and contains the outlet Returning reactor main body of the underflow of particle in the settling tank bottom.
CN1433838A discloses the method that separative element is set in reactor body, make slurries realize liquid-solid separation, and proposes to apply high-intensity magnetic field to quicken liquid-solid separating rate in the bottom of sedimentation unit.But utilize single sedimentation techniques to realize liquid-solid completely separation, obtain the minimum product liquid of solid content and need the very big sedimentation device of volume, to guarantee enough sedimentation times, this has just caused the most of area and the space of equipment to be taken by sedimentation device, and production efficiency is lower; Catalyst particle size is more little in addition, help reaction more and carry out, simultaneously in course of reaction because catalyst abrasion can produce the minimum pressed powder of particle diameter, but sedimentation techniques are that the separating effect of the littler catalyst granules of several microns or particle diameter is not good for particle diameter; Because Fischer-Tropsch synthesis device diameter is quite big, thereby magnetic field device is difficult in and produces uniform magnetic field in the reactor, and the equipment heaviness involves great expense, and can't carry out demagnetization to stop the reunion of magnetization catalyst to producing magnetized catalyst, influence the normal running of reactor.
WO 94/16807 discloses in reactor the method for using filter assemblies to realize liquid-solid separation, in case but catalyst granules stops up filter assemblies, the regeneration difficulty of filter assemblies then, thereby be unsuitable for large-scale continuous production.
CN1589957A discloses at inside reactor the one-level separative element has been set, the secondary separative element is set outside reactor realizes the method for liquid-solid separation, and the continued operation of back flush unit to realize filtering is set outside reactor, so not only taken the reaction compartment in the reactor, also cause the device structure complexity, operate complicated.
US 2005/0027021 discloses a kind of liquid-solid piece-rate system, realize liquid-solid separation by the filter element that vertical placement is set outside reactor, what play main filtration is the filter cake that is deposited on the filter element, by regulating the thickness that the slurries flowing velocity is regulated filter cake.But, element space of living in size determined because being design, come controlled filter speed to make adjustable range very limited by the outside slurry flow rate of regulating element merely, and the easy blocking filtering medium of fine grained and do not have effective back-flushing method to make filter process be difficult to realize serialization.
US 2005/0000861 discloses a kind of filter element that can be placed on inside reactor and/or outside, this element is divided into coarse filtration district and fine filtering district, and the two is coaxial with vertically placement of footpath, block oarse-grained catalyst outside filtering area in coarse filtration district, top, Returning reactor recycles again again, carries out further isolated by filtration and can directly enter the fine filtering district that is located at below the coarse filtration district through the filtrate of coarse filtration.This solid separation method need be by exterior power, and detailed back-flushing method is not provided, and is difficult to realize that liquid-solid continuous effective separates.
Utilize sedimentation method need take bigger area as can be known merely by above analysis, even valuable reaction compartment; And utilize the method for filtering to be difficult to realize continued operation, and also can reduce separative efficiency owing to higher solid content even realized continued operation, also can make the equipment complexity, investment and operating cost increase.
Summary of the invention
The purpose of this invention is to provide a kind of slurry bed circulatory flow reactor of realizing that simple and effectively gas-liquid-solid three-phase is separated continuously.
Another object of the present invention provides the method that a kind of gas-liquid-solid three-phase that is used for paste state bed reactor is separated continuously, and the reaction liquid product can be discharged continuously.
Three of purpose of the present invention provides a kind of application slurry attitude bed and carries out the synthetic method of producing liquid hydrocarbon or paraffin of Fischer-Tropsch.
Slurry bed circulatory flow reactor provided by the invention, comprise tedge and at least one down-comer 3, described tedge is made up of the decanting zone 2 that reaction zone 1 and caliber enlarge, the top of decanting zone 2 is provided with exhaust outlet 13, be filtered medium 4 in the every down-comer 3 and be divided into filtrate district 5 and slurries district 6, wherein filtrate district 5 is communicated with liquid outlet opening 10, the two ends in slurries district 6 are connected with the two ends of tedge 1, has the baffle plate that roughly vertically is provided with in the described decanting zone 2, the top edge of wherein said baffle plate accounts for 1/10～9/10 of described decanting zone total height apart from the distance at the top of described decanting zone, the decanting zone above part of inherent described baffle plate top edge is a gas-liquid separation zone, the decanting zone then is divided into turbulent flow area 20 and current stabilization district 19 by described baffle plate in this part below top edge, wherein said turbulent flow area 20 is close to reaction zones 1 and directly is communicated with reaction zone 1, and the top in described current stabilization district 19 directly is communicated with described turbulent flow area, 19 bottoms, described current stabilization district directly are communicated with reaction zone 1 through perforate 18 or mozzle 17, and described down-comer 3 is communicated with described tedge through tube connector 16 on the top in described current stabilization district 19.And the scope that described tube connector 16 connects the current stabilization zone position be described baffle plate top edge with 1/10 to 9/10 scope of the vertical distance of described perforate 18 or mozzle 17 and baffle plate link position in, be preferably in 1/3 to 2/3 scope.
