CN1272405C - Descending catalytic cracking reactor - Google Patents
Descending catalytic cracking reactor Download PDFInfo
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- CN1272405C CN1272405C CN 03137924 CN03137924A CN1272405C CN 1272405 C CN1272405 C CN 1272405C CN 03137924 CN03137924 CN 03137924 CN 03137924 A CN03137924 A CN 03137924A CN 1272405 C CN1272405 C CN 1272405C
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Abstract
The present invention relates to a descending catalytic cracking reactor which comprises the members, such as a regenerated catalyst conveying pipe (1), a top cap (2), a raw material nozzle (3), an outer cylinder (6), a pre-lift medium distributor (8), a descending reaction pipe (9) and a catalyst pre-lift pipe (14), wherein the outlet end for the upper part of the catalyst pre-lift pipe (14) is positioned in the outer cylinder (6), and the lower part of the catalyst pre-lift pipe (14) is communicated with the regenerated catalyst conveying pipe (1); the pre-lift medium distributor (8) is positioned at the bottom of the catalyst pre-lift pipe (14), and the upper end of the outer cylinder is hermetically connected with the top cap along the circumferential direction; the descending reaction pipe (9) is fixedly connected with the lateral wall or the bottom of the outer cylinder, or communicated with the lateral wall or the bottom of the outer cylinder by an additional pipe symmetrically arranged; the raw material nozzle is arranged on the lateral wall of the outer cylinder and/or the top cap which are/is positioned above the outlet of the catalyst pre-lift pipe.
Description
Technical field
The invention belongs to the catalyst cracker of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is a kind of Desending catalytic cracking reactor.
Background technology
Along with expanding economy, countries in the world are that the demand of the low-carbon alkene of raw material will constantly increase to vehicle fuel with the oil.Because petroleum resources are limited, the deep processing of development heavy oil, the supply that increases light-end products and low-carbon alkene will be the significant development strategy of 21 century oil refining industry.Catalytically cracked material wide adaptability, depth of conversion are big, when heavy feed stock is converted into automobile-used fuel such as vapour, diesel oil, contain more low-carbon alkene in the liquefied gas of generation, are that mink cell focus is carried out the most important technology of secondary processing.The catalytic cracking unit scale is big, facility investment is less relatively, is the pillar of all refinery's economic benefits in the world.The product that improves catalytic cracking unit distributes and product selectivity, for the economic benefit and the market competitiveness that improve oil refining enterprise crucial meaning is arranged all, is the target that all refineries lay siege to.
Because the value of petroleum chemicals is far above refined oil product, oil-refining chemical is integrated to be the important channel of improving utilization of resources, increasing the oil refining enterprise economic benefit, also is the development trend of current international petroleum processing industry.Because the demand of propylene increases sharply,, all pay attention to both at home and abroad in recent years by the FCC apparatus propylene enhancing in order to satisfy the demand in market.
On promoting the tubular type catalyst cracker by adopting high temperature, the reaction conditions of high agent-oil ratio and the productive rate that appropriate catalyst can increase low-carbon alkene in the product.In the riser reactor, hydrocarbon oil crude material sprays in the dense-phase catalyst bed of riser tube bottom by nozzle, is difficult to all atomize fully and vaporization in time.In order to make conversion that whole raw materials obtain enough degree of depth, must there be the long reaction times to generate more low-carbon alkene.Simultaneously, because catalyzer contrary gravity direction in riser tube flows, exist more serious back-mixing.Under such reaction environment, raw material has also generated a large amount of dry gas and coke when generating more low-carbon alkene, and the result causes the yield of high value added product to reduce.
In the down pipe reactor, oil gas and catalyzer flow along gravity direction, are approximately plug flow, and back-mixing seldom.The back-mixing degree of catalyzer reduces reduces its surperficial carbon distribution, thereby helps improving its catalytic activity and to the selectivity of high value added product.Since the eighties, external famous oil company is as Exxon, Mobil, UOP, Stone ﹠amp; Webster etc. have successively developed down-flow reactor separately, are used for improving the product selectivity of catalytic cracking or catalytic cracking reaction, and have applied for a series of patent.
