CN104549071B - Fixed fluidized-bed reactor and using method thereof - Google Patents
Fixed fluidized-bed reactor and using method thereof Download PDFInfo
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- CN104549071B CN104549071B CN201310495171.1A CN201310495171A CN104549071B CN 104549071 B CN104549071 B CN 104549071B CN 201310495171 A CN201310495171 A CN 201310495171A CN 104549071 B CN104549071 B CN 104549071B
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- bed reactor
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- coking
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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
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
Abstract
The invention discloses a kind of fixed fluidized-bed reactor and using method thereof, this fixed fluidized-bed reactor includes pushing up part sealing structure, reactor body and the outlet connected with described reactor body and feed pipe, described reactor body includes settling section from top to bottom, conversion zone and oil preparation initial contact section, wherein, coking inhibitor injection part it is provided with bottom described settling section, this coking inhibitor injection part includes the circumferentially disposed taper type baffle plate along described settling section bottom interior wall, connect the top of taper type baffle plate and the annular filter plate of the inwall of reactor body and coking inhibitor inlet, taper type baffle plate, cavity is formed between annular filter plate and the inwall of reactor body, and described coking inhibitor inlet connects with this cavity.Use fixed fluidized-bed reactor of the present invention, and inject coking inhibitor by coking inhibitor injection part, can substantially reduce the productivity of coke.
Description
Technical field
The present invention relates to a kind of fixed fluidized-bed reactor, and the using method of this fixed fluidized-bed reactor.
Background technology
Deep catalytic cracking technology is owing to raw material sources are wide, olefin product structure easily adjusts, energy consumption is low and CO2 emission
The advantage such as few, deep catalytic cracking technology achieves in recent years and develops faster.Around the process exploitation of this technical field, catalyst
Develop, or different material oil, screening of catalyst evaluation, all it be unable to do without laboratory room small-sized evaluating apparatus.At present, fixing fluidisation
Bed apparatus is real because its simple in construction, operating flexibility are good, bed isothermal, heat transfer efficiency advantages of higher are widely used in catalytic cracking
Test research.
Fixed fluidized-bed reactor is the nucleus equipment that laboratory room small-sized is fixed fluidized bed, is that in experimental implementation, temperature is the highest
Component, in reactor, carry out catalytic cracking reaction and the burning process of hydro carbons.During catalytic cracking reaction propylene,
The unsaturated hydrocarbons such as butadiene at high temperature through dehydrogenation, isomerization, be cyclized, overlap and the secondary response such as condensation inevitably draws
Play coking；Fe-Cr-Ni alloy material is typically used to make due to reactor, the catalytic effect of the metallic such as Fe, Ni therein
Make cracking stock and the hydro carbons Deep catalytic dehydrogenation that is cracked to form thus cause coking, wherein, the freedom in catalytic pyrolysis process
Base junction Jiao forms the main cause of coke.It is unreasonable that coking amount too much directly results in products distribution, coke and dry gas in product
Yield, ethylene, propylene Isoquant are low, and the highest coking makes reactor wall thermal resistance increase, heat transfer coefficient reduces, wall temperature raises and goes out
Current situation portion superheating phenomenon.
The generation of inwall coking makes Wall Temperature raise, decrease in oxygen partial pressure, reaches at lasting high temperature and environment carbon activity
After certain value, the Cr that wall surface is stable2O3Protecting film will react with carbon, lose the protective effect of film, cause carburization phenomena.
Carburized layer volumetric expansion, thermal coefficient of expansion reduces so that wall mechanical properties decrease, cracks, even ruptures, especially
Stress cataclysm when being that post-reactor is rapidly heated and lowers the temperature on pretreatment, it is easier to crack.Carburizing causes wall mechanical property
Can decline, crack, shorten the service life of reactor, the stability of impact experiment.
Coking and carburizing are common problems in cracking of ethylene and catalytic cracking/solution technique, also form many special
Profit technology is for the coking during large-scale production or medium-sized test and carburizing.
CN101274873A discloses a kind of technology added coking inhibitor and strengthen ethylene cracking tube heat transfer；
CN102399571, CN102399572A disclose one and improve pipe furnace material, form the technology of oxidation film at tube skin；
CN101880544A discloses a kind of online coating technology, in the coating of tube skin deposition compact and add coking inhibitor
Patented technology.The above technology all has certain effect in terms of suppression coking and carburizing, the most industry of some technology
Change, but these technology are split with the catalysis of laboratory mainly for cracking of ethylene, its experimental provision, operating condition and technological parameter
Solve entirely different, it is most important that catalytic pyrolysis is the deep pyrolytic reaction under catalyst action, needs to consider catalyst pair
Suppression coking and the impact of carburizing.
CN1236827A discloses a kind of guard method suppressing coking, in this method, with organic after coke cleaning operates
The pretreating agent counterincision such as sulphur compound, organic phosphorus compound, organo-tin compound, organophosphor sulphur compound, organo-silicon compound
Solve boiler tube and carry out pretreatment, wherein effect most preferably organophosphor sulphur compound.This patent application only to cracking furnace pipe at
Reason, mainly suppresses catalytic coking, but Free radical coke is the main aspect of coking in cracking process.
CN102041096A discloses a kind of by sinking the catalysis improving suppression heavy oil of the configuration of settling section and structure
The method and apparatus of fall device coking.This technology is mainly for the coking of the settler of catalytic cracking riser, with consolidating of laboratory
Determine the gap of fluidized bed plant relatively big, and this technology improves, not from reaction mechanism only for the configuration of settling section
Angle suppression coking and the generation of carburizing.