In the reactor provided by the invention, the shape of wherein said baffle plate can be flat board, circular arc, cylinder, truncated cone, infundibulate or other suitable shape, the perhaps combination of above-mentioned shape.And described " roughly vertically being provided with " is meant that described baffle plate has at least a part and perpendicular tangent, and described baffle plate is divided into the part of described decanting zone in the space of two or more substantial horizontal distributions.
A kind of preferred set-up mode of baffle plate described in the above-mentioned reactor is: described turbulent flow area 20 and current stabilization district 19 are separated by cylindrical baffle, and described baffle plate bottom is connected with the inwall of described tedge.Described turbulent flow area 20 is positioned at described cylindrical baffle inside, and described current stabilization district 19 be looped around described turbulent flow area 20 around, be the annular region that described cylindrical baffle and decanting zone 2 outer walls surround.19 bottoms, described current stabilization district are connected with the bottom of reaction zone 1 by perforate 18 or mozzle 17.The diameter of wherein said cylindrical baffle bottom can be identical or different with the diameter of these plate washer other parts, that is, described " cylindric " not only comprises the cylindric of standard, also comprises the truncated cone shape, perhaps other similar shape, the perhaps combination of above-mentioned shape.
The another kind of preferred set-up mode of baffle plate described in the above-mentioned reactor is: turbulent flow area described in the reactor 20 is separated by tapered cylinder shape baffle plate with current stabilization district 19, and described tapered cylinder shape baffle plate is fixed on the inwall of described tedge by support 21.Described current stabilization district 19 is positioned at described tapered cylinder shape baffle interior, and described turbulent flow area 20 be looped around described current stabilization district around, be the annular region that described tapered cylinder shape baffle plate and decanting zone 2 outer walls surround.Described current stabilization district 19 is connected with the bottom of reaction zone 1 by the mozzle 17 of tapered cylinder bottom." tapered cylinder shape " described here is meant a kind of like this shape, it can be considered to the downward taper in summit usually, also be " infundibulate " and the shape that combines as top defined " cylindric ", the top edge of wherein said tapering part and the lower limb of described cylindric part combine.Certainly, described " tapered cylinder shape " also comprises simple " infundibulate "." support " described here is meant can be with the device of described baffle plate and tedge inwall physical fixation, thereby and its between described baffle plate and described inwall, reserve enough spaces fluid freely passed through.
In above-mentioned reactor provided by the invention, the slurries that flow into from reaction zone 1 enter described decanting zone 2 through described turbulent flow area 20.Finish gas-liquid (slurry) at this and separate, gas is discharged reactor from the exhaust outlet 13 at top.Thicker particle relies on gravitational settling can directly turn back in the reaction zone 1 at turbulent flow area 20, perhaps after flowing into current stabilization district 19 with slurry, rely on gravitational settling to be enriched in the bottom in current stabilization district 19, the slurries that contain more particle then can turn back in the reaction zone 1 through tube wall perforate 18 or mozzle 17, preferably get back to the bottom of reaction zone by mozzle 17.Typically, when normal running, the slurries that carry a large amount of bubbles rise to the turbulent flow area 20 on its top from reaction zone 1, liquid level flushes with the baffle plate upper edge basically, the baffle plate another side, the liquid level in current stabilization district 19 and baffle plate upper edge flush or are lower than the baffle plate upper edge slightly, slurries by turbulent flow area 20 in the process of current stabilization district 19 overflows, most of bubble is because mobile tending towards stability breaks away from the gas-liquid separation zone that slurries enter top, because the enlarged meeting in gas-liquid separation zone space reduces the speed of gas, has reduced droplets entrained in the bubble.Slowing down of slurry flow rate makes wherein solid particles sediment to 19 bottoms, current stabilization district in the current stabilization district, enrichment the slurries of solid particle can be in 19 bottoms, current stabilization district return reaction zone and continue to participate in reaction through opening 18 or mozzle 17.And can entering filtration fraction by down-comer 16, the slurries of having got rid of bubble and bigger solid particle carry out Separation of Solid and Liquid.
