CN104560140B - A kind of residual hydrogenation method - Google Patents
A kind of residual hydrogenation method Download PDFInfo
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- CN104560140B CN104560140B CN201310498832.6A CN201310498832A CN104560140B CN 104560140 B CN104560140 B CN 104560140B CN 201310498832 A CN201310498832 A CN 201310498832A CN 104560140 B CN104560140 B CN 104560140B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
- C10G49/16—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles according to the "fluidised-bed" technique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of residual hydrogenation method, the method carries out in fluidized bed reactor, three-phase separation area it is disposed with from top to bottom in described fluidized bed reactor, boiling section and circulating-area, described residual hydrogenation method includes: inject the first boiling bed hydrogenation catalyst from the top of described circulating-area, the second boiling bed hydrogenation catalyst and suspension bed hydrogenation catalyst is injected from the top of described boiling section, residual oil and hydrogen is made to carry out hydrogenation reaction in described fluidized bed reactor, wherein, the particle diameter 0.05-0.8mm bigger than the particle diameter of described second boiling bed hydrogenation catalyst of described first boiling bed hydrogenation catalyst, in corresponding oxide, active metal component content 10-80% lower than the active metal component content in described second boiling bed hydrogenation catalyst in described first boiling bed hydrogenation catalyst.Preferably reaction effect can be obtained according to residual hydrogenation method of the present invention.
Description
Technical field
The present invention relates to a kind of residual hydrogenation method, in particular it relates to a kind of method adopting interior circulation type fluidized bed reactor that residual oil is carried out hydrotreatment, the method is particularly suitable for processing poor residuum.
Background technology
The day by day seriously market demand sustainable growth to light-end products of the weight of world's crude oil, in poor quality, therefore residual hydrogenation is as the effective means of residua upgrading and lighting, one of development priority having become as petroleum refining industry.Current industrial the most frequently used residual hydrogenation technology includes bed technology and ebullated bed technology, and wherein boiling bed hydrogenation technique has the advantage that and can process high tenor, the weight of high carbon residue, inferior raw material；Temperature of reactor is easily-controllable and uniform, and pressure drop is low and constant；Can adding online and take out catalyst, therefore catalyst performance can keep constant in the whole operation cycle；Higher conversion ratio and longer operation cycle can be reached.But boiling bed hydrogenation technique there is also obvious shortcoming, highlighting and be reflected in complex process, reaction efficiency is low, and product quality is also poor.This can be analyzed from the reason of fluidized bed reactor and catalyst grating technology two aspect.
The core of boiling bed hydrogenation technique is in that fluidized bed reactor.Existing industrialization boiling bed hydrogenation technology includes H-oil technique and LC-Fining technique etc., is provided with circulation cup and carries out gas-liquid separation in the fluidized bed reactor of both technique, and isolated oil product is circulated through circulation down-comer and circulating pump.Therefore, existing boiling bed hydrogenation technique also exists following deficiency: (1) complex operation, it is necessary to use complicated charge level monitor controller and oil circulating pump；System stability is poor, and when oil circulating pump breaks down, catalyst can settle to reactor bottom because fluidizing, and causes device to be forced to stop work.(2) catalyst in reactor reserve is relatively low, and space reactor utilization rate is low.(3) energy consumption is big, and the fluidisation of solid catalyst is squeezed into substantial amounts of recycle oil by oil circulating pump and realized.(4) in circulation down-comer, hydrogen is little, and for non-hydrogen environment, liquid at high temperature can occur second pyrolysis reaction coking to reduce product quality.
The direction that fluidized bed reactor improves specifically includes that the complexity reducing operation, improves the space availability ratio of reactor, reduces energy consumption, improves the operating flexibility etc. of reactor.CN1448212A proposes a kind of novel fluidized bed reactor, and this fluidized bed reactor eliminates charge level monitor controller and the oil circulating pump of complexity, therefore has the feature such as simple in construction, processing ease.But owing to this reactor uses particle diameter to be the solid catalyst of 0.1-0.2mm, therefore operating flexibility is less, and reactor easily taken out of by catalyst, the operational stability of influential system.
In fluidized bed reactor, material is in three-phase back-mixing state, if using the combination of multiple catalysts in same reactor, these catalyst substantially can be evenly distributed in reaction zone, the catalyst that so some aperture is less, hold metal ability poor also can run into raw material more inferior at reactor inlet, metal and carbon deposit that aperture can quickly be deposited block, causing hydrogenation activity rapid decrease, those apertures catalyst activity reduction relatively big, that appearance metal ability is stronger then can be a lot of slowly.Such different catalysts inactivation is asynchronous, and cannot both catalyst be made a distinction when taking out decaying catalyst, will ultimately result in catalyst utilization low, deficiency in economic performance.Therefore, a kind of catalyst can only generally be used in existing single fluidized bed reactor, it is impossible to using the combination of multifunction catalyst as fixed-bed process, in existing ebullated bed, the technology of different catalysts grating realizes generally by multistage reactor.
CN1458234A discloses a kind of Cascade boiling bed residual oil method of hydrotreating and equipment, by arranging of inner member, single fluidized bed reactor is divided into two or more, every section individually adds row's catalyst, it is possible to realize HDM and the grating of the catalyst such as hydrodesulfurization, denitrogenation in single reactor.But the method uses a large amount of inner members, and the device volume efficiency that responds is low, the shortcomings such as Operating Complexity height is low with stability.
CN102443414A discloses a kind of heavy oil feed oil boiling bed hydrogenation processing method, its be characterized by same fluidized bed reactor use at least two catalyst mixed catalyst, catalyst A's can several apertures be 15-30nm, the hole of aperture 30-300nm accounts for the 35%-60% of total pore volume, and the bore dia of catalyst B at least accounts for the 70% of total pore volume in the hole of 5-20nm.Although the method achieves the Gradation Optimization of multiple hydrogenation catalyst in same fluidized bed reactor, but owing to two kinds of catalyst of mixing all can directly with the inferior raw material haptoreaction having just enter into reactor, catalyst B has substantial amounts of aperture, it is poor that it holds metal ability, metal and carbon deposit that aperture can quickly be deposited block, causing hydrodesulfurization activity rapid decrease, catalyst A activity decrease then can be a lot of slowly.Such two kinds of catalysqt deactivations are asynchronous, and cannot both catalyst be made a distinction when taking out decaying catalyst, will ultimately result in catalyst utilization low, deficiency in economic performance.
CN102453525A discloses a kind of Multi-stage boiling bed hydrogenation process, and the reactor of its use at least includes an inner circulation zone, and inner circulation zone is made up of circular sleeve and taper diffuser and a guide frame.In its a kind of embodiment, the inner circulation zone from reactor bottom to top uses the activity of catalyst to increase successively, particle size reduction.Owing to the liquid speed difference between each inner circulation zone is not only small, the back-mixing in each race way of varigrained catalyst meeting larger proportion, therefore still cannot avoid the asynchronous problem that but cannot distinguish extraction of catalysqt deactivation.
Summary of the invention
The invention aims to overcome Problems existing in existing Residue Hydrotreating Technology, it is provided that a kind of new residual hydrogenation method.