USP4514285 discloses a kind of down pipe and dilute phase riser regenerated catalytic-cracking reaction system.After catalyzer is regenerated by dilute phase riser, in the regeneration degassing vessel, remove flue gas, improve density of catalyst, after forming dense-phase bed, enter descending reaction tubes by the catalyst distribution plate, stock oil distributes endless tube by hydrocarbon oil feed, radially sprays into descending reaction tubes through multitube, contact with the catalyzer in the free-falling process, and in descending reaction tubes, carry out cracking reaction.Catalyst concentration was lower when this down pipe reactor initially contacted with catalyzer owing to raw material hydrocarbon, and finish contacts, blended efficient is not ideal enough, and feed stock conversion is lower.
USP5296131, CN1205028A disclose a kind of down pipe reactor.In this reactor, regenerated catalyst flows out a formation annular " curtain " by the spool and the circumferential weld between the valve seat of conical-plug valve, stock oil by the nozzle radial spray of circumferentially evenly arranging under the conical surface to catalyzer " curtain ", contact with the catalyzer cross-flow, enter in the down-flow reactor then and react.Although this down-flow reactor has been strengthened the mixing of catalyzer and stock oil by the cross-flow contact, but, hydrocarbon oil crude material contacts because being still after nozzle ejection with catalyzer in the freely falling body process, catalyst concentration is still very low, and the quantity in the active centre that is provided is very limited.Therefore, the heavy oil conversion performance of this reactor is not good enough yet.
USP4985136, USP5462652 have disclosed a kind of ultrashort contact catalysis cracking method, i.e. MSCC.In the method, catalyzer flows downward with the form of curtain, and petroleum hydrocarbon vertically sprays in this catalyzer curtain, after reaction product and levels of catalysts are passed reaction zone, and finish mixture sharp separation; Catalyzer behind the part stripping directly enters the catalyst mix device without regeneration, with the catalyst mix after the holomorphosis, with the rising agent oil ratio.Though this method has improved the initial contact segment catalyst concentration of agent oil a little by the way that adds high agent-oil ratio, but, therefore also exist the agent oil problem that contact efficiency is not high, the heavy oil conversion degree of depth is not enough because catalyzer can not reach heavy oil and fully transform needed concentration in the freely falling body process.
USP5997726 has disclosed a kind of catalyst cracker of downstriker.Regenerated catalyst removes the regenerated flue gas of being carried secretly through degassing vessel, makes that catalyst density is improved in the degassing vessel; Above-mentioned catalyzer enters in the down-flow reactor by the plug valve of a control regenerated catalyst flow.In the finish exposure chamber that catalyzer falls into the bottom from the spool and the annulus between the valve seat of plug valve.Stock oil is sprayed onto in the agent oil exposure chamber by the hydrocarbon ils nozzle and is on the catalyzer of curtain shape freely falling body, enters down pipe reactor internal reaction together with catalyzer then.Though regenerated catalyst density after the degassing of holder gas tank can be improved in this reactor, but it still is free falling body state when initially contacting with stock oil, can't reach the needed concentration of hydrocarbon oil conversion, so the contact efficiency of finish is still not high enough, the changing effect of hydrocarbon ils is also not ideal enough.
Number of research projects is also being done by domestic units such as Qinghua university aspect the exploitation of down-flow reactor, and has applied for several patents of invention.
CN1265937A discloses a kind of at the telescopic reactor that promotes inner concentric tube installation down pipe.In this reactor, there are two kinds of schemes the position that hydrocarbon oil crude material sprays into beds, first kind of scheme is that hydrocarbon oil crude material is sprayed into ring catalyst lifting zone between riser tube and the down pipe by nozzle, in this annular region, contact to react and rise to the down pipe inlet simultaneously with catalyzer, flow into down pipe again, parallel flowing downward reacted simultaneously in down pipe; Second kind of scheme is that hydrocarbon oil crude material is directly sprayed in the down pipe, contacts with catalyzer in the freely falling body process.Thereby though the efficient that first kind of scheme can the catalyst concentration rising agent oil contact of the initial zone of action of rising agent oil, but the heavy hydrocarbon oil raw material is sprayed in the annular chuck district between riser tube and the down pipe by nozzle, hydrocarbon ils can be ejected on the outside wall surface of down pipe in the chuck inevitably, thereby cause heavy oil serious coking on the wall of chuck, influence the normal operation of device; And contact with catalyzer and stream on the catalyzer that is ejected in the freely falling body process owing to hydrocarbon oil crude material remains in second kind of scheme, because catalyst concn is low, the efficient that agent oil contacts is not high, the ability of heavy oil conversion also just can not be desirable.