In the reactor provided by the invention, the caliber ratio of decanting zone 2 and tedge lower reaction zone 1 is 1: 1.1～10.0, preferred 1: 1.2～3.0.
In the reactor provided by the invention, filtrate district 5 is communicated with liquid outlet opening 10 in the described down-comer 3, and liquid outlet opening 10 can connect the backwashing system that is used for the washing and filtering element through valve 9, and wherein the preferred liquid discharging opening is positioned at the lower end in filtrate district; Connect simultaneously on the pipeline 7 of down-comer 3 and tedge lower end and can be provided with solid drain hole 11 and solid feed inlet 12.
In the reactor provided by the invention, the tedge bottom is the reaction zone 1 of reactor, and the decanting zone 2 on tedge top and down-comer 3 are the Disengagement zone of reactor.Wherein, reactor comprises at least one down-comer 3.When down-comer 3 is many, many down-comers can by switching make at least one in running order.
In the reactor provided by the invention, described filter medium can adopt the form of self-filtering pipe, when adopting the form of self-filtering pipe, decanting zone 2 can be to communicate (as shown in Figure 1) with the self-filtering pipe through the pipeline 16 and the mode of communicating of down-comer 3, also can communicate with the outer tube of down-comer 3 (as shown in Figure 4), when communicating with the self-filtering pipe, connect liquid outlet opening 10 on the outer tube, in down-comer 3, liquid is the tube wall by the self-filtering pipe radially from inside to outside, and finally draws through pipeline as product; Simultaneously outer tube top is connected with decanting zone 2 top gas enrichment regions through pipeline 8, with the balance that keep-ups pressure, prevents that gas from assembling in down-comer.When tedge communicates with the outer tube of down-comer 3, connect liquid outlet opening 10 on the screen pipe, in down-comer 3, the liquid ecto-entad is the tube wall by the self-filtering pipe radially, and finally draws through pipeline as product.
The outer tube inside of every down-comer 3 comprises at least one screen pipe.When down-comer 3 inside comprise many screen pipes: at least two screen pipes can be connected in parallel on the catch tray and form a filter element and use, as Fig. 5, shown in Figure 6, Fig. 5 is the vertical view that many screen pipes are connected in parallel on the filter element on the catch tray, and Fig. 6 is connected in parallel on the side view of the filter element on the catch tray for many screen pipes; Also can adopt the form of a plurality of filter element combinations.Adopt the form of filter element and filter element combination can save the space effectively, improve filter efficiency.
When adopting the form of a plurality of filter element combinations, the combination of filter element in outer tube is distributed with following several form: vertically place a plurality of filter elements (accompanying drawing 7) vertically; Or a plurality of filter elements of radially parallel distribution (accompanying drawing 8); Or the many groups of placement vertically are with a plurality of filter elements (accompanying drawing 9) of the parallel distribution of radial form.Each filter element can be provided with independently backwashing system, also each filter element can be connected a shared cover backwashing system by pipeline.
In the reactor provided by the invention, described solid drain hole 11 and solid feed inlet 12 are used for handling more neatly catalyst.When the catalyst granules in the reactor needs to change owing to inactivation or drawing small, can discharge by solid drain hole 11, also can pass through solid feed inlet 12 fresh makeup catalyst.
In the reactor provided by the invention, to the material of filter medium 4 without limits, can use the filtering material of sintered metal mesh micropore filter material, sintering metal powder micropore filter material, metal micro-holes membrane material, sintered metal fiber poromerics, micropore ceramics material, ceramic membrane material or other type.The pore diameter range of filter medium can be changed by the scale of the kind of the catalyst granules of concrete use, reactor and the reaction type that is carried out, for example within filter areas such as micro-filtration, ultrafiltration, nanofiltration.
The application process of reactor provided by the invention, raw material enters reactor by charging aperture 14, mix with the slurries in the tedge reaction zone 1, mixed slurries react in reaction zone 1, upwards flow simultaneously, at first flow to the turbulent flow area 20 of decanting zone 2 from the reaction zone 1 upper end mouth of pipe, again by turbulent flow area 20 overflows to current stabilization district 19, at described turbulent flow area 20, the gas-liquid separation zone on current stabilization district 19 and top carries out gas-liquid separation, gas is discharged reactor from the exhaust outlet 13 at top, thicker particle relies on gravitational settling, directly turn back in the reaction zone 1 by described turbulent flow area 20, perhaps be deposited to 19 bottoms, current stabilization district, get back in the reaction zone 1 via perforate 18 or mozzle 17 again, contain more fine grain slurries and enter the down-comer 3 from 19 tops, current stabilization district through connecting inclined tube 16; The slurries main body flows downward in slurries district 6 vertically, and wherein a part of liquid enters filtrate district 5 by filter medium 4 under the promotion of filter medium 4 both sides pressure reduction, and finally draw as product, solid catalyst particle then continues to flow downward with the slurries main body and turns back to continuation participation reaction in the tedge 1 by pipeline 7.