The invention provides a kind of residual hydrogenation method, the method carries out in fluidized bed reactor, three-phase separation area it is disposed with from top to bottom in described fluidized bed reactor, boiling section and circulating-area, described residual hydrogenation method includes: inject the first boiling bed hydrogenation catalyst from the top of described circulating-area, the second boiling bed hydrogenation catalyst and suspension bed hydrogenation catalyst is injected from the top of described boiling section, residual oil and hydrogen is made to carry out hydrogenation reaction in described fluidized bed reactor, wherein, the particle diameter 0.05-0.8mm bigger than the particle diameter of described second boiling bed hydrogenation catalyst of described first boiling bed hydrogenation catalyst, in corresponding oxide, active metal component content 10-80% lower than the active metal component content in described second boiling bed hydrogenation catalyst in described first boiling bed hydrogenation catalyst.
Residual hydrogenation method according to the present invention, technological operation is easy, and energy consumption is low, operating flexibility is big, and the hydrogenation catalyst that simultaneously can realize difference in functionality carries out grating in same fluidized bed reactor so that its reaction efficiency is higher, and product quality is better.
In the preferred case, the fluidized bed reactor implementing residual hydrogenation method of the present invention includes: housing, three phase separation parts, interior pipe and gas-liquid distributor, described three-phase separation area, described boiling section and described circulating-area are arranged at the inside of described housing, described three phase separation parts are arranged at described three-phase separation area, said inner tube is arranged at described circulating-area, described gas-liquid distributor is arranged at the bottom of said inner tube, wherein, described three phase separation parts include the conical baffled and hollow revolving body being arranged at this conical baffled top circumferentially formed, described conical baffled on be provided with through hole, described through hole to the minimum range of longitudinal center's axis of described housing more than the inner side of described hollow revolving body to the minimum range of longitudinal center's axis of described housing, the top of described hollow revolving body is inversed taper platform shape, bottom is taper type, the surrounding of described three phase separation parts separates with the inwall of described housing, and corresponding to the sidewall of the housing of described hollow revolving body is provided with liquid outlet.
In above-mentioned preferred fluidized bed reactor, by arranging interior pipe in housing, and make gas-liquid distributor be positioned at the bottom of said inner tube, make to be formed in reactor circulating-area, material circulation of circulating-area in reactor can be promoted by the density contrast of material in the kinetic energy of entrance material and tedge (i.e. said inner tube) and down-comer (ring pipe being namely made up of said inner tube and described housing) completely jointly, such that it is able to cancel the circulating pump that energy consumption is big；In addition, by arranging boiling section as the buffering between circulating-area and three-phase separation area on circulating-area top, can farthest reduce the circulating-area logistics at high speed impact to three-phase separation area, simultaneously by optimizing three phase separation parts, improve efficiency and the elasticity of three phase separation, such that it is able to cancel the charge level monitor controller of complicated operation.The improvement of above-mentioned several aspect makes fluidized bed reactor more energy-conservation in course of reaction, and operates easier.
And, in the running of above-mentioned fluidized bed reactor, it is the state that coexists of gas-liquid-solid three-phase in down-comer, thus still can react in down-comer, thus substantially increasing the utilization ratio of reactor；And also ensure that the nitrogen atmosphere of facing of down-comer, thus greatly reduce the generation of heat scission reaction under non-hydrogen environment, such that it is able to avoid the coking produced due to the heat scission reaction of non-hydrogen atmosphere.
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, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below.In the accompanying drawings:
Fig. 1 is the structural representation of the preferred implementation of the fluidized bed reactor used in residual hydrogenation method of the present invention；
Fig. 2 is the structural representation of the preferred implementation of the fluidized bed reactor used in residual hydrogenation method of the present invention；
Fig. 3 is the structural representation of the preferred implementation of the fluidized bed reactor used in residual hydrogenation method of the present invention；
Fig. 4 is the parameter schematic diagram of the fluidized bed reactor shown in Fig. 3；
Fig. 5 is the structural representation of the preferred implementation of the fluidized bed reactor used in residual hydrogenation method of the present invention；
Fig. 6 is the structural representation of a kind of embodiment of gas-liquid distributor.
Description of reference numerals
Pipe in 1 housing 2 three phase separation parts 3
4 gas-liquid distributor 5 boiling bed hydrogenation catalyst entrances
6 catalyst exit line 7 charging aperture 8 air vents
9 liquid outlet 10 nozzle 14 suspension bed catalyst inlets
16 catalyst outlet 17 boiling bed hydrogenation catalyst entrances
The conical baffled 22 hollow revolving bodies of 20 taper type baffle plates 21
24 gas separation pipe 25 through holes
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
In the present invention, when not making contrary explanation, the noun of locality of use typically refers to reference to shown in the drawings upper and lower such as " upper and lower "；It is inside and outside that " inside and outside " refers to relative to the profile of each parts itself.
Described residual hydrogenation method provided by the invention carries out in fluidized bed reactor, is disposed with three-phase separation area, boiling section and circulating-area in described fluidized bed reactor from top to bottom.
Under preferable case, as Figure 1-5, described fluidized bed reactor includes housing 1, three phase separation parts 2, interior pipe 3 and gas-liquid distributor 4, described three-phase separation area, described boiling section and described circulating-area are arranged at the inside of described housing 1, described three phase separation parts 2 are arranged at described three-phase separation area, said inner tube 3 is arranged at described circulating-area, described gas-liquid distributor 4 is arranged at the bottom of said inner tube 3, wherein, described three phase separation parts 2 include circumferentially being formed conical baffled 21 and be arranged at this hollow revolving body 22 above conical baffled 21, it is provided with through hole 25 on described conical baffled 21, described through hole 25 to the minimum range of longitudinal center's axis of described housing 1 more than the inner side of described hollow revolving body 22 minimum range to longitudinal center's axis of described housing 1, the top of described hollow revolving body 22 is inversed taper platform shape, bottom is taper type, the surrounding of described three phase separation parts 2 separates with the inwall of described housing 1, and corresponding to the sidewall of the housing 1 of described hollow revolving body 22 is provided with liquid outlet 9.
In the present invention, described housing 1 can optionally from the housing of conventional fluidized bed reactor, for instance, described housing 1 can be straight tube shape housing.There is no particular limitation for the size of described housing 1, it is possible to determines according to needs of production.
In the present invention, described three-phase separation area refers to the region from the bottom of described three phase separation parts 2 to the top of described housing 1, described circulating-area refers to the region from the top of said inner tube 3 to the bottom of described housing 1, and described boiling section refers to the region from the bottom of described three phase separation parts 2 to the top of said inner tube 3.Axial along described housing 1, the height of described three-phase separation area can be the 5-20% of described housing 1 total height, it is preferred to 7-15%；The ratio of the height of described boiling section and the height of described circulating-area is 0.1-4:1, it is preferred to 0.1-1:1.
In the present invention, the upper end open of said inner tube 3 all connects with housing 1 with lower ending opening.Arranging said inner tube 3 to be primarily in described housing 1 and form circulating-area, therefore, there is no particular limitation for the size of said inner tube 3, forms circulating-area as long as being capable of in described housing 1.Under preferable case, in described circulating-area, the diameter (d of said inner tube 32) with the diameter (d of described housing 11) ratio be 0.55-0.84:1.Height (the h of said inner tube 32) with the height sum (h of described circulating-area and described boiling section2+h3) ratio can be 0.2-0.9:1, it is preferred to 0.5-0.9:1.Here, when said inner tube 3 is multiple, the height (h of said inner tube 32) refer to that the bottom of interior pipe of bottom is to the distance at the top of the interior pipe of the top.