In sum, prior art is split mainly for the catalysis of large-scale production or the cracking of ethylene of medium-sized test and mink cell focus
Coking in metallization processes and carburizing, be not particularly suited for laboratory room small-sized fixed fluidized-bed reactor.
Summary of the invention
It is an object of the invention to for laboratory fixed fluidized-bed reactor when carrying out the catalytic cracking reaction of hydro carbons
In pyrocarbon atmosphere, wall coking is serious, and coke in product, dry gas yied are higher, and the inside carburizing caused by coking is existing
As, a kind of fixed fluidized-bed reactor and using method thereof are proposed so that ensureing target product yield, do not affecting catalyst
Suppress coking and the carburizing of wall in the case of activity, reduce coke and dry gas yield in product.
To achieve these goals, the invention provides a kind of fixed fluidized-bed reactor, this fixed fluidized-bed reactor
Including top part sealing structure, reactor body and the outlet connected with described reactor body and feed pipe, described reaction
Device main body includes settling section, conversion zone and oil preparation initial contact section from top to bottom, wherein, is provided with knot bottom described settling section
Burnt inhibitor injection part, this coking inhibitor injection part includes the circumferentially disposed cone along described settling section bottom interior wall
Annular filter plate and the coking inhibitor of the inwall of platform shape baffle plate, the top of connection taper type baffle plate and reactor body inject
Mouthful, taper type baffle plate, annular filter plate and the inwall of reactor body between formed cavity, and described coking inhibitor inlet with
This cavity connects.
Preferably, described annular filter plate level is arranged.
Preferably, the material of described annular filter plate is metal high temperature resistant, corrosion resistant.
Preferably, the 5-20%, more preferably 7-15% of the height that height is described settling section of described taper type baffle plate.
Preferably, the described annular internal diameter of filter plate is 0.5-0.9, more preferably 0.7-0.8 with the ratio of external diameter.
Preferably, the number of described coking inhibitor inlet is 1-6, more preferably 2-4.
Present invention also offers the using method of above-mentioned fixed fluidized-bed reactor, the method includes: noted by hydrocarbon raw material
Enter and described fixed fluidized-bed reactor carries out catalytic cracking reaction, wherein, injecting before described hydrocarbon raw material and/or the phase
Between, the coking inhibitor carrier gas of liquid is injected described fixed fluidized-bed reactor by described coking inhibitor inlet
In, described coking inhibitor is at least one sulfur-containing compound.
In the present invention, Binding experiment room catalytic cracking reaction mechanism, the feature of green coke and gas-solid fluidization contact shape
State, is optimized the configuration of fixed fluidized-bed reactor, and devises independent coking inhibitor injection part so that adopt
Preferably suppression can be obtained during carrying out hydrocarbon raw material catalytic cracking reaction with the fixed fluidized-bed reactor of the present invention
Coking and the effect of carburizing.Specifically, the fixed fluidized-bed reactor of the present invention and the advantage of using method thereof are mainly manifested in
The following aspects:
(1) the sulfur-containing compound decomposable asymmetric choice net in coking inhibitor goes out HS free radical, on the one hand changes Free radical coke
The reaction mechanism mechanism of reaction, suppresses homogeneous green coke；On the other hand the metal sulfide activity that HS free radical participation reaction generates is low, Bu Huiying
Ring other reactions in catalytic cracking process.
(2) inject coking inhibitor from the bottom of reactor settling section, on the one hand can suppress settling section oil gas and catalyst
Linear speed is relatively low and the secondary response such as polycondensation, condensation occurs mainly in settling section, and easily at settling section, especially this section tube wall is easily tied
Burnt problem；On the other hand coking inhibitor only contacts with the catalyst entering settling section, reduces coking inhibitor to catalyst
The impact of activity；Simultaneously do not affect conversion zone, the hydrocarbon partial pressure of oil preparation initial contact section and fluidized state, it is to avoid because adding knot
Burnt inhibitor and negative effect that primary response is brought.
(3) after coking inhibitor enters inlet, by fixing the filter plate entrance reactor being connected with ring baffle, one
Aspect can make coking inhibitor be distributed uniformly along wall；On the other hand, it is possible to decrease enter settling section is loaded with coking inhibitor
The linear speed of gas, will not affect effect of settling because of the injection of carrier gas.
(4) design has the ring baffle (i.e. taper type baffle plate) at certain inclination angle, the reactor bottom catalyst fluidized
Conversion zone be can partly return under the effect of baffle plate, and the oil gas of settling section and the linear speed of catalyst are lowered into, on the one hand can
To improve due to the limited height of settling section and to enter the oil gas of settling section and catalyst linear speed is higher, the product caused with urge
Agent is longer for time of contact, the problem of the coking that the secondary response such as polycondensation, condensation causes.On the other hand conversion zone can be improved
Catalyst and the contact condition of oil gas.
(5) carrier gas enters reactor with coking inhibitor through screen plate, is on the one hand possible to prevent catalyst to enter annular empty
Chamber and inlet, block inlet.On the other hand the linear gas velocity of settling section can be lowered into, in order to avoid affecting effect of settling.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not intended that limitation of the present invention.In the accompanying drawings:
Fig. 1 is the structural representation of fixed fluidized-bed reactor of the present invention；
Fig. 2 is the structural representation of the coking inhibitor injection part in fixed fluidized-bed reactor of the present invention.