In the method provided by the invention, mozzle 17 with enrichment the slurries of the catalyst granules bottoms of introducing reaction zone, form new interior circulation form owing to what contain that a large amount of bubbles have than low-density formation density contrast in the high density that it is inner and the reaction zone 1.In this circulation form can make in the bed catalyst with the natural circulation of slurries distribute more even.In addition, the circulation cycle amount that mozzle has reduced down-comer is set, has improved the filter effect in the down-comer.
In the method provided by the invention, the superficial gas velocity of gas in tedge lower reaction zone 1 that enters reactor is 0.01～1.0 meter per second, preferred 0.04～0.5 meter per second.Wherein superficial gas velocity refers to the blank pipe gas speed in tedge 1 of air-flow, and control gas speed can make slurries stir, mix in this scope, and the motive force that provides slurries to circulate between tedge and down-comer 3, keeps reactor internal reaction pressure.Lower pressure forms the pressure reduction of filter medium 4 both sides in the filtrate district 5 of pressure that inside reactor is higher relatively and down-comer 3, and the slurries that promotion is isolated behind the gas pass filter medium 4, realizes Separation of Solid and Liquid.
In the method provided by the invention, carry out with reaction, the pressure reduction of filter medium 4 both sides rises along with thickening of filter cake, when pressure reduction is higher than first setting value, backwashing system is started working, liquid outlet opening late gate 15 is closed at this moment, liquid outlet opening 10 is communicated with through valve 9 and recoil pipeline, the backwash medium is back flush filter medium 4 under the reverse pressure reduction that adds promotes, constantly reduce with the reverse pressure reduction of removing of filter cake, when being lower than second setting value, flushing process finishes, this moment, liquid outlet opening 10 back valves 9 cut out, and system returns to normal operating state.
Pressure reduction first setting value that wherein begins to start backwashing system is 0.1～1.0Mpa, pressure reduction second setting value when closing recoil is 0.05～0.8Mpa, the backwashing pressure also different according to its filtration pressure difference scope of different filtering materials, that different materials is corresponding different.To same filter core and equipment, first setting value must be greater than second setting value, and for the filter process of normal running, the both sides pressure differential range is 0.05～1.0MPa.The unlatching of described backwash process and end can also can manually be carried out automatically.
Wherein said backwash medium can be a gas, also can be liquid, preferred product clear liquid or reaction end gas, more preferably product clear liquid.
In the method provided by the invention, under the situation that does not influence reaction process, can selectively thinner catalyst granules be shifted out by described solid drain hole 11, and replenish the part fresh catalyst through solid feed inlet 12.
Method provided by the invention is in the synthetic application of producing in liquid hydrocarbon or the paraffin of Fischer-Tropsch, it is characterized in that raw material is a synthesis gas, the activity of such catalysts component contains Fe and/or Co, operating condition in the tedge reaction zone 1 is: temperature is 200～300 ℃, preferred 230～280 ℃, pressure is 1.0～5.5Mpa, preferred 1.7～3.5Mpa, is 1.0～8.0Nlg with respect to the raw material air speed of catalyst quality
-1h
-1, preferred 2.0～5.0Nlg
-1h
-1
Slurry bed circulatory flow reactor provided by the invention can realize that the continuous high-efficient of solid catalyst particle, liquid form product and reacting gas separates, the continuous discharging of gas-liquid-solid three-phase; The decanting zone is divided into turbulent flow area and quasistatic decanting zone has reduced the disturbance of the air-flow that rises by reaction zone sedimented particle in the decanting zone, thereby improved the separative efficiency of decanting zone, reduced the load that down-comer filters, thereby improved the treating capacity and the separative efficiency of whole reactor, and prolonged backwashing period.Reactor of the present invention and application process thereof are applicable to gas-liquid-solid phase reaction and need isolate the chemical reaction process of fluid product from slurries, as adopting hydrocarbon oil hydrogenation, certain embodiments and the Fischer-Tropsch building-up process of suspension bed or paste state bed reactor.