In the preferred case, as shown in Figures 2 and 4, in described circulating-area, it is disposed with multiple interior pipe 3 from top to bottom, namely said inner tube 3 is multistage.In this preferred implementation, multiple circulation can be formed in described circulating-area by arranging pipe in multistage, thus multiple conversion zone can be formed in course of reaction in circulating-area, thus being more beneficial for the carrying out of reaction.Specifically, the number of said inner tube 3 can be 2-6, it is preferred to 2-3.
In a preferred embodiment, as shown in Figures 2 and 4, in described circulating-area, the sidewall of described housing 1 is provided with at least one nozzle 10, Open Side Down for this nozzle 10, namely is provided with at least one nozzle 10 that Open Side Down on the ring pipe between described housing 1 and said inner tube 3.In this preferred implementation, in course of reaction, spray into hydrogen-rich gas by nozzle 10 and be possible not only to increase the kinetic energy of circulation, and may also operate as hydrogen make-up to avoid the effect of coking produced due to the heat scission reaction of non-hydrogen atmosphere.It is further preferred that described nozzle 10 is arranged on the upper end of interior pipe 3.When said inner tube 3 is multiple, it is preferable that be respectively provided with nozzle in the upper end of each interior pipe 3.
Described nozzle can be gas nozzle commonly used in the art, and usually, the gas nozzle of employing should have the setting of anti-backflow.Described nozzle is preferably in rotationally symmetrical distribution, and generally often group nozzle is at least 4, and the size according to reactor diameter, described nozzle can also be multiple rows of distribution in concentric circles.Described nozzle can provide extra gas and kinetic energy for reactor, it is also possible to supplements and injects new hydrogen.Preferably, the gas flow injected by nozzle accounts for the 5-40 volume % of total gas flow.
When said inner tube 3 is multistage, in each section, the internal diameter of pipe 3 is preferably identical.It is highly preferred that distance between pipe 3 is 0.2-2:1, more preferably 0.3-1.0:1 with the diameter ratio of said inner tube 3 in adjacent two sections.
In the present invention, as Figure 1-5, the bottom of described housing 1 is further typically provided with charging aperture 7, and the gas-liquid mixture of question response is by described charging aperture 7 and enters in described fluidized bed reactor through described gas-liquid distributor 4.The top of described housing 1 is further typically provided with air vent 8, for discharging reactor through the isolated gas of described three phase separation parts 2.
In the present invention, as Figure 1-5, in order to increase the stability of reactor, the outlet of described gas-liquid distributor 4 is preferably placed at more than the lower ending opening of said inner tube 3, namely the outlet of gas-liquid distributor 4 is fully located at the inside of said inner tube 3.In this case, the gas-liquid mixture injected by described gas-liquid distributor 4 can fully enter the inside (also referred to as tedge) of said inner tube 3, and flow up in this tedge, thus being conducive to formation circulation between described tedge and described down-comer, described down-comer refers to the ring pipe being made up of said inner tube 3 and described housing 1.
Described gas-liquid distributor 4 can be various routines can make gas and the uniform structure of liquid distribution, for instance can be annular bubble cap structure.Specifically, as shown in Figure 6, the opening of described gas-liquid distributor 4 can be arranged on internal ring.
In the present invention, described three phase separation parts 2 are mainly used for carry out gas-solid-liquid three phase separation through described circulating-area and the reacted material of described boiling section, with by reaction produce gas and liquid is separated and discharges respectively through air vent 8 and liquid outlet 9.In described three phase separation parts 2, arrange described conical baffled 21 and be primarily to the gas-liquid separation region (i.e. the inner space of the inversed taper platform shape on hollow revolving body 22 top) avoiding substantial amounts of solid catalyst to enter three phase separation parts 2 top, and overflow across the entrance liquid collection region, top (space namely constituted between outside and the inwall of housing 1 of hollow revolving body 22) of three phase separation parts 2, and then discharged by liquid outlet 9, because described fluidized bed reactor in course of reaction in the flow velocity of logistics directly over pipe 3 very fast, without baffle, the logistics of this part entrained solids catalyst granules will directly be broken through three phase separator 2 and enter the gas-liquid separation region on three phase separation parts 2 top.In described three phase separation parts 2, why make through hole on described conical baffled 21 25 to the minimum range of longitudinal center's axis of described housing 1 more than the inner side of described hollow revolving body 22 minimum range to longitudinal center's axis of described housing 1, directly break through three phase separator 2 also for the logistics with solid catalyst particle avoided from interior pipe 3 and enter the gas-liquid separation region on three phase separation parts 2 top.
Described conical baffled 21 can be taper conical, square or triangular pyramidal.Preferably, described conical baffled 21 is cone.When described conical baffled 21 is cone, the big opening diameter (d of described conical baffled 216) with the internal diameter (d of described housing 11) ratio can be 0.8-0.97:1, the angle (β) of the axis of the described bus of conical baffled 21 and described housing 1 can be 30-85 DEG C.
Through hole 25 on described conical baffled 21 can be multiple, and total aperture area of described through hole 25 can be the 5-40% that the radial section of described housing 1 is long-pending.
Preferably, described through hole 25 arrives the minimum range (d of longitudinal center's axis of described housing 17/ 2) more than the radius (d of described housing 11/ 2) 40%, more preferably the radius (d of described housing 11/ 2) 45-75%.
In the present invention, described hollow revolving body 22 can be made up of (namely the little opening of the little opening of inversed taper platform shape baffle plate and taper type baffle plate is directly connected to) the taper type baffle plate of the inversed taper platform shape baffle plate on top and bottom, it is also possible to is the structure being formed by connecting by transition connection portion part by the taper type baffle plate of the inversed taper platform shape baffle plate on top Yu bottom.The inversed taper platform shape baffle plate on top and the taper type baffle plate of bottom can be each truncated cone or square cone.Under preferable case, described hollow revolving body 22 is made up of the rounding taper type baffle plate on top and the truncated cone baffle plate of bottom.Under this preferable case, the little opening diameter (d of the truncated cone baffle plate of bottom9) with the internal diameter (d of described housing 11) ratio can be 0.4-0.7:1, the big opening diameter (d of the truncated cone baffle plate of bottom8) with the internal diameter (d of described housing 11) ratio can be 0.8-0.97:1, and the angle (ω) of the axis of the bus of the truncated cone baffle plate of bottom and described housing 1 can be 30-85 DEG C；The little opening diameter of the rounding taper type baffle plate on top is equal with the little opening diameter of the truncated cone baffle plate of bottom, and the big opening diameter (d of the rounding taper type baffle plate on top10) with the internal diameter (d of described housing 11) ratio can be 0.8-0.97:1, and the angle (φ) of the axis of the bus of the truncated cone baffle plate on top and described housing 1 can be 30-85 DEG C.
In a preferred embodiment, described three phase separation parts 2 also include being arranged at the taper type baffle plate 20 below described conical baffled 21.By arranging described taper type baffle plate 20, it is possible to cushion the logistics of circulating-area from below and boiling section further.It is highly preferred that described through hole 25 arrives the minimum range (d of longitudinal center's axis of described housing 17/ 2) more than the top of the described taper type baffle plate 20 minimum range (d to longitudinal center's axis of described housing 15/ 2).Described taper type baffle plate 20 can be truncated cone or square cone, it is preferred to truncated cone.When described taper type baffle plate 20 is truncated cone, the little opening diameter (d of described taper type baffle plate 205) with the internal diameter (d of described housing 11) ratio can be 0.4-0.7:1, the big opening diameter (d of described taper type baffle plate 203) with the internal diameter (d of described housing 11) ratio can be 0.8-0.97:1, the angle (α) of the axis of the bus of described taper type baffle plate 20 and described housing 1 can be 30-85 DEG C.