CN1275434 discloses a kind of catalyst inlet device that is suitable for the gas-solid cocurrent flow descending bed reactor.This apparatus features is its shell and the coaxial installation of descending-bed reactor main body, and the top of shell is gas-solid biphase turbulent flow mixing zone, and carrier gas inlet is arranged on the following side wall of outer shell of down pipe reactor inlet.Carrier gas mixes the gas-solid two-phase turbulent flow mixing zone that the catalyzer of the pre-lifting zone of ring catalyst between shell and the down pipe is blown into cover top portion, enters in the down pipe reactor again and reacts.Hydrocarbon oil crude material contacts with the catalyzer of the unrestrained state of dilute phase in nozzle sprays into down pipe.Though this catalyst inlet device can make the catalyst distribution in the down pipe more even, but can't improve the catalyst concn in the down pipe, thereby still having the low problem of finish contact efficiency, the transformation efficiency of hydrocarbon oil crude material on the down-flow reactor that adopts this entrance structure is on the low side.
In sum, existing down-flow reactor exists to some extent all that the finish contact efficiency is low, heavy oil conversion performance is not enough or catalyzer back-mixing and the serious problem of equipment coking tendency, up to now, can properly settle the good down-flow reactor of the problems referred to above and reactivity worth does not appear in the newspapers as yet.
Summary of the invention
The object of the present invention is to provide a kind of Desending catalytic cracking reactor, in order to improve the atomizing effect of hydrocarbon oil crude material, improve the contact efficiency of hydrocarbon oil crude material and catalyzer, and the back-mixing of oil gas and catalyzer and the cracking level of raw material be controlled in the suitable scope, thereby when improving heavy oil conversion performance, increase the productive rate of low-carbon alkene in the product, reduce dry gas and coke in the product.
Down-flow reactor provided by the present invention comprises with lower member: regenerated catalyst 1, top cover 2, raw material nozzles 3, outer cylinder body 6, promote dielectric distribution device 8, descending reaction tubes 9, the pre-riser tube 14 of catalyzer in advance; Wherein, the top exit end of the pre-riser tube 14 of catalyzer is positioned at outer cylinder body 6 inside, and its underpart is communicated with regenerated catalyst 1; The pre-medium that promotes arranges that device 8 is positioned at the pre-riser tube of catalyzer 14 bottoms; The outer cylinder body upper end is connected with top cover is along the circumferential direction airtight; Descending reaction tubes 9 is fixedlyed connected with the sidewall or the bottom of outer cylinder body, or makes the two connection by symmetrically arranged arm 15; Raw material nozzles is arranged on the outer cylinder body sidewall of the pre-riser tube of catalyzer outlet top and/or on the top cover.
Compared with prior art, downstriker reactor for catalytic conversion of hydrocarbon oil provided by the present invention mainly has the advantage of following several respects:
1, in the down-flow reactor of the present invention hydrocarbon ils after nozzle ejection, at first in having the cavity of granules of catalyst, reactor head do not atomize, this atomizing raw materials mode has not only been improved the atomizing raw materials effect, and can make the raw material particle size size that initially contacts with catalyzer more even, thereby the boil-off rate of all raw materials and to reach the required time of certain depth of conversion also roughly the same, this has created favourable condition for the productive rate maximization that makes high value added product by controlling reaction time.
2, the initial contact on the surface of dense phase fluidized bed of raw material and catalyzer carried out in the down-flow reactor of the present invention, thereby can guarantee that it contacts with abundant catalyst active center, and hightails the bed reaction zone after finishing cracking reaction.So both bring into play the high advantage of bed reaction finish contact efficiency, overcome common bed catalysts back-mixing important disadvantages again, thereby can be so that catalyzer keeps high reactivity and good product selectivity when obtaining high heavy oil conversion rate.