Description of drawings
Fig. 1 is the circulation flow reactor schematic diagram that bottom, current stabilization district is communicated with reaction zone through perforate;
Fig. 2 is the schematic diagram that bottom, current stabilization district is communicated with reaction zone through mozzle;
Fig. 3 is for being divided into the decanting zone by tapered cylinder the schematic diagram of current stabilization district and turbulent flow area;
The slurry bed circulatory flow reactor schematic diagram that Fig. 4 communicates with the outer tube of down-comer through pipeline for the decanting zone;
Fig. 5 is the schematic top plan view of filter element with the catch tray parallel connection for many interior pipes;
Fig. 6 is the schematic side view of filter element with the catch tray parallel connection for many interior pipes;
Fig. 7 is the schematic diagrames of a plurality of filter elements along the down-comer axial arranging;
The schematic diagram that Fig. 8 radially arranges along down-comer for a plurality of filter elements;
Fig. 9 be a plurality of filter elements in down-comer radially with the schematic diagram of axial arranging;
The circulation flow reactor schematic diagram that Figure 10 is adopted for embodiment 1.
The specific embodiment
Specify the continuous separation method that slurry bed circulatory flow reactor provided by the invention is used for Fischer-Tropsch building-up process liquid and solid particle below in conjunction with accompanying drawing, but therefore the present invention is not restricted.
As shown in Figure 2: the tedge bottom of circulation flow reactor is slurry attitude bed reaction zone 1, the reactant synthesis gas enters reactor from the underfeed mouth 14 of tedge, mix with the slurries in the tedge reaction zone 1, mix, contact with catalyst granules in the slurries, in uphill process, finish chemical reaction, product and unnecessary reactant rise to reactor top with catalyst, at first flow to the turbulent flow area 20 of decanting zone 2 from the reaction zone 1 upper end mouth of pipe, again by turbulent flow area 20 overflows to current stabilization district 19, slurry flow rate reduces, at described turbulent flow area 20, the gas-liquid separation zone on current stabilization district 19 and top carries out gas-liquid separation, gas is discharged reactor from the exhaust outlet 13 at top, thicker particle relies on gravitational settling, is directly turned back in the reaction zone 1 by described turbulent flow area 20, perhaps is deposited to 19 bottoms, current stabilization district, get back in the reaction zone 1 via perforate 18 or mozzle 17 again, contain more fine grain slurries and enter the down-comer 3 from 2 tops, current stabilization district through connecting inclined tube 16; The slurries main body flows downward in slurries district 6 vertically, and wherein a part of liquid enters filtrate district 5 by filter medium 4 under the promotion of filter medium 4 both sides pressure reduction, and finally draw as product, solid catalyst particle then continues to flow downward with the slurries main body and turns back to continuation participation reaction in the tedge 1 by pipeline 7.
Solid particle then is arrested on the screen pipe inwall, because the souring of liquid flow, part filter cake on the screen pipe inwall constantly comes off and flows downward with slurries and turns back in the tedge reaction zone 1, the filter cake of part difficult drop-off can be trapped on the inwall of screen pipe, along with constantly thickening of filter cake, pressure reduction between the inner and outer pipes rises, and when pressure reduction was higher than first setting value, 0.1～1.0Mpa, backwashing system was started working.The valve 15 that be positioned at behind the liquid drain hole 10 this moment cuts out, valve 9 is opened, under the promotion that adds reverse pressure reduction, the backwash medium introduce in the outer tube 5 and radially ecto-entad pass through screen pipe, sprung back in the slurries attached to the filter cake on the screen pipe inwall, and returned tedge along with slurries flow downward.When the pressure reduction of inner and outer pipes was lower than second setting value, 0.05～0.8Mpa, flushing process finished, and the valve 9 on the backwash this moment medium inlet tube is closed, and valve 15 and the valve on communicating pipe 8 behind the liquid drain hole are opened, and system returns to normal operating state.
The embodiment of the specific embodiment of the slurry bed circulatory flow reactor shown in the accompanying drawing 3 and reactor as shown in Figure 2 is basic identical, different is: in tedge, the annular region that tapered cylinder and decanting zone 2 outer walls surround is a turbulent flow area 20, here, thicker particle relies on gravitational settling can directly turn back in the reaction zone 1, in addition, zone in the tapered cylinder is current stabilization district 19, enrichment more more coarse grained slurries directly turn back to reaction zone 1 bottom through 19 bottoms, current stabilization district, mozzle 17.
The following examples illustrate further to method provided by the invention, but not thereby limiting the invention.
Comparative Examples 1
The separating effect of the circulation flow reactor of baffle plate is not set in the Comparative Examples 1 explanation decanting zone.