In a preferred embodiment, described three phase separation parts 2 also include gas separation pipe 24, and the lower ending opening of described gas separation pipe 24 is positioned on described conical baffled 21, and upper end open is positioned at the top of described hollow revolving body 22.
In another kind of preferred implementation, described three phase separation parts 2 also include gas separation pipe 24, and the lower ending opening of described gas separation pipe 24 is positioned on described taper type baffle plate 20, and upper end open is positioned at the top of described hollow revolving body 22.
Described gas separation pipe 24 can be one or more, it is preferred to many as at least 4, can be such as specifically 4-20 root.When described gas separation pipe 24 is many, described gas separation pipe 24 can be rotationally symmetrical distribution, it is also possible in some circle distributions, and the 2-50% that the radial section that the gross area of the lower ending opening of described gas separation pipe 24 can be described housing 1 amasss.Preferably, described gas separation pipe 24 arrives the minimum range minimum range more than described through hole 25 to longitudinal center's axis of described housing 1 of longitudinal center's axis of described housing 1.It is highly preferred that described gas separation pipe 24 arrives the minimum range (d of longitudinal center's axis of described housing 14/ 2) for the radius (d of described housing 11/ 2) 60-90%.
In described fluidized bed reactor, between outside and the inwall of described housing 1 of described hollow revolving body 22, constitute liquid collection region.
In described fluidized bed reactor, described conical baffled 21, described hollow revolving body 22, said inner tube 3 and described taper type baffle plate 20 are preferably with described housing 1 and are coaxially disposed.
In described fluidized bed reactor, liquid outlet 9 is arranged on the sidewall of the housing 1 corresponding to described hollow revolving body 22, namely described liquid outlet 9 is arranged on the sidewall of housing corresponding to described liquid collection region 1.Preferably, described liquid outlet 9 is 1:0.8-10 to distance and the described liquid outlet 9 of the upper end of described hollow revolving body 22 to the ratio of distances constant of the lower end of described hollow revolving body 22, it is preferred to 1:1-5.
In described fluidized bed reactor, top corresponding to the sidewall of the described housing 1 of described boiling section is provided with boiling bed hydrogenation catalyst entrance 5 and suspension bed hydrogenation catalyst entrance 14, bottom corresponding to the sidewall of the described housing 1 of described boiling section is provided with catalyst outlet 16, top corresponding to the sidewall of the described housing 1 of described circulating-area is provided with boiling bed hydrogenation catalyst entrance 17, and the bottom of described housing 1 is provided with catalyst exit line 6.In this case, the catalyst being injected boiling section by boiling bed hydrogenation catalyst entrance 5 can be discharged by catalyst outlet 16, the catalyst being injected circulating-area by boiling bed hydrogenation catalyst entrance 17 can be discharged by catalyst exit line 6, thus realizing online more catalyst changeout.
It can be 1:1-100 that described boiling bed hydrogenation catalyst entrance 5 arrives the distance of the lower end of described three phase separation parts 2 with the ratio of distances constant of described boiling bed hydrogenation catalyst entrance 5 to the upper end of said inner tube 3, it is preferred to 1:2-20.
Preferably, described suspension bed hydrogenation catalyst entrance 14 is arranged at the top of described boiling bed hydrogenation catalyst entrance 5.
In the described fluidized bed reactor of the present invention, the statistical average speed of boiling section logistics has the advantages that middle flash wall is low, so the logistics speed at boiling section center is very fast, entrained solid concentration is also higher.As illustrated in fig. 1 and 2, when described three phase separation parts 2 do not include the taper type baffle plate 20 below conical baffled 21, in the running of described fluidized bed reactor, described conical baffled 21 are directly rushed at through described circulating-area and the reacted gas-liquid-solid mixture of described boiling section, when the inwall at described conical baffled 21 tops is encountered in center speed and the higher logistics of solid concentration, logistics direction changes with the direction of inwall, namely by upwards transferring Xiang Bianbi to and downward, the ability of the logistics upwards entrained solids after the change of direction substantially dies down, therefore, the effect of described conical baffled 21 cores is in that to rely on change logistics direction to carry out separating most solid；Relatively small from the logistics speed immediately below through hole 25, its entrained solid concentration is relatively low, center logistics after this fraction of stream and part change direction enters the region (being called " gas-liquid-solid Disengagement zone ") constituted by described conical baffled 21 with the taper type baffle plate being positioned at described hollow revolving body 22 bottom from through hole 25, owing to space expands rapidly, liquid velocity declines rapidly, cannot upwards entrained solids again, simultaneously because be positioned at the restriction of the taper type baffle inner wall of described hollow revolving body 22 bottom, logistics direction also changes, it is downward that major part liquid then bearing both solid and small portion of gas start baffling, and small amount of liquids and major part gas enter upper space by the little opening of described hollow revolving body 22；The logistics major part that wherein baffling is downward returns described boiling section from the space between described conical baffled 21 and described housing 1, partially liq enters the liquid collection region being made up of the outer wall of described hollow revolving body 22 and the inwall of described housing 1 from the space between taper type baffle plate and the described housing 1 in described hollow revolving body 22 bottom, owing to described gas-liquid-solid Disengagement zone liquid speed upwards is much smaller than making solids fluidized critical liquid speed, so not having solid catalyst to enter described liquid collection region；The logistics being entered upper space by the little opening of hollow revolving body 22 can cause because sectional area expands rapidly that liquid speed reduces rapidly, and overflow in gas from liquid surface, it is seen that this segment space (is called " gas-liquid separation zone ") and mainly completes gas-liquid separation process.It should be noted that, even if owing to the logistics of the described gas-liquid separation zone of reason entrance of operation fluctuation is entrained with fraction solids, as reducing rapidly and returning to described gas-liquid-solid Disengagement zone of liquid velocity, affect described liquid collection region without taking out of from the top of described gas-liquid separation zone.As shown in Figures 3 and 4, when described three phase separation parts 2 include the taper type baffle plate 20 below conical baffled 21, the three-phase logistics separation process in three-phase separation area is similar with the process of above-mentioned embodiment, it is distinctive in that: in the process of above-mentioned embodiment, all of logistics all directly rushes at described conical baffled 21, and the logistics in non-central region rushes at the taper type baffle plate 20 being positioned at below described conical baffled 21 in the process of present embodiment, and there is baffling.
Visible, the described fluidized bed reactor of the present invention is in running, except the gas enrichment region at the top of described gas-liquid separation zone, described liquid collection region and described housing 1, the form that the logistics at all the other positions is all the mixture with gas-liquid-solid three-phase exists, thus catalytic reaction can both occur.Therefore, the described fluidized bed reactor adopting the present invention substantially can be avoided catalyst solid to pass through liquid outlet 9 taking out of, but also the utilization ratio of fluidized bed reactor can be improved further, greatly reduce the generation of heat scission reaction under non-hydrogen environment simultaneously.