Description of reference numerals
1 taper type baffle plate 2 annular filter plate 3 coking inhibitor inlet
4 filter tube 5 lower flange 6 sealing gaskets
7 filter tube seal receptacle 8 outlet 9 upper flange plates
10 bolt 11 feed pipe 12 distribution grids
13 thermocouple temperature measurement pipe I settling section II conversion zones
III oil preparation initial contact section
Detailed description of the invention
Below in conjunction with accompanying drawing, the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of fixed fluidized-bed reactor, as it is shown in figure 1, this fixed fluidized-bed reactor includes top
Seal structure, reactor body and the outlet 8 connected with described reactor body and feed pipe 11, described reactor body
Include settling section I, conversion zone II and oil preparation initial contact section III from top to bottom, wherein, be provided with bottom described settling section I
Coking inhibitor injection part, it is circumferentially disposed that this coking inhibitor injection part includes along described settling section I bottom interior wall
Taper type baffle plate 1, the annular filter plate 2 connecting the inwall of the top of taper type baffle plate 1 and reactor body and inhibition of coke formation
Agent inlet 3, taper type baffle plate 1, formation cavity between annular filter plate 2 and the inwall of reactor body, and described inhibition of coke formation
Agent inlet 3 connects with this cavity.
In described fixed fluidized-bed reactor, as in figure 2 it is shown, between described taper type baffle plate 1 and the inwall of settling section I
Angle α be preferably no greater than 45 DEG C, more preferably no more than 35 DEG C.
In described fixed fluidized-bed reactor, the height of described taper type baffle plate 1 can be the height of described settling section I
5-20%, preferably 7-15%.
In the present invention, described taper type baffle plate 1 can be truncated cone or square cone, preferably truncated cone.
In described fixed fluidized-bed reactor, described annular filter plate 2 can be horizontally disposed with, it is also possible at a slight angle
It is obliquely installed.Preferably, described annular filter plate 2 is horizontally disposed with.In the present invention, what " level " can not be on geometric meaning is exhausted
To level, as long as substantially achieving the degree of level and naked eyes are not seen substantially tilting.
In described fixed fluidized-bed reactor, as in figure 2 it is shown, when described taper type baffle plate 1 is truncated cone and described
Annular filter plate 2 is when being horizontally disposed with, by taper type baffle plate 1, the cavity edge that formed between annular filter plate 2 and the inwall of reactor body
The axial cross section of reactor is triangular in shape.
In described fixed fluidized-bed reactor, the material gold the most high temperature resistant, corrosion resistant of described annular filter plate 2
Belong to, such as ultra-low-carbon steel, specifically, ultra-low-carbon steel can be such as 00Cr17Ni14Mo2,0Cr23Ni13,0Cr18Ni10Ti,
0Cr18Ni11Nb etc..
In described fixed fluidized-bed reactor, the described annular internal diameter of filter plate 2 can be 0.5-0.9 with the ratio of external diameter,
It is preferably 0.7-0.8.
In described fixed fluidized-bed reactor, the number of described coking inhibitor inlet 3 can be 1-6, is preferably
2-4.When the number of described coking inhibitor inlet 3 is multiple, preferably these inlets are uniformly distributed circumferentially.
The present invention to the described feed pipe 11 installation site on reactor without particular/special requirement, the various installations of prior art
Position all can realize the goal of the invention of the present invention, such as, may be mounted at the top of fixed fluidized-bed reactor of the present invention
(as described in can pass hermetically, the top of reactor connects with reactor body), it is also possible to be arranged on described fixed fluidized bed
The sidewall of reactor.For the present invention, under preferable case, as it is shown in figure 1, described feed pipe 11 and oil preparation initial contact section III
Bottom port connects.Feed pipe 11 is designed and connects at the bottom port with oil preparation initial contact section III, use the side of lower charging
Formula, is directly entered reactor after oil gas is preheated and contacts with catalyst, can accurately control feeding temperature, decrease simultaneously
Oil gas heat scission reaction at high temperature, reduces dry gas and the content of coke in product, improves products distribution.
The present invention to the described outlet 8 installation site on reactor without particular/special requirement, the various installations of prior art
Position all can realize the goal of the invention of the present invention, for example, it is possible to be arranged on the top of fixed fluidized-bed reactor of the present invention
(as connected through the top of reactor body with reactor body), it is also possible to be arranged on of the present invention fixed fluidized bed
The sidewall of reactor.For the present invention, in order to effectively suppress small-numerator olefin polycondensation under catalytic action, reduce settling section
Highly, it is preferable that described outlet 8 inserts the top of settling section I hermetically through top cover flange 9, and the most described outlet 8 is close
Close through reactor plan vertical insert settling section I top.
According to the invention it is preferred to described outlet 8 has multiple, and this outlet 8 multiple uniformly divides on reactor body
Cloth.
According to the invention it is preferred to be provided with filter tube in one end being located at least in reactor body of described outlet 8
4, thus by filter tube 4, catalyst filtration is got off, and reaction oil gas continues through outlet 8 and discharges fixed fluidized bed reaction
Outside device.Wherein, the installation of described filter tube 4 and fixed form can use the method for well known to a person skilled in the art to carry out, and press
According to a kind of detailed description of the invention of the present invention, as it is shown in figure 1, described filter tube 4 includes being positioned at outlet 8 in reactor body
The polycrystalline substance of end and the pipe portion structure being arranged on the outer circle wall of this section port pipe 8, and the pipe portion of Partial filtration pipe 4
Structure upwardly extends along the length direction of outlet 8, and higher than upper flange plate 9(i.e., the top through this reactor is exposed to
The outside of described reactor body), it is further preferred that the pipe portion structure of the described Partial filtration pipe 4 higher than upper flange plate 9 is by filtering
Seal of tube seat 7 seals and is fixed on the top of reactor.In order to be applicable to the operating condition of naphtha catalytic cracking higher temperature,
Under preferable case, described filter tube 4 selects that heat resistance is good, length in service life, resistance to thermal shocks are good, be difficult to the corundum that bursts
Material is made.