Adopt slurry bed circulatory flow reactor as shown in figure 10, it is 1.5: 1 that tedge decanting zone and reaction zone get the caliber ratio, and the chimney filter that is adopted in down-comer is the sintered porous metal chimney filter, this chimney filter external diameter 50mm, long 1000mm, average pore size 1 μ m.The particle size range of the catalyst that is adopted is 1～100 μ m, and raw material is a synthesis gas, and the pressure reduction between the down-comer inner and outer pipes is during greater than 0.5MPa.Backwashing system brings into operation, and with pump the product clear liquid is introduced outer tube, and enters interior pipe by filtering tube wall, filter cake is flushed in the slurries, and returns tedge along with slurries flow downward.This process continues several seconds, and when the pressure reduction between inner and outer pipes was lower than 0.1MPa, backwashing system was closed, and paste state bed reactor returns to normal operating state.In this process, the clear liquid flow of being drawn by pipeline 10 is: 60L/h, and backwashing period is 48 hours, and the content of solid particle is less than 5 μ g/ml in the liquid form product, and the maximum gauge of particle is 2 μ m.Separative efficiency is more than 99%.
Wherein separative efficiency is calculated by following formula:
η＝(S
m-S
f)/S
m
Wherein: S
mSolid content in the=raw material (slurries before filtering); S
fSolid content in the=product (clear liquid that draw in the filtrate district).
Embodiment has baffle plate in 1～3 explanation decanting zone 2, the decanting zone is divided into the separating effect of the circulation flow reactor of turbulent flow area, current stabilization district and gas-liquid separation zone.
Adopt reactor as shown in Figure 1, described turbulent flow area 20 and current stabilization district 19 are separated by cylindrical baffle, and 19 bottoms, described current stabilization district are passed through the baffle plate bottom opening and are communicated with reaction zone.Wherein, reaction zone is of a size of
70 * 3200mm; Decanting zone expanding reach caliber is 150mm, and height is 1000mm; Cylindrical baffle is of a size of
70 * 700mm, the baffle plate bottom has 6
12 hole; The down-comer size of outer tube is
70 * 2000mm, inner filtration tubing matter is the metal micro-holes film, this chimney filter is of a size of
30 * 1800mm, average pore size 1.0 μ m.
Consisting of of catalyst: the Co that contains 20.3 weight %
2O
3, the SiO of 76.1 weight %
2, the MgO of 3.6 weight %.The preparation method will contain Co (NO
3)
3And Mg (NO
3)
2Solution impregnation SiO
2Microsphere supported, left standstill 24 hours, 120 ℃ of dryings then, and obtained the catalyst that particle size range is 1～100 μ m in 6 hours in 400 ℃ of roastings.
The catalyst useful load is 15% (volumn concentration).Raw material is synthesis gas (H
2: the mol ratio of CO is 2: 1), be 2.0NLg with respect to the air speed of catalyst quality
-1h
-1, pressure be 3.0MPa, temperature be under 200～220 ℃ the condition with the catalyst haptoreaction.When the pressure reduction between the down-comer inner and outer pipes during greater than 0.5MPa, backwashing system brings into operation, and with pump the product clear liquid is introduced outer tube, and enters interior pipe by filtering tube wall, filter cake is flushed in the slurries, and returns tedge along with slurries flow downward.This process continues several seconds, and when the pressure reduction between inner and outer pipes was lower than 0.1MPa, backwashing system was closed, and paste state bed reactor returns to normal operating state.Clear liquid is after fractionation is handled, and product is distributed as: contain the dry gas of 6.3 weight %, the liquefied gas of 3.6 weight %, the naphtha of 13.4 weight %, the diesel oil of 30.7 weight %, the hard wax of 46 weight %.
In this process, the clear liquid flow of being drawn by pipeline 10 is: 1.7L/h, and backwashing period is 120 hours, the CO conversion per pass is 92.4% in the synthesis gas.The content of solid particle is less than 3 μ g/ml in the liquid form product, and the maximum gauge of particle is 1 μ m.Separative efficiency is 99.5%.
Adopt reactor as shown in Figure 2, described turbulent flow area 20 and current stabilization district 19 are separated by cylindrical baffle, and 19 bottoms, described current stabilization district are passed through mozzle 17 and are communicated with the reaction zone bottom.Wherein, reaction zone is of a size of
280 * 3600mm; Decanting zone expanding reach caliber is 450mm, and height is 1000mm; Cylindrical baffle is of a size of
Totally 6 of 280 * 700mm, mozzle, size is respectively
12 * 3000mm and
12 * 1500mm is staggered; The down-comer size of outer tube is
280 * 2000mm, inner filtration tubing matter is the metal micro-holes film, average pore size is 0.2 μ m, 7 parallel connections as shown in Figure 6, every is of a size of
30 * 1000mm.