Therefore, compared with existing fluidized bed reactor, above-mentioned preferred fluidized bed reactor is characterised by including at least one strong circulating-area and a boiling section.Described circulating-area includes middle tedge (in namely pipe 3) and annular space down-comer, and described annular space down-comer is made up of the annular space in the middle of middle tedge and reactor direct tube section shell wall.Owing to live gas all only passes in middle tedge, there is density contrast in middle tedge and annular space down-comer, additionally circulating-area is with the restriction of middle tedge, material is little more than boiling section in the circulation area of tedge and down-comer, therefore three phase materials form strong circulation at circulating-area, and the linear velocity of material is very fast.Part three phase materials therefrom between tedge top enter boiling section, owing to boiling section does not have the restriction of middle tedge, therefore gas trends towards uniformly in the distribution of boiling section, but still can there is certain difference in center and wall place, limit, therefore can there is a weak circulation at boiling section in material on the whole, but the linear velocity of material is less.The existence of strong circulating-area and weak circulating-area objectively makes reactor define the conversion zone of multistage, adds the liquid time of staying in reactor, improves reaction efficiency.It addition, the difference of circulating-area and boiling section material linear velocity also provides the basis using different-diameter catalyst: at circulating-area, the linear velocity of material is very fast, minor diameter catalyst is easy to bring into boiling section from middle tedge top；At boiling section, the linear velocity of material is relatively slow, and major diameter catalyst is easy to sink to circulating-area from annular space tedge top.It addition, fluidized bed reactor of the present invention is respectively provided with corresponding catalyst inlet/outlet at circulating-area and boiling section.Therefore, most major diameter catalyst is concentrated in circulating-area distribution, and the catalyst of most minor diameter is concentrated in boiling section distribution.
And, in preferred embodiment, by arranging gas nozzle in annular space down-comer, can play and improve the effect of the hydrogen content of gas in annular space down-comer, and by regulating the gas distribution that the gas flow of gas nozzle can also regulate in reactor, thus improving reaction efficiency further.
In the present invention, described residual oil can be the inferior raw materials such as reduced crude, decompression residuum, deasphalted oil, coal tar, coal liquefaction heavy oil.
Described residual hydrogenation method provided by the invention includes: inject the first boiling bed hydrogenation catalyst from the top of described circulating-area, inject the second boiling bed hydrogenation catalyst and suspension bed hydrogenation catalyst from the top of described boiling section, make residual oil and hydrogen carry out hydrogenation reaction in described fluidized bed reactor.Specifically, described first boiling bed hydrogenation catalyst is injected by boiling bed hydrogenation catalyst entrance 17, described second boiling bed hydrogenation catalyst is injected by boiling bed hydrogenation catalyst entrance 5, and described suspension bed hydrogenation catalyst is injected by suspension bed hydrogenation catalyst entrance 14.
In the present invention, the particle diameter 0.05-0.8mm bigger than the particle diameter of described second boiling bed hydrogenation catalyst of described first boiling bed hydrogenation catalyst, it is preferable that 0.1-0.6mm.Specifically, the particle diameter of described first boiling bed hydrogenation catalyst can be 0.15-1mm, and the particle diameter of described second boiling bed hydrogenation catalyst can be 0.10-0.95mm.
In the present invention, in corresponding oxide, the active metal component content 10-80% lower than the active metal component content in described second boiling bed hydrogenation catalyst in described first boiling bed hydrogenation catalyst, it is preferable that 20-60%.Specifically, in corresponding oxide, the active metal component content in described first boiling bed hydrogenation catalyst can be 2-25 weight %, and the active metal component content in described second boiling bed hydrogenation catalyst can be 5-30 weight %.
Described first boiling bed hydrogenation catalyst can be identical with conventional boiling bed hydrogenation catalyst with the composition of described second boiling bed hydrogenation catalyst, for instance, the two can contain carrier and active metal component independently of one another.Described carrier can be the carrier that this area is conventional, for instance can be selected from least one in aluminium oxide, silicon oxide and titanium oxide.Described active metal component can be selected from least one in vib base metal and group VIII base metal, it is preferred to nickel-tungsten combination, nickel-tungsten-cobalt combination, nickel-molybdenum combination or cobalt-molybdenum combination.
Described first boiling bed hydrogenation catalyst and described second boiling bed hydrogenation catalyst can be the extrudate shape or spherical of various routine.The bulk density of the two can be each 0.3-1g/cm3, specific surface area can be each 50-300m2/g。
In described method provided by the invention, by controlling injection circulating-area and the particle diameter of hydrogenation catalyst of boiling section, catalyst pores distribution and active metal component content, circulating-area and boiling section can be made to realize different hydrogenating functions, the catalyst such as making circulating-area mainly realizes the hydrodesulfurization function of dominant, makes the catalyst of boiling section mainly realize hydrodesulfurization function.In one more preferably embodiment, described first boiling bed hydrogenation catalyst and described second boiling bed hydrogenation catalyst are respectively provided with the pore structure of bimodal distribution.Owing to fluidized bed reactor inevitably existing the situation of catalyst back-mixing, and when the hydrogenation catalyst used has the pore structure of bimodal distribution, it is possible to slow down the loss of activity that catalyst back-mixing causes.
In described method provided by the invention, the volume ratio of the consumption of described first boiling bed hydrogenation catalyst and described second boiling bed hydrogenation catalyst can be 0.3-9:1, it is preferred to 1-5:1.
In described method provided by the invention, by introducing suspension bed hydrogenation catalyst, its hydrogenating function and boiling bed hydrogenation catalyst can play good complementary action, thus being conducive to the Hydrogenation of raising system, increase light oil yield.
In the preferred case, described suspension bed hydrogenation catalyst adds with the form carrying the distillate of this suspension bed hydrogenation catalyst.In such a case, it is possible to avoid when boiling section top occur catalyst concn too low even without catalyst, such that it is able to significantly improve the utilization rate of reactor, greatly reduce the generation of heat scission reaction under non-hydrogen environment simultaneously.
In the distillate carrying suspension bed hydrogenation catalyst, the content (by metal agent) of suspension bed hydrogenation catalyst can be 100-3000 μ g/g.
In the present invention, described suspension bed hydrogenation catalyst can be homogeneous catalyst commonly used in the art.Described suspension bed hydrogenation catalyst can be water miscible or oil-soluble.Wherein, water miscible suspension bed hydrogenation catalyst can be at least one in the phosphate of nickel, molybdenum, cobalt and tungsten, assorted multi-carboxylate or ammonium salt, and oil-soluble suspension bed hydrogenation catalyst can be at least one in many carboxylic salts of nickel, molybdenum, cobalt and tungsten or naphthenate.
In the distillate carrying suspension bed hydrogenation catalyst, the boiling range of distillate can be 250-530 DEG C.Preferably, described distillate is selected from catalytic wax oil, wax tailings and liquefied coal coil.
In described method provided by the invention, relative to the consumption of the described residual oil of 100 weight portions, the consumption carrying the distillate of suspension bed hydrogenation catalyst can be 3-25 weight portion.
In the present invention, there is no particular limitation for the condition of described hydrogenation reaction, it is possible to boiling bed hydrogenation reaction condition conventionally is implemented.In the preferred case, the condition of described hydrogenation reaction includes: reaction temperature is 300-480 DEG C, and hydrogen dividing potential drop is 6-25MPa, and during liquid, volume space velocity is 0.05-4h-1, hydrogen to oil volume ratio is 100-1500.In the present invention, pressure refers to absolute pressure.