According to the present invention, in order to accurately measure reaction temperature, described fixed fluidized-bed reactor also includes thermocouple
Temperature tube 13, the present invention to the described thermocouple temperature measurement pipe 13 installation site on reactor without particular/special requirement, prior art
Various installation sites all can realize the goal of the invention of the present invention, for example, it is possible to described conversion zone is inserted at the top through reactor
In II, for measuring the temperature in reactor.For the present invention, for the ease of installing and can preferably monitor reaction temperature,
Described thermocouple temperature measurement pipe 13 inserts described reactor body through the plan vertical of described fixed fluidized-bed reactor hermetically
In, and extend to the bottom of conversion zone II in described reactor body.Under preferable case, described thermocouple temperature measurement pipe 13 along
The central axis of described reactor inserts in described reactor body.For described thermocouple temperature measurement pipe 13 in reactor body
Insertion depth, for the conventional design of this type of reactor of this area, do not repeat them here.
According to the present invention, in order to further enhance uniform point in fixed fluidized-bed reactor of the present invention of catalyst
Cloth and fluidized state, under preferable case, as it is shown in figure 1, described fixed fluidized-bed reactor also includes distribution grid 12, this distribution grid
12 lower ends being fixed on described thermocouple temperature measurement pipe 13.So fluidizing agent can be uniform by described fluidizing agent distribution grid 12
Ground in reactor body with catalyst counter current contacting, thus greatly strengthen catalyst of the present invention fixed fluidized bed instead
Answer the fluidized state in device.In the case of Jin Yibuyouxuan, described distribution grid 12 is sieve tray, and is perpendicular to described fixed fluidized bed
The direction of the central axis of reactor, the perforate on described sieve tray is uniformly distributed, and the most described sieve tray is circular, described sieve
The bore dia of orifice plate is 0.3-0.9:1 with the ratio of the internal diameter of the reactor cross-section of its place height, and percent opening is 5-50%, hole
A diameter of 0.2-3mm.
In the present invention, described top part sealing structure can be configured according to the sealing structure that this area is conventional, such as,
As it is shown in figure 1, described top part sealing structure is flange plate seal structure, described flange plate seal structure includes upper flange plate 9 He
Lower flange 5, and described reactor head is upper flange plate 9.And the top of reactor is made by upper flange plate 9 and lower flange 5
Portion and reactor body seal, and make the outlet 8 of oil gas after discharging reaction, for the thermocouple temperature measurement pipe 3 of thermometric
It is both secured to upper flange plate 9 and passes hermetically inside upper flange plate 9 insertion reaction device.
According to the present invention, the mode using flangeseal is known to those skilled in the art, and upper flange plate, purgation
The form of blue dish and material all use the conventional design of this type of reactor of this area.It is directed to the present invention, uses flangeseal
The device simple structure of mode, and dismounting transformation is convenient.It is well known by those skilled in the art that and can generally use welding or spiral shell
Tether and the mode such as connect upper flange plate 9 and lower flange 5 are fixed, seal from the top making reactor body.
According to a kind of detailed description of the invention of the present invention, under preferable case, as it is shown in figure 1, for the ease of described fixing stream
The structure of fluidized bed reactor, described lower flange 5 is arranged on the open-topped perisporium of reactor body, described upper flange plate
9 cover the top at reactor body, and make upper flange plate 9 be connected with lower flange 5 bolt by bolt 10.Additionally, usual feelings
Under condition, in order to make upper flange plate 9 and lower flange 5 by bolt 10 connect tightr, it is possible to play cushioning effect, upper
Sealing gasket 6 it is additionally provided with between ring flange 9 and lower flange 5.
It is further preferred that in order to beneficially reactor body preferably seals, described lower flange 5 is integrated with reactor body
's.
In described fixed fluidized-bed reactor, described settling section I, described conversion zone II and described oil preparation initial contact section
The structure (including shape, height etc.) of III each all can use the conventional design of this type of reactor of this area.Such as, described heavy
The shape of fall section I can be truncated cone-shaped or cylinder, preferably cylindrical；The shape of described conversion zone II can be inversed taper platform
Shape, preferably rounding taper type；The shape of described oil preparation initial contact section III can be inverted cone, preferably turbination.
In the preferred case, as it is shown in figure 1, described settling section I is cylindrical, the blade diameter length ratio of described settling section I is 1:
1.5-2.5, more preferably 1:1.8-2.2, the 31-35% that height is total reactor height of described settling section I；Described conversion zone
II is rounding taper type, and the height of described conversion zone II is the 58-62% of total reactor height；Described oil preparation initial contact section
III is turbination, the 3-11% that height is total reactor height of described oil preparation initial contact section III.
Present invention also offers the using method of above-mentioned fixed fluidized-bed reactor, the method includes: noted by hydrocarbon raw material
Enter and described fixed fluidized-bed reactor carries out catalytic cracking reaction, wherein, injecting before described hydrocarbon raw material and/or the phase
Between, the coking inhibitor carrier gas of liquid is injected described fixed fluidized-bed reactor by described coking inhibitor inlet 3
In, described coking inhibitor is at least one sulfur-containing compound.