3, down-flow reactor of the present invention is by being provided with the structure of bubble in the broken beds such as porous plate, grid or filler in the pre-riser tube of catalyzer, can be in suitable scope with the extent control of the initial zone of action of agent oil catalyzer back-mixing, thus selectivity of catalyst further improved.
4, down-flow reactor of the present invention has improved the device reliability of operation by anti-scorch steam distributor is set, can plays the effect that prevents oil gas serious coking in spray chamber near nozzle.
5, down-flow reactor inner catalyst of the present invention flows into a narrow relatively annular cavity from the pre-riser tube outlet of the catalyzer that is positioned at the central zone, and adopt the base arrangement be in tilted layout or with a plurality of arms with catalyzer in the annular cavity and oil gas introducing down pipe, can make catalyzer in descender, distribute more evenly, further improve the consistence of reaction conditions.
6, the These characteristics of down-flow reactor provided by the invention makes it have very strong heavy oil conversion performance, and has good product selectivity.Adopt Desending catalytic cracking reactor provided by the invention can significantly improve the productive rate of light-end products in the catalytic cracking process product or light olefin.
Description of drawings
The structural representation of Fig. 1-13 down-flow reactor provided by the present invention.
The schematic flow sheet of Figure 14-18 down-flow reactor provided by the present invention in catalytic cracking unit.
Embodiment
Through research and experiment repeatedly, we recognize: the major cause that the down-flow reactor heavy oil conversion performance is low is that the initial zone of action of finish density of catalyst is low, generally only is 10kg/m
2S can not provide abundant active centre for hydrocarbon oil crude material carries out cracking reaction.In Desending catalytic cracking reactor, if the density of heavy petroleum hydrocarbon and the formed finish mixture of catalyzer can be controlled at 150～500kg/m in the stage that hydrocarbon oil crude material and regenerated catalyst initially contact
2Scope in, and control oil gas and catalyzer well in initial contact segment back-mixing degree, just can obtain comparatively ideal heavy oil conversion performance and better products selectivity.
Describe the constructional feature of down-flow reactor provided by the present invention in detail below in conjunction with accompanying drawing, but therefore the present invention is not subjected to any restriction.
Figure 1 shows that a kind of structure formation of the present invention.In this form, the pre-riser tube 14 of catalyzer stretches into outer cylinder body inside from the end opening of outer cylinder body 6, and and outer cylinder body 6 disalignments, pipe is suitable for reading opens wide the end opening sealing for this.Suitable for reading and the top cover 2 of outer cylinder body is fixedlyed connected.Regenerated catalyst by transfer lime 1 after the flowrate control valve dominant discharge in the pre-riser tube of inflow catalyst.The pre-lifting enters the pre-riser tube of catalyzer after medium distributes by sparger 8, makes the catalyst fluidization in the pre-riser tube get up and make progress under pressure balanced effect to flow.Nozzle 3 sprays into catalytically cracked material in the cavity of top cover below from the sidewall of outer cylinder body and the top cover certain angle that tilts.This structure formation does not have special requirement to the layout of raw material nozzles, as long as can make hydrocarbon oil crude material be sprayed onto pre-riser tube outlet of catalyzer and peripheral region more equably, for example the central shaft with the pre-riser tube 14 of catalyzer is that symmetry axis is arranged nozzle on top cover 2 and outer cylinder body 6.The slit is closed with base plate 16 between the pre-riser tube of outer cylinder body end opening and catalyzer.Cavity between the pre-riser tube of outer cylinder body and catalyzer is bigger at a Side Volume of having arranged down pipe 9, helps catalyzer like this and flows into down pipe swimmingly.