In described method provided by the invention, according to the scale that device processes, one or more fluidized bed reactor can be set, can use in parallel or series as required when multiple fluidized bed reactor is set, can also connect after fluidized bed reactor one or more fixed bed reactors, but at least one fluidized bed reactor uses above-mentioned preferred fluidized bed reactor and operating procedure.
Compared with existing residual hydrogenation method, the advantage of residual hydrogenation method provided by the invention is:
(1) fluidized bed reactor adopted is at least provided with a circulating-area, and material circulation of circulating-area in reactor is promoted jointly by the kinetic energy of entrance material and the density contrast of tedge and down-comer, and energy consumption reduces.Eliminate circulating pump and the charge level monitor controller of complicated operation, simple to operate.Compared with the same other technologies cancelling circulating pump, under identical energy consumption, this reactor can support higher catalyst concn, improves the utilization ratio of reactor.
(2) three phase separator of the fluidized bed reactor adopted uses two separate structure, and organically combines with reactor content outlet, greatly reduces catalyst taking-out amount, improves the operating flexibility of three phase separator.
(3) fluidized bed reactor adopted is provided with at least one circulating-area and a boiling section, defines multistage conversion zone, adds the liquid time of staying in reactor, improves reaction efficiency.
(4) fluidized bed reactor adopted is provided with at least one circulating-area and a boiling section, the material speed of circulating-area and boiling section is otherwise varied, this makes circulating-area and boiling section can adopt different-diameter and the catalyst of activity, the grating of multi-functional boiling-bed catalyst is achieved in same fluidized bed reactor, improve reaction efficiency, improve product quality.
(5) in a preferred embodiment, the distillate carrying suspension bed hydrogenation catalyst squeezed into by the fluidized bed reactor adopted on boiling section top, the too low situation even without catalyst of catalyst concn is not so had on boiling section top, substantially increase the utilization ratio of reactor, greatly reduce the generation of heat scission reaction under non-hydrogen environment simultaneously.
(6) hydrogenating function of the suspension bed catalyst adopted and conventional boiling-bed catalyst can play good complementary action, are conducive to the Hydrogenation of raising system, increase light oil yield.
(7) in a preferred embodiment, gas nozzle is set in annular space down-comer, it is possible to improve the material cycle kinetic energy at circulating-area；And, the hydrogen content of gas in annular space down-comer can be improved by gas nozzle hydrogen make-up such that it is able to improve reaction efficiency further；It addition, by regulating the tolerance ratio in gas nozzle, it is possible to regulate the density contrast of tedge and down-comer, such that it is able to adapt to different catalyst particle size scopes and catalyst concn as required, improve the operating flexibility of reactor.
Further residual hydrogenation method of the present invention is described in detail below in conjunction with embodiment.
The reactor that fluidized bed reactor is structure as shown in Figure 5 used in following example, specifically, the agent structure of this fluidized bed reactor is housing 1, three-phase separation area, boiling section and circulating-area it is followed successively by from top to bottom in housing 1, three-phase separation area is provided with three phase separation parts 2, circulating-area is provided with interior pipe 3, the bottom of interior pipe 3 is provided with gas-liquid distributor 4, the upper end open of said inner tube 3 all connects with housing 1 with lower ending opening, and the opening of described gas-liquid distributor 4 is positioned at the top of the lower ending opening of said inner tube 3；Described three phase separation parts 2 include circumferentially formed conical baffled 21, it is arranged at this taper type baffle plate 20 below conical baffled 21, it is arranged at this hollow revolving body 22 above conical baffled 21, and along the symmetrical multiple gas separation pipes 24 of longitudinal center's axis of described housing 1, it is provided with along the symmetrical multiple through holes 25 of longitudinal center's axis of described housing 1 on described conical baffled 21, described through hole 25 to the minimum range of longitudinal center's axis of described housing 1 more than the inner side of described hollow revolving body 22 minimum range to longitudinal center's axis of described housing 1, the top of described hollow revolving body 22 is inversed taper platform shape, bottom is taper type, the surrounding of described three phase separation parts 2 separates with the inwall of described housing 1, and corresponding to the sidewall of the housing 1 of described hollow revolving body 22 is provided with liquid outlet 9；The lower ending opening of described gas separation pipe 24 is positioned on described taper type baffle plate 20, and upper end open is positioned at the top of described hollow revolving body 22；Described housing 1, said inner tube 3, described conical baffled 21, described taper type baffle plate 20 and described hollow revolving body 22 are coaxially disposed；Top corresponding to the sidewall of the described housing of described boiling section is provided with boiling bed hydrogenation catalyst entrance 5 and suspension bed hydrogenation catalyst entrance 14, bottom corresponding to the sidewall of the described housing of described boiling section is provided with catalyst outlet 16, top corresponding to the sidewall of the described housing of described circulating-area is provided with boiling bed hydrogenation catalyst entrance 17, the bottom of described housing 1 is provided with catalyst exit line 6, and the top of described housing 1 is provided with air vent 8；Said inner tube 3 includes two sections, and the top of pipe 3 is provided with 4 nozzles 10 in rotationally symmetrical distribution in every section.
The running of above-mentioned fluidized bed reactor is as follows: portion gas and residual oil raw material are entered reactor by charging aperture 7, enter in first paragraph in pipe 3 together with the gas-liquid-solid three-phase logistics come with the circulation of annular space down-comer after the gas-liquid distributor 4 at middle part, and in first paragraph pipe 3 in also stream flow up.In first paragraph, the gas-liquid raw material in pipe 3 carries out catalytic hydrogenation reaction under the catalysis of the solid catalyst injected by catalyst inlet 17, reacting rear material flows out from pipe in first paragraph 3 top exit, enter first paragraph annular space down-comer together with the gas that part three-phase logistics is squeezed into this section of gas nozzle 10 and continue reaction, then loop back pipe 3 in first paragraph from reactor bottom；Part three-phase logistics then enters and continues reaction in second segment in pipe 3.Flow out from top exit after material reaction in pipe 3 in second segment, enter second segment annular space down-comer together with the gas that part three-phase logistics is squeezed into this section of gas nozzle 10 and continue reaction, then loop back pipe 3 in second segment；Part three-phase logistics then enters boiling section and continues reaction.Interior pipe 3 and annular space down-comer constitute circulating-area.Circulating-area and boiling section are reaction zone, and both Catalyst packing total amounts are at least the 20% of reactor dischargeable capacity, are generally 40-70%, it is preferred to 50-65%.Enter three phase materials of boiling section, the solid catalyst injected by catalyst inlet 5 and the distillate hybrid reaction carrying suspension bed catalyst injected by catalyst inlet 14, enter three-phase separation area at the reacted oil gas of boiling section entrainment of partially catalyzed agent to go forward side by side the liquid-solid three phase separation of circulation of qi promoting, isolated supernatant liquid is from liquid outlet 9 discharger, and the liquid of major part entrained solids catalyst returns to boiling section by the gap between the inwall of three phase separation parts 2 and housing 1 and continues to participate in reaction；In course of reaction, the catalyst that the particle diameter that added by catalyst inlet 17 is bigger can pass through catalyst exit line 6 after the deactivation and discharge, the catalyst that the particle diameter that added by catalyst inlet 5 is less can pass through catalyst outlet 16 after the deactivation and discharge, and changes online realizing catalyst.