In using method of the present invention, the weight ratio of the injection rate of described coking inhibitor and described hydrocarbon raw material
Can be 1 × 10-3To 5 × 10-3, preferably 2 × 10-3To 4 × 10-3。
In the present invention, described coking inhibitor be preferably selected from sulfate, thiosulfate, hydrogen sulfide, Carbon bisulfide, two
At least one in methyl sulfoxide, Methyl disulfide, thiophene, dimethyl disulfide, mercaptan and diphenyl sulfide, be more preferably selected from hydrogen sulfide,
At least one in Carbon bisulfide, dithioglycol, dimethyl disulfide and Methyl disulfide.
In the present invention, described hydrocarbon raw material is preferably sulfur content and is not more than the hydrocarbon raw material of 1 weight %, more preferably contains
The Petroleum of sulfur content no more than 1 weight %, light diesel fuel and at least one done in the heavy oil product below 500 DEG C.
In using method of the present invention, described coking inhibitor is permissible with the weight ratio of the injection rate of described carrier gas
It is 0.5 × 10-6To 5 × 10-6, preferably 1 × 10-6To 3 × 10-6。
In the present invention, described carrier gas can be selected from least one in steam, nitrogen and noble gas, preferably water
Steam or nitrogen.
In a preferred embodiment, the using method specific operation process of described fixed fluidized-bed reactor is as follows:
Cracking catalyst introduces in reactor under condition of negative pressure, with in air, steam, nitrogen and helium
Plant or multiple gaseous mixture is fluidizing agent, the Cracking catalyst in fluidized reactor.Hydrocarbon raw material after preheating is through entering
Material pipe 11 injects in the beds reaching assigned temperature, contacts with Cracking catalyst, and at the operation bar set
Carrying out catalytic cracking reaction under part, these operations and reaction condition all use this field customary way.
While hydrocarbon raw material starts charging, open carrier gas and (be used for diluting and carrying coking inhibitor, the method for the present invention
Preferably steam or nitrogen are as carrier gas) control valve, it is passed through inlet 3 after carrier gas preheating, under the effect of taper type baffle plate 1,
Carrier gas is evenly distributed in toroidal cavity with the coking inhibitor of gasification, is entered the settling section of reactor by annular filter plate 2
I.After hydrocarbon raw material has fed, carrier gas proceeds with the injection of coking inhibitor, until stripping phase starts.Enter anti-
The coking inhibitor answering device contacts with reactor wall, can passivating metallic surfaces；Coking inhibitor under diffusion with catalyst
And hydrocarbon product contact, the generation of suppression Free radical coke.The temperature rise period from reactor can also be used to start to inject knot
Burnt inhibitor, until stripping phase starts.
The oil gas entering reactor mixes and fluidization in oil preparation initial contact section III with the catalyst in reactor, with
The generation of reaction, volume expansion, make to be in fluidised catalyst and oil gas with faster linear speed along reactor center
Axis flowing from bottom to top, the catalyst at conversion zone II top is lowered whole fluidizing gas in the effect of taper type baffle plate 1 and urges
The flow direction of agent and speed, in order to reduce enter settling section I catalytic amount, be lowered into settling section I reaction oil gas and
The speed of catalyst, to improve effect of settling, reduces the coking that secondary response causes.The catalyst of conversion zone II can be at taper type
Forming back-mixing under the effect of baffle plate 1, beneficially gas-solid uniformly mixes, and improves the productivity of purpose product.
The most of catalyst granules entering settling section I returns in conversion zone II, and fluidizing gas is discharged anti-through filter
Answering device, the air-flow of discharge is collected through subsequent product recovery system, metering.
Reacted catalyst can strip with stripping fluid (such as steam, nitrogen or helium), stripping fluid and
The reaction oil gas that institute's air stripping goes out also passes through filter tube 4 and reactor outlet pipe 8 is discharged.Afterwards, introduce oxygen, air or contain aerobic
The mixed gas of gas carries out catalyst coke burning regeneration operation.After catalyst coke burning regeneration terminates, the reaction of above-mentioned steps capable of circulation.
By the following examples invention is described further.
In following example, the configuration of the fixed fluidized-bed reactor of use is as it is shown in figure 1, specifically, described fixing fluidisation
The structure of bed reactor is as follows:
Reactor body is followed successively by settling section I, conversion zone II and oil preparation initial contact section III from top to bottom, and settling section I is
Cylinder, the blade diameter length ratio of settling section I is 1:1.8；Conversion zone II is rounding taper type；Oil preparation initial contact section III is inverted cone
Shape, the cone angle of oil preparation initial contact section III is 40 °；The height of settling section I is the 31% of total reactor height；The height of conversion zone II
Degree is the 58% of total reactor height；Height is total reactor height the 11% of oil preparation initial contact section III.
The bottom of settling section I is provided with coking inhibitor injection part, and this coking inhibitor injection part includes along institute
State the circumferentially disposed taper type baffle plate 1 of settling section I bottom interior wall, the top connecting taper type baffle plate 1 and reactor body
The annular filter plate 2 of inwall and coking inhibitor inlet 3, taper type baffle plate 1, annular filter plate 2 and the inwall of reactor body
Between form cavity, and described coking inhibitor inlet 3 connects with this cavity.