Introduce 160 liters in slurries containing solid particle in the reactor in advance, the grain diameter scope is 1～100 μ m in the slurries, and the superficial gas velocity that air is introduced behind the reactor is 0.06 meter per second.The clear liquid of being drawn by pipeline 10 is from the bottom Returning reactor.When the pressure reduction between the down-comer inner and outer pipes during greater than 0.5MPa, backwashing system brings into operation, and with pump the product clear liquid is introduced outer tube, and enters interior pipe by filtering tube wall, filter cake is flushed in the slurries, and returns tedge along with slurries flow downward.This process continues several seconds, and when the pressure reduction between inner and outer pipes was lower than 0.1MPa, backwashing system was closed, and paste state bed reactor returns to normal operating state.
In this process, the clear liquid flow of being drawn by pipeline 10 is: 210L/h, and backwashing period is 100 hours, and the content of solid particle is less than 5 μ g/ml in the liquid form product, and the maximum gauge of particle is 1 μ m.Separative efficiency is 99.9%.
Adopt reactor as shown in Figure 3, described turbulent flow area 20 is separated by tapered cylinder shape baffle plate with current stabilization district 19, described tapered cylinder shape baffle plate is fixed on the described tedge inwall by support 21, and 19 bottoms, described current stabilization district are communicated with the reaction zone bottom by mozzle 17.Wherein, reaction zone is of a size of
280 * 3600mm; Decanting zone expanding reach caliber is 450mm, and height is 1500mm; The funnel-form baffle plate that has mozzle is of a size of for big mouthful
150 * 750mm, mozzle is of a size of
40 * 2800mm; The down-comer size of outer tube is
100 * 1200mm, inner filtration tubing matter is the metal micro-holes film, average pore size is 1 μ m, 7 parallel connections as shown in Figure 6, every is of a size of
30 * 1000mm.
Introduce 160 liters in slurries containing solid particle in the reactor in advance, the grain diameter scope is 1～100 μ m in the slurries, and gas phase is that air is introduced reactor from charging aperture 14, superficial gas velocity at reaction zone is 0.08 meter per second, and the clear liquid of being drawn by pipeline 10 turns back to reactor from the bottom.When the pressure reduction between the down-comer inner and outer pipes during greater than 0.5MPa, backwashing system brings into operation, and with pump the product clear liquid is introduced outer tube, and enters interior pipe by filtering tube wall, filter cake is flushed in the slurries, and returns tedge along with slurries flow downward.This process continues several seconds, and when the pressure reduction between inner and outer pipes was lower than 0.1MPa, backwashing system was closed, and paste state bed reactor returns to normal operating state.
In this process, the clear liquid flow of being drawn by pipeline 10 is: 250L/h, and backwashing period is 100 hours, and the content of solid particle is less than 5 μ g/ml in the liquid form product, and the maximum gauge of particle is 1 μ m.Separative efficiency is 99.9%.
Claims (15)
1, a kind of slurry bed circulatory flow reactor, comprise tedge and at least one down-comer (3), it is characterized in that tedge is made up of the decanting zone (2) that reaction zone (1) and caliber enlarge, the top of decanting zone (2) is provided with exhaust outlet (13), be filtered medium (4) in the every down-comer (3) and be divided into filtrate district (5) and slurries district (6), wherein filtrate district (5) are communicated with liquid outlet opening (10), the two ends in slurries district (6) are connected with the two ends of tedge (1) respectively, has the baffle plate that roughly vertically is provided with in the described decanting zone (2), the top edge of wherein said baffle plate accounts for 1/10～9/10 of described decanting zone total height apart from the distance at the top of described decanting zone, the decanting zone above part of inherent described baffle plate top edge is a gas-liquid separation zone, the decanting zone then is divided into turbulent flow area (20) and current stabilization district (19) by described baffle plate in this part below top edge, described turbulent flow area (20) is close to reaction zone (1) and directly is communicated with reaction zone (1), and the top in described current stabilization district (19) directly is communicated with described turbulent flow area, bottom, described current stabilization district (19) directly is communicated with reaction zone (1) through perforate (18) or mozzle (17), and described down-comer (3) is communicated with described tedge through tube connector (16) on the top in described current stabilization district (19), and described tube connector (16) connects 1/10 to 9/10 scope of position, current stabilization district (19) in the vertical distance of described baffle plate top edge and described perforate (18) or mozzle (17) and baffle plate link position.