Embodiment 1
The concrete size of the fluidized bed reactor used in the present embodiment is as shown in table 1 below.
Table 1
| Code name | Numerical value | Code name | Numerical value |
| d1/mm | 400 | h1/mm | 3600 |
| d2/mm | 300 | h2/mm | 2400 |
| d3/mm | 380 | h3/mm | 600 |
| d4/mm | 340 | α/° | 45 |
| d5/mm | 240 | β/° | 45 |
| d6/mm | 380 | ω/° | 45 |
| d7/mm | 260 | φ/° | 45 |
| d8/mm | 380 | Total aperture area/mm of gas separation pipe2 | 12000 |
| d9/mm | 240 | Total aperture area/mm of through hole2 | 20000 |
| d10/mm | 380 |
Above-mentioned fluidized bed reactor is adopted to carry out cold work die, wherein, the solid-phase catalyst added by catalyst inlet 5 is particle diameter is the spheric catalyst of 0.2mm, the solid-phase catalyst added by catalyst inlet 17 is particle diameter is the spheric catalyst of 0.3mm, and the color of both catalyst is otherwise varied is beneficial to experimental observation.Catalyst general reserve is the 60% of reactor dischargeable capacity.Liquid phase uses virgin kerosene, and volume space velocity is 0.25-3.0h-1.Gas phase uses nitrogen, and gas-oil ratio is 20-150.Gas nozzle 10 arranges 8, and the gas flow that gas nozzle is squeezed into accounts for the 15% of total gas flow.Test result indicate that in condition excursion, the drag-out of solid-phase catalyst is extremely low, is 2.0 μ g/g to the maximum.Meanwhile, it is observed that little particle size of catalyst concentrates on boiling section substantially in experiment, and big particle size of catalyst concentrates on circulating-area substantially.
Embodiment 2
The concrete size of the fluidized bed reactor used in the present embodiment is as shown in table 2 below.
Table 2
| Code name | Numerical value | Code name | Numerical value |
| d1/mm | 300 | h1/mm | 3000 |
| d2/mm | 240 | h2/mm | 1500 |
| d3/mm | 280 | h3/mm | 900 |
| d4/mm | 260 | α/° | 60 |
| d5/mm | 150 | β/° | 60 |
| d6/mm | 285 | ω/° | 60 |
| d7/mm | 170 | φ/° | 60 |
| d8/mm | 285 | Total aperture area/mm of gas separation pipe2 | 8000 |
| d9/mm | 160 | Total aperture area/mm of through hole2 | 15000 11 --> |
| d10/mm | 290 |
Above-mentioned fluidized bed reactor is adopted to carry out cold work die, wherein, the solid-phase catalyst added by catalyst inlet 5 is particle diameter is the spheric catalyst of 0.4mm, the solid-phase catalyst added by catalyst inlet 17 is particle diameter is the spheric catalyst of 0.6mm, and the color of both catalyst is otherwise varied is beneficial to experimental observation.Catalyst general reserve is the 50% of reactor dischargeable capacity.Liquid phase uses virgin kerosene, and volume space velocity is 0.25-3.0h-1.Gas phase uses nitrogen, and gas-oil ratio is 20-150.Gas nozzle 10 arranges 8, and the gas flow that gas nozzle is squeezed into accounts for the 20% of total gas flow.Test result indicate that in condition excursion, the drag-out of solid-phase catalyst is extremely low, is 1.7 μ g/g to the maximum.Meanwhile, it is observed that little particle size of catalyst concentrates on boiling section substantially in experiment, and big particle size of catalyst concentrates on circulating-area substantially.
Can be seen that from the result of embodiment 1-2, in bigger catalyst particle size and bigger inlet amount excursion, the fluidized bed reactor of the present invention can support the catalyst of high concentration, and the drag-out of catalyst is very low, little particle size of catalyst concentrates on boiling section substantially, and particle size of catalyst concentrates on circulating-area substantially greatly, this shows that the fluidized bed reactor performance of the present invention is outstanding, it is possible to meet industrial needs.
Embodiment 3-5
Embodiment 3 and 4 adopts the medium-sized hot reactor made according to the ratio of embodiment 1, embodiment 5 adopts the medium-sized hot reactor made according to the ratio of embodiment 2, wherein, the solid-phase catalyst and the physico-chemical property passing through the solid-phase catalyst that catalyst inlet 17 adds that are added by catalyst inlet 5 are as shown in table 3, two kinds of solid-phase catalyst amount of fill are the 55% of reactor dischargeable capacity, and the volume ratio of the consumption of two kinds of solid-phase catalysts is about 1:1.Residual oil raw material character is as shown in table 4.The distillate carrying suspension bed hydrogenation catalyst is injected as shown in table 5 by catalyst inlet 14.The tolerance injected by nozzle 10 accounts for 20 volume % of total tolerance.Reaction condition and result of the test in reactor are as shown in table 6.
Table 3
Table 4
| Character | Numerical value |
| Density (20 DEG C)/(g/cm3) | 1.029 |
| Carbon residue/weight % | 19.61 |
| Sulfur content/weight % | 4.53 |
| Nitrogen content/weight % | 0.23 |
| (Ni+V) content/(μ g/g) | 275.8 |
| Asphalitine (C7Not tolerant)/weight % | 6.5 |
Table 5
| Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Boiling range | 350-500℃ | 300-510℃ | 250-450℃ |
| Hydrogenation catalyst | Molybdenum naphthenate | Molybdenum naphthenate | Nickel naphthenate |
| Catalyst concn (μ g/g) | 1200 | 1500 | 1000 |
| Injection rate (accounts for the percentage ratio of residual oil raw material) | 10 weight % | 10 weight % | 15 weight % |
Comparative example 1-2
Method according to embodiment 3 carries out residual hydrogenation, institute the difference is that, respectively with in CN102453525A embodiment 1 fluidized bed reactor and in CN1458234A the fluidized bed reactor of embodiment 1 replace the fluidized bed reactor used in embodiment 3.Reaction condition and result of the test in reactor are as shown in table 6.
Comparative example 3
Method according to embodiment 3 carries out residual hydrogenation, institute the difference is that, be not injected into circulating-area catalyst.Reaction condition and result of the test in reactor are as shown in table 6.
Comparative example 4
Method according to embodiment 3 carries out residual hydrogenation, institute the difference is that, be not injected into boiling section catalyst.Reaction condition and result of the test in reactor are as shown in table 6.
Comparative example 5
Method according to embodiment 3 carries out residual hydrogenation, institute the difference is that, be not injected into carrying the distillate of suspension bed hydrogenation catalyst.Reaction condition and result of the test in reactor are as shown in table 6.
Table 6: technology assessment condition and evaluation result
By the data of table 6 it can be seen that preferably reaction effect can be obtained according to residual hydrogenation method of the present invention.
Claims (28)
1. a residual hydrogenation method, it is characterized in that, the method carries out in fluidized bed reactor, three-phase separation area it is disposed with from top to bottom in described fluidized bed reactor, boiling section and circulating-area, described residual hydrogenation method includes: inject the first boiling bed hydrogenation catalyst from the top of described circulating-area, the second boiling bed hydrogenation catalyst and suspension bed hydrogenation catalyst is injected from the top of described boiling section, residual oil and hydrogen is made to carry out hydrogenation reaction in described fluidized bed reactor, wherein, the particle diameter 0.05-0.8mm bigger than the particle diameter of described second boiling bed hydrogenation catalyst of described first boiling bed hydrogenation catalyst, in corresponding oxide, active metal component content 10-80% lower than the active metal component content in described second boiling bed hydrogenation catalyst in described first boiling bed hydrogenation catalyst.