Described feed pipe 11 connects with the bottom port of oil preparation initial contact section III.
Described thermocouple temperature measurement pipe 13 is hermetically through the top (that is, upper flange plate 9) of described fixed fluidized-bed reactor
It is inserted perpendicularly in (along the central axial direction of described reactor) described reactor body, and extends to described reactor body
The bottom of interior conversion zone II；Described fixed fluidized-bed reactor also includes distribution grid 12, and this distribution grid 12 is fixed on described heat
The lower end of galvanic couple temperature tube 13, described distribution grid 12 is circular sieve tray, and is perpendicular to described fixed fluidized-bed reactor
Central axis, the diameter of described sieve tray is 0.3:1 with the ratio of the internal diameter of the reactor cross-section of its place height, and percent opening is
5%, bore dia is 0.2mm.
Three outlets 8 are inserted perpendicularly into through the top (that is, upper flange plate 9) of described fixed fluidized-bed reactor hermetically
The top of settling section I, connects with this reactor.The one end being positioned at reactor body at described outlet 8 is separately installed with three
Individual filter tube 4, three filter tubes 4 include the polycrystalline substance being positioned at outlet 8 end in reactor body respectively and are arranged on
Pipe portion structure on the outer circle wall of this section port pipe 8, and the pipe portion structure of Partial filtration pipe 4 is along the length of outlet 8
Direction upwardly extends, and higher than upper flange plate 9(i.e., the top through this reactor is exposed to outside described reactor body
Portion), the pipe portion structure of the described Partial filtration pipe 4 higher than upper flange plate 9 is sealed by filter tube seal receptacle 7 and is fixed on reaction
The top of device.
Embodiment 1
In described fixed fluidized-bed reactor, the relative dimensions bag of the coking inhibitor injection part bottom settling section I
Include: taper type baffle plate 1 is 35 ° with the angle α of settling section wall；The height of taper type baffle plate is the 7% of settling section height altogether；
The annular internal diameter of filter plate 2 is 0.8 with the ratio of external diameter；The quantity of coking inhibitor inlet is 2；The material of annular filter plate is
00Cr17Ni14Mo2。
Steam is selected in carrier gas, and coking inhibitor is made up of Carbon bisulfide, dithioglycol and dimethyl disulfide, its mass ratio
For 2:1:1；Coking inhibitor is 2 × 10 with the weight ratio of hydrocarbon raw material (straight-run naphtha, character is shown in Table 1)-3, coking inhibitor
It is 3 × 10 with the weight ratio of carrier gas-6；Catalyst uses catalytic cracking catalyst, and trade names are CEP-1, the character of catalyst
As shown in table 2, operating condition is as shown in table 3.
After straight-run naphtha is preheated, feed pump it is injected into the above-mentioned fixed fluidized bed reaction equipped with CEP-1 catalyst
In device, two coking inhibitor inlets it is injected simultaneously into coking inhibitor and carrier gas thereof.Make reactor in the condition shown in table 3
Under carry out catalytic cracking reaction.Gaseous product analyzes its composition by on-line chromatograph, and product liquid is carried out by off-line chromatograph
Simulation distillation is also analyzed, and deposited the catalyst of coke through on-line decoking, passes through CO2CO in flue gas measured by in-line analyzer2Contain
Amount, draws coke output, and analysis result is as shown in table 4.
Embodiment 2
In described fixed fluidized-bed reactor, the relative dimensions bag of the coking inhibitor injection part bottom settling section I
Include: taper type baffle plate 1 is 35 ° with the angle α of settling section wall；The height of taper type baffle plate is the 15% of settling section height altogether；
The annular internal diameter of filter plate 2 is 0.7 with the ratio of external diameter；The quantity of coking inhibitor inlet is 4；The material of annular filter plate is
00Cr17Ni14Mo2。
Be made up of Carbon bisulfide, dithioglycol and dimethyl disulfide using steam as carrier gas, coking inhibitor, its quality it
Ratio is 2:1:1；.Coking inhibitor injection rate is 4 × 10 with the weight ratio of hydrocarbon raw material (straight-run naphtha, character is shown in Table 1)-3；
Coking inhibitor is 3 × 10 with the weight ratio of carrier gas-6；Catalyst uses catalytic cracking catalyst, and trade names are CEP-1, urge
The character of agent is as shown in table 2, and operating condition is as shown in table 3.
After straight-run naphtha is preheated, feed pump it is injected into the above-mentioned fixed fluidized bed reaction equipped with CEP-1 catalyst
In device, two coking inhibitor inlets it is injected simultaneously into coking inhibitor and carrier gas thereof.Make reactor in the condition shown in table 3
Under carry out catalytic cracking reaction.Gaseous product analyzes its composition by on-line chromatograph, and product liquid is carried out by off-line chromatograph
Simulation distillation is also analyzed, and deposited the catalyst of coke through on-line decoking, passes through CO2CO in flue gas measured by in-line analyzer2Contain
Amount, draws coke output, and analysis result is as shown in table 4.
Comparative example 1
The fixed fluidized-bed reactor used the difference is that only, at settling section with the reactor in embodiment 1 and 2
The bottom of I is not provided with described coking inhibitor injection part.And, using steam as carrier gas, coking inhibitor is by curing
Carbon, hydrogen sulfide and dithioglycol composition, its mass ratio is 2:1:1；Coking inhibitor and hydrocarbon raw material (straight-run naphtha, property
Matter is shown in Table 1) weight ratio be 2 × 10-3；Coking inhibitor is 1 × 10 with the weight ratio of carrier gas-6；Catalyst uses catalytic pyrolysis
Catalyst, trade names are CEP-1, and the character of catalyst is as shown in table 2, and operating condition is as shown in table 3.