2, according to the reactor of claim 1, it is characterized in that described turbulent flow area (20) and described current stabilization district (19) are separated by cylindrical baffle, and described baffle plate bottom is connected with the inwall of described tedge, described turbulent flow area (20) is positioned at described cylindrical baffle inside, described current stabilization district is looped around described cylindrical baffle outside, and bottom, described current stabilization district (19) is passed cylindrical wall by mozzle (17) and directly is communicated with reaction zone (1) bottom.
3,, it is characterized in that the diameter of the diameter of described cylindrical baffle bottom and these other parts of baffle plate is identical or different according to the reactor of claim 2.
4, according to the reactor of claim 1, it is characterized in that described turbulent flow area (20) and described current stabilization district (19) are separated by tapered cylinder shape baffle plate, described tapered cylinder shape baffle plate is fixed on the inwall of described tedge by support (21), described current stabilization district (19) is positioned at described tapered cylinder shape baffle interior, and described turbulent flow area (20) is positioned at funnel-form baffle plate outside, and described current stabilization district (19) directly is communicated with the bottom of reaction zone (1) by the mozzle (17) of funnel-form baffle plate bottom.
5, according to claim 1,2,3 or 4 reactor, it is characterized in that the caliber ratio of tedge lower reaction zone (1) and decanting zone, top (2) is 1: 1.1～10.
6,, it is characterized in that described liquid outlet opening (10) connects backwashing system through valve (9) according to claim 1,2,3 or 4 reactor.
7, according to claim 1,2,3 or 4 reactor, it is characterized in that the pipeline (7) that connects down-comer (3) and tedge (1) lower end is provided with solid drain hole (11) and solid feed inlet (12).8, the application process of the reactor of claim 1～5, it is characterized in that raw material enters reactor by charging aperture (14), mix with the slurries in the tedge reaction zone (1), mixed slurries react in reaction zone (1), upwards flow simultaneously, at first flow to the turbulent flow area (20) of decanting zone (2) from reaction zone (1) the upper end mouth of pipe, again by turbulent flow area (20) overflow to current stabilization district (19), in described turbulent flow area (20), the gas-liquid separation zone on current stabilization district (19) and top carries out gas-liquid separation, gas is discharged reactor from the exhaust outlet (13) at top, thicker particle relies on gravitational settling, directly turn back in the reaction zone (1) by described turbulent flow area (20), perhaps be deposited to bottom, current stabilization district (19), get back in the reaction zone (1) via perforate (18) or mozzle (17) again, contain more fine grain slurries and enter the down-comer (3) from top, current stabilization district (19) through connecting inclined tube (16); The slurries main body flows downward in slurries district (6) vertically, and wherein a part of liquid enters filtrate district (5) by filter medium (4) under the promotion of filter medium (4) both sides pressure reduction, and finally draw as product, solid particle then continues to flow downward with the slurries main body and turns back to continuation participation reaction in the tedge (1) by pipeline (7).
9,, it is characterized in that the superficial gas velocity of gas feed in tedge reaction zone (1) is 0.01～1.0 meter per second according to the method for claim 8.
10,, it is characterized in that described superficial gas velocity is 0.04～0.5 meter per second according to the method for claim 9.
11, according to the method for claim 8, it is characterized in that when filter medium layer both sides pressure reduction is higher than first setting value, backwashing system is started working, the upper end in filtrate district this moment (5) and the connection of decanting zone (2) are cut off, and liquid outlet opening (10) and recoil pipeline are communicated with backwash medium back flush filter medium (4), when pressure reduction is lower than second setting value, flushing process finishes, and this moment, liquid outlet opening and backwash pipeline disconnected, and system returns to normal operating state.
12, according to the method for claim 11, it is characterized in that the scope of described first setting value is 0.1～1.0Mpa, the scope of described second setting value is 0.05～0.8Mpa.
13,, it is characterized in that described backwash medium is gas or liquid according to the method for claim 11.
14,, it is characterized in that described backwash medium is product clear liquid or reaction end gas according to the method for claim 13.
15,, it is characterized in that described backwash medium is the product clear liquid according to the method for claim 14.
16, the method for claim 9 is in the synthetic application of producing in liquid hydrocarbon or the paraffin of Fischer-Tropsch, it is characterized in that raw material is a synthesis gas, the activity of such catalysts component contains Fe and/or Co, operating condition in the tedge reaction zone (1) is: temperature is 200～300 ℃, pressure is 1.0～5.5Mpa, is 1.0～8.0Nlg with respect to catalyst quality raw material air speed
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