Figure 2 shows that another kind of way of realization of the present invention.Pre-riser tube 14 of catalyzer and outer cylinder body 6 coaxial arrangement in this form.For the catalyzer in the annular cavity between pre-riser tube 14 and the outer cylinder body 6 can be flowed in the roughly the same time in the down pipe 9, the base plate 16 in this structure formation preferably is in tilted layout with horizontal direction is angled as shown in the figure.Raw material nozzles is symmetry axis symmetric arrangement on top cover 2 with the medullary ray of outer cylinder body preferably in this structure formation, and number of nozzle can be as shown in the figure 5,3,7 or more a plurality of.In order to prevent hydrocarbon oil crude material in the bottom of top cover 2 or the top coking of outer cylinder body 6, the arranged beneath at top cover 2 in this structure has anti-scorch steam distributor 5 in addition.The structure formation of this sparger and decoration form can be routinely the anti-scorch steam distributor at settling vessel top of catalytic cracking unit design.
Figure 3 shows that another kind of way of realization of the present invention.The pre-riser tube of catalyzer also is and outer cylinder body 6 coaxial arrangement in this structure formation, and its top cover 2 is a back taper, and raw material nozzles all is arranged in the top of outer cylinder body 6.The number of nozzle can be as shown in the figure 4, also can be 2,6,8 or more a plurality of, and these nozzles are preferably with the medullary ray symmetric arrangement of outer cylinder body or the pre-riser tube of catalyzer.In order to prevent that the air pocket that forms in the pre-riser tube 14 of catalyzer from breaking in the exit of pre-riser tube, the catalyzer of bed face is thrown to the space of top, cause the excessive back-mixing of catalyzer that contacts with raw material, this structure is provided with the inner member of bubble crushing on the top of pre-riser tube, this inner member can be a perforated panel structure 17 as shown in the figure, also can be grid, filler etc. other can make the structure of bubble breaking in the bed.
The difference of way of realization shown in Figure 4 and above-mentioned three kinds of ways of realization is that mainly this structure all arranging raw material nozzles on the top cover 2 He on the outer cylinder body 6.In addition, thus contact the form of the top of the pre-riser tube of catalyzer employing expansion tube in this structure efficiently with catalyzer for raw material is sprayed onto on the dense-phase catalyst bed of pre-riser tube outlet as much as possible.Cause the serious back-mixing of catalyzer that contact with raw material for the air pocket that prevents to form in the pre-riser tube of catalyzer breaks at the bed face of pre-riser tube outlet, this structure also is provided with the inner member of bubble crushing in the extension diameter section of riser tube in advance.The form of this inner member can be a cell structure 19 as shown in the figure, also can be that perforated panel, filler or other can make the structure of bubble breaking in the bed.In order to prevent that catalyzer from forming the mobile dead band in the bottom of annular cavity, this structure formation also between the lowest part of base plate and down pipe, be provided with one thin together with pipe 20.
Figure 5 shows that a kind of structure formation of reactor when the present invention adopts single raw material nozzles.
The present invention can directly be communicated with down pipe 9 and outer cylinder body 6 with oil gas in the annular cavity and catalyzer introducing down pipe internal reaction to shown in Figure 5 as Fig. 1, can also outer cylinder body 6 and down pipe 9 be communicated with the arm of a plurality of symmetric arrangement.The arm number that adopts is many more, and catalyzer flowing in annular cavity is just even more.Fig. 6, Fig. 7 and the structure formation that is respectively this reactor when adopting 2,3 and 4 to be communicated with arm 15 shown in Figure 8.When adopting a plurality of arms to be communicated with annular cavity and down pipe, the pre-riser tube 14 of outer cylinder body 6 and catalyzer can adopt isodiametric cylindrical shell, but preferably as Fig. 6 to change diameter cylindrical shell shown in Figure 8, and make the two coaxial.The base plate 16 of closes annular cavity end opening can adopt the structure of ring plate, dish or ellipsoidal head form, but preferably adopts truncated cone-shaped structure as shown in Figure 6 and Figure 7.In addition, also illustrated to be provided with the inner member form of bubble in porous plate 17 or filler 18 these two kinds of broken beds among Fig. 6 and Fig. 7 respectively on the top of the pre-riser tube 14 of catalyzer.