Mix with the steam being loaded with coking inhibitor after straight-run naphtha is preheated, pump be injected into and urge equipped with CEP-1
In the laboratory routine fixed fluidized-bed reactor of agent, feed and continued to inject coking inhibitor and steam afterwards, directly
Start to stripping phase.Gaseous product analyzes its composition by on-line chromatograph, and product liquid is simulated by off-line chromatograph
Distill and analyze, deposited the catalyst of coke through on-line decoking, pass through CO2CO in flue gas measured by in-line analyzer2Content,
Drawing coke output, analysis result is as shown in table 4.
Comparative example 2
The fixed fluidized-bed reactor used the difference is that only, at settling section with the reactor in embodiment 1 and 2
The bottom of I is not provided with described coking inhibitor injection part.And, using steam as carrier gas, coking inhibitor is by curing
Carbon, hydrogen sulfide and dithioglycol composition, its mass ratio is 2:1:1；Coking inhibitor and hydrocarbon raw material (straight-run naphtha, property
Matter is shown in Table 1) weight ratio be 4 × 10-3；Coking inhibitor is 3 × 10 with the weight ratio of carrier gas-6；Catalyst uses catalytic pyrolysis
Catalyst, trade names are CEP-1, and the character of catalyst is as shown in table 2, and operating condition is as shown in table 3.
Mix with the steam being loaded with coking inhibitor after straight-run naphtha is preheated, pump be injected into and urge equipped with CEP-1
In the laboratory routine fixed fluidized-bed reactor of agent, feed and continued to inject coking inhibitor and steam afterwards, directly
Start to stripping phase.Gaseous product analyzes its composition by on-line chromatograph, and product liquid is simulated by off-line chromatograph
Distill and analyze, deposited the catalyst of coke through on-line decoking, pass through CO2CO in flue gas measured by in-line analyzer2Content,
Drawing coke output, analysis result is as shown in table 4.
Comparative example 3
Method according to embodiment 1 carries out catalytic cracking to straight-run naphtha, except that, do not pass through coking inhibitor
Injection part injects coking inhibitor, namely does not take the means of any slagging prevention.Reactor enters under the conditions shown in Table 3
Row catalytic cracking reaction.Gaseous product analyzes its composition by on-line chromatograph, and product liquid is simulated by off-line chromatograph
Distill and analyze, deposited the catalyst of coke through on-line decoking, pass through CO2CO in flue gas measured by in-line analyzer2Content,
Drawing coke output, analysis result is as shown in table 4.
Table 1
Table 2
| Project | CEP-1 catalyst |
| Quality composition/% | |
| Al2O3 | 46.7 |
| SiO2 | 49.8 |
| Physical property | |
| Specific surface area/(m2·g-1) | 177 |
| Micropore surface amasss/(mL g-1) | 80 |
| Pore volume/(mL g-1) | 0.182 |
| Micro pore volume/(mL g-1) | 0.045 |
Table 3
| Project | Numerical value |
| Raw oil | Straight-run naphtha |
| Catalyst | CEP-1 |
| Reaction temperature, DEG C | 670 |
| Oil ratio | 8 |
| Air speed, 1/h | 7 |
| Water filling (accounts for raw material), weight % | 20 |
Table 4
| Coke | Dry gas | Hydrogen | Ethylene+propylene | Coke descent rate | |
| Embodiment 1 | 3.52 | 15.52 | 1.22 | 17.23 | 72.3% |
| Embodiment 2 | 3.28 | 16.24 | 1.08 | 15.87 | 74.2% |
| Comparative example 1 | 7.23 | 22.24 | 2.67 | 13.54 | 43.1% |
| Comparative example 2 | 7.56 | 21.15 | 2.31 | 14.38 | 40.5% |
| Comparative example 3 | 12.71 | 28.62 | 4.91 | 15.74 | - |
From the analysis result of table 4, use fixed fluidized-bed reactor of the present invention, and pass through coking inhibitor
Injection part injects coking inhibitor, can substantially reduce coke and the yield of dry gas in product, greatly reduce the product of coke
Rate, also improves the yield of target product ethylene and propylene simultaneously.
Claims (19)
1. a fixed fluidized-bed reactor, this fixed fluidized-bed reactor include push up part sealing structure, reactor body and
The outlet (8) connected with described reactor body and feed pipe (11), described reactor body includes settling section from top to bottom
(I), conversion zone (II) and oil preparation initial contact section (III), it is characterised in that described settling section (I) bottom is provided with coking
Inhibitor injection part, it is circumferentially disposed that this coking inhibitor injection part includes along described settling section (I) bottom interior wall
The annular filter plate (2) of the inwall of taper type baffle plate (1), the top of connection taper type baffle plate (1) and reactor body and coking
Inhibitor inlet (3), taper type baffle plate (1), formation cavity between annular filter plate (2) and the inwall of reactor body, and institute
State coking inhibitor inlet (3) to connect with this cavity.
Fixed fluidized-bed reactor the most according to claim 1, wherein, described annular filter plate (2) is horizontally disposed with.
Fixed fluidized-bed reactor the most according to claim 1 and 2, wherein, the material of described annular filter plate (2) is resistance to height
Metal warm, corrosion resistant.