2. method according to claim 1, wherein, described fluidized bed reactor includes housing (1), three phase separation parts (2), interior pipe (3) and gas-liquid distributor (4), described three-phase separation area, described boiling section and described circulating-area are arranged at the inside of described housing (1), described three phase separation parts (2) are arranged at described three-phase separation area, said inner tube (3) is arranged at described circulating-area, described gas-liquid distributor (4) is arranged at the bottom of said inner tube (3), wherein, described three phase separation parts (2) include conical baffled (21) that circumferentially formed and the hollow revolving body (22) being arranged at top, these conical baffled (21), described conical baffled (21) are provided with through hole (25), described through hole (25) to the minimum range of longitudinal center's axis of described housing (1) more than the inner side of described hollow revolving body (22) to the minimum range of longitudinal center's axis of described housing (1), the top of described hollow revolving body (22) is inversed taper platform shape, bottom is taper type, the surrounding of described three phase separation parts (2) separates with the inwall of described housing (1), and corresponding to the sidewall of the housing (1) of described hollow revolving body (22) is provided with liquid outlet (9).
3. method according to claim 2, wherein, described housing (1) is straight tube shape.
4. according to the method in claim 2 or 3, wherein, axial along described housing (1), the height of described three-phase separation area is the 5-20% of described housing (1) total height, and the ratio of the height of described boiling section and the height of described circulating-area is 0.1-4:1.
5., according to the method in claim 2 or 3, wherein, in described circulating-area, it is disposed with multiple interior pipe (3) from top to bottom.
6. according to the method in claim 2 or 3, wherein, in described circulating-area, the sidewall of described housing (1) being provided with at least one nozzle (10), Open Side Down for this nozzle (10).
7., according to the method in claim 2 or 3, wherein, in described circulating-area, the diameter ratio of the diameter of said inner tube (3) and described housing (1) is 0.55-0.84:1.
8. according to the method in claim 2 or 3, wherein, described three phase separation parts (2) also include being arranged at the taper type baffle plate (20) below described conical baffled (21).
9. method according to claim 8, wherein, described through hole (25) to the minimum range of longitudinal center's axis of described housing (1) more than the top of described taper type baffle plate (20) to the minimum range of longitudinal center's axis of described housing (1).
10. according to the method in claim 2 or 3, wherein, described three phase separation parts (2) also include gas and separate pipe (24), described gas separates the lower ending opening of pipe (24) and is positioned on described conical baffled (21), and upper end open is positioned at the top of described hollow revolving body (22).
11. method according to claim 8, wherein, described three phase separation parts (2) also include gas and separate pipe (24), described gas separates the lower ending opening of pipe (24) and is positioned on described taper type baffle plate (20), and upper end open is positioned at the top of described hollow revolving body (22).
12. method according to claim 10, wherein, described gas separates the pipe (24) minimum range to longitudinal center's axis of described housing (1) more than the described through hole (25) minimum range to longitudinal center's axis of described housing (1).
13. according to the method described in any one in claim 2-3,9 and 11-12, wherein, described through hole (25) is for multiple, and the 5-40% that the radial section that total aperture area of described through hole (25) is described housing (1) is long-pending.
14. according to the method described in any one in claim 2-3,9 and 11-12, wherein, described conical baffled (21), described hollow revolving body (22) and said inner tube (3) are coaxially disposed with described housing (1).
15. according to claim 2-3, 9 and 11-12 in method described in any one, wherein, top corresponding to the sidewall of the described housing of described boiling section is provided with boiling bed hydrogenation catalyst entrance (5) and suspension bed hydrogenation catalyst entrance (14), bottom corresponding to the sidewall of the described housing of described boiling section is provided with catalyst outlet (16), top corresponding to the sidewall of the described housing of described circulating-area is provided with boiling bed hydrogenation catalyst entrance (17), the bottom of described housing (1) is provided with catalyst exit line (6), the top of described housing (1) is provided with air vent (8).
16. method according to claim 1, wherein, the particle diameter 0.1-0.6mm bigger than the particle diameter of described second boiling bed hydrogenation catalyst of described first boiling bed hydrogenation catalyst.
17. the method according to claim 1 or 16, wherein, the particle diameter of described first boiling bed hydrogenation catalyst is 0.15-1mm, and the particle diameter of described second boiling bed hydrogenation catalyst is 0.10-0.95mm.
18. method according to claim 1, wherein, in corresponding oxide, the active metal component content 20-60% lower than the active metal component content in described second boiling bed hydrogenation catalyst in described first boiling bed hydrogenation catalyst.
19. the method according to claim 1 or 16, wherein, in corresponding oxide, the active metal component content in described first boiling bed hydrogenation catalyst is 2-25 weight %, and the active metal component content in described second boiling bed hydrogenation catalyst is 5-30 weight %.
20. according to the method described in any one in claim 1,16 and 18, wherein, described first boiling bed hydrogenation catalyst and described second boiling bed hydrogenation catalyst contain carrier and active metal component independently of one another, at least one in described support selected from alumina, silicon oxide and titanium oxide, described active metal component at least one in vib base metal and group VIII base metal.
21. method according to claim 20, wherein, described active metal component is nickel-tungsten combination, nickel-tungsten-cobalt combination, nickel-molybdenum combination or cobalt-molybdenum combination.
22. according to the method described in any one in claim 1,16,18 and 21, wherein, described first boiling bed hydrogenation catalyst and described second boiling bed hydrogenation catalyst are respectively provided with the pore structure of bimodal distribution.
23. according to the method described in any one in claim 1,16,18 and 21, wherein, the volume ratio of the consumption of described first boiling bed hydrogenation catalyst and described second boiling bed hydrogenation catalyst is 0.3-9:1.
24. method according to claim 1, wherein, described suspension bed hydrogenation catalyst adds with the form carrying the distillate of this suspension bed hydrogenation catalyst, and in the distillate carrying suspension bed hydrogenation catalyst, the content of suspension bed hydrogenation catalyst is 100-3000 μ g/g.
25. method according to claim 24, wherein, described suspension bed hydrogenation catalyst is water miscible or oil-soluble, water miscible suspension bed hydrogenation catalyst is at least one in the phosphate of nickel, molybdenum, cobalt and tungsten, assorted multi-carboxylate or ammonium salt, and oil-soluble suspension bed hydrogenation catalyst is at least one in many carboxylic salts of nickel, molybdenum, cobalt and tungsten or naphthenate.
26. method according to claim 24, wherein, the boiling range of described distillate is 250-530 DEG C.
27. the method according to any one in claim 24-26, wherein, relative to the consumption of the described residual oil of 100 weight portions, the consumption carrying the distillate of suspension bed hydrogenation catalyst is 3-25 weight portion.
28. method according to claim 1, wherein, the condition of described hydrogenation reaction includes: temperature is 300-480 DEG C, and hydrogen dividing potential drop is 6-25MPa, and during liquid, volume space velocity is 0.05-4h-1, hydrogen to oil volume ratio is 100-1500.
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