Fixed fluidized-bed reactor the most according to claim 1, wherein, the height of described taper type baffle plate (1) is described
The 5-20% of the height of settling section (I).
Fixed fluidized-bed reactor the most according to claim 4, wherein, the height of described taper type baffle plate (1) is described
The 7-15% of the height of settling section (I).
Fixed fluidized-bed reactor the most according to claim 1, wherein, internal diameter and the external diameter of described annular filter plate (2) it
Ratio is 0.5-0.9.
Fixed fluidized-bed reactor the most according to claim 6, wherein, internal diameter and the external diameter of described annular filter plate (2) it
Ratio is 0.7-0.8.
Fixed fluidized-bed reactor the most according to claim 1, wherein, the number of described coking inhibitor inlet (3)
For 1-6.
Fixed fluidized-bed reactor the most according to claim 8, wherein, the number of described coking inhibitor inlet (3)
For 2-4.
10. the using method of fixed fluidized-bed reactor described in any one in claim 1-9, the method includes: by hydrocarbon
Class raw material injects and carries out catalytic cracking reaction in described fixed fluidized-bed reactor, wherein, before injecting described hydrocarbon raw material
And/or period, the coking inhibitor carrier gas of liquid is injected described fixing fluidisation by described coking inhibitor inlet (3)
In bed reactor, described coking inhibitor is at least one sulfur-containing compound.
11. usings method according to claim 10, wherein, described coking inhibitor and the injection rate of described hydrocarbon raw material
Weight ratio be 1 × 10-3To 5 × 10-3。
12. usings method according to claim 11, wherein, described coking inhibitor and the injection rate of described hydrocarbon raw material
Weight ratio be 2 × 10-3To 4 × 10-3。
13. according to the using method described in any one in claim 10-12, and wherein, described coking inhibitor is selected from sulphuric acid
Salt, thiosulfate, hydrogen sulfide, Carbon bisulfide, dimethyl sulfoxide, Methyl disulfide, thiophene, dimethyl disulfide, mercaptan and hexichol
At least one in sulfur.
14. usings method according to claim 13, wherein, described coking inhibitor is selected from hydrogen sulfide, Carbon bisulfide, second
At least one in two mercaptan, dimethyl disulfide and Methyl disulfide.
15. according to the using method described in any one in claim 10-12, and wherein, described hydrocarbon raw material is Petroleum, light
Diesel oil and do in the heavy oil product below 500 DEG C at least one, and the sulfur content of described hydrocarbon raw material is not more than 1 weight
Amount %.
16. usings method according to claim 10, wherein, the weight of the injection rate of described coking inhibitor and described carrier gas
Amount ratio is 0.5 × 10-6To 5 × 10-6。
17. usings method according to claim 16, wherein, the weight of the injection rate of described coking inhibitor and described carrier gas
Amount ratio is 1 × 10-6To 3 × 10-6。
18. according to the using method described in any one in claim 10 and 16-17, wherein, described carrier gas be steam and/
Or noble gas.
19. usings method according to claim 18, wherein, described noble gas is nitrogen.
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| CN109705905B (en) * | 2017-10-25 | 2021-04-06 | 中国石油化工股份有限公司 | Method and device for producing more low-carbon olefins |
| CN114471385B (en) * | 2022-02-14 | 2023-04-28 | 聊城市鲁西化工工程设计有限责任公司 | Method and device for controlling synthesis reaction of polymerized fluidized organosilicon |
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| US4534851A (en) * | 1983-06-02 | 1985-08-13 | Exxon Research And Engineering Co. | Feed injection method to prevent coking on the walls of transfer line reactors |
| US4708787A (en) * | 1986-04-14 | 1987-11-24 | Amoco Corporation | Method for supplying a uniform liquid and gaseous mixture |
| US5284994A (en) * | 1993-01-13 | 1994-02-08 | Phillips Petroleum Company | Injection of antifoulants into thermal cracking reactors |
| US5346133A (en) * | 1993-03-25 | 1994-09-13 | The M. W. Kellogg Company | High temperature liquid injection apparatus |
| ZA976925B (en) * | 1996-08-06 | 1998-03-19 | Emr Microwave Technology Corp | Method and apparatus for optimization of energy coupling for microwave treatment of metal ores and concentrates in a microwave fluidized bed reactor. |
| RU2119524C1 (en) * | 1997-10-08 | 1998-09-27 | Товарищество с ограниченной ответственностью Научно-производственная фирма "Пальна" | Unit for introduction of solution of carbon deposition inhibitor in tube furnaces of pyrolysis of hydrocarbon raw materials |
| CA2365871A1 (en) * | 1999-03-18 | 2000-09-21 | Jackson I. Ito | Improved fcc feed injector fan tip design |
| DE102005019444B4 (en) * | 2005-04-21 | 2008-02-28 | Glatt Gmbh | Spray nozzle for a fluidized bed device |
| CN201064712Y (en) * | 2007-06-27 | 2008-05-28 | 中国石油化工股份有限公司 | Fixing fluid bed reactor for experimental investigation |
| CN201077829Y (en) * | 2007-07-19 | 2008-06-25 | 中国石油化工集团公司 | Coke tower bottom feeder |
| CN201912925U (en) * | 2010-11-18 | 2011-08-03 | 中国石油天然气股份有限公司 | Fixed fluidized bed reactor for experimental study on low-carbon olefin preparation through heavy oil catalytic cracking |
| CN202438304U (en) * | 2012-02-20 | 2012-09-19 | 中国石油化工股份有限公司 | Fixed fluidized bed reactor |
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