The present invention can also adopt way of realization as shown in Figure 9.The characteristics of this form are the inside that the pre-riser tube 14 of catalyzer all is positioned at outer cylinder body 6, catalyst transport 1 is fixedlyed connected with the pre-riser tube 14 of outer cylinder body 6 and catalyzer, and the slit and the pre-riser tube of catalyzer that pass between pre-riser tube of catalyzer and the outer cylinder body are communicated with.The inlet of down pipe 9 is fixedlyed connected with the end opening of the outer cylinder body 6 with variable-diameter structure and is interconnected.
The pre-riser tube 14 of catalyzer can also can be to form an angle with vertical direction as shown in figure 10 as Fig. 1 to shown in Figure 9 being arranged vertically in the down-flow reactor of the present invention, bend pipe that can also be as shown in figure 11 or U-shaped pipe shown in Figure 12.In a word, no matter take the pre-riser tube of catalyzer of which kind of structure formation, as long as can catalyst transport be overflowed in the outer cylinder body 6 to outer cylinder body inside and from the suitable for reading of this transfer lime by this pipe.When the pre-riser tube of catalyzer stretches into outer cylinder body when inner from the end opening of outer cylinder body, the slit between the pre-riser tube of outer cylinder body end opening and catalyzer is with base plate 16 sealings, and the sidewall of down pipe and outer cylinder body is fixedlyed connected and interconnected; If it is inner or when all being positioned at outer cylinder body that the pre-riser tube of catalyzer stretches into outer cylinder body from the sidewall of outer cylinder body, then the end opening of outer cylinder body and down pipe suitable for reading fixedlyed connected and is interconnected.
Catalyst transport can adopt an inclined tube in the down-flow reactor of the present invention, also can be as shown in figure 13, after the flowrate control valve of a vertically arranged catalyst transport, draw 2 arms symmetrically, catalyst transport is arrived in the vertically arranged pre-riser tube 14.Certainly, in this structure, the number of arm can for example, 3,4 or more, can be determined according to the size of unit scale flexibly more than 2.
Figure 14 is that the pre-riser tube of catalyzer is the layout synoptic diagram of descending structure of reactor in the catalytic cracking reaction-regeneration system that erect riser, down pipe directly are connected with the sidewall of outer cylinder body.
Figure 15 is that the pre-riser tube of catalyzer is the layout synoptic diagram of descending structure of reactor in the catalytic cracking reaction-regeneration system that erect riser, down pipe are connected with outer cylinder body by a plurality of arms.
Figure 16 is the layout synoptic diagram of descending structure of reactor in the catalytic cracking reaction-regeneration system that the pre-riser tube of catalyzer is in tilted layout.
Figure 17 is that the pre-riser tube of catalyzer is the layout synoptic diagram of descending structure of reactor in the catalytic cracking reaction-regeneration system of U-shaped pipe.
Figure 18 is that catalyst transport is divided into 2 arms with descending structure of reactor the layout synoptic diagram catalytic cracking reaction-regeneration system in of catalyst transport in the pre-riser tube.
The invention provides the downstriker reactor for catalytic conversion of hydrocarbon oil does not have special requirement to the catalyzer that is adopted, and any catalyzer in catalytic cracking field that is applicable to all can be used for reactor provided by the invention.For example, the active ingredient of catalyst system therefor can be selected from: contain or do not contain Y type, HY type or USY type zeolite, β zeolite, the ZSM-5 zeolite of rare earth or in other supersiliceous zeolite with five-membered ring structure one or more.
Downstriker catalytic conversion method of hydrocarbon oil main technique condition provided by the present invention is as follows: 500～700 ℃ of down pipe reactor outlet temperature, preferred 530～650 ℃; Agent-oil ratio 4～30, preferred 6～25; Finish duration of contact is less than 0.2～1.5 second, preferably less than 0.3～1 second in the descending reaction tubes; Stock oil atomizing steam amount accounts for 3～30 heavy % of total feed, preferred 5～20 heavy %; The anti-scorch steam injection rate in atomizing raw materials chamber accounts for 3～30 heavy % of total feed, preferred 5～20 heavy %; Pre-2～20 heavy % that medium (water vapour or dry gas) accounts for total feed, preferred 3～15% of promoting.Reaction pressure (absolute pressure) 0.05～0.25MPa, preferred 0.07～0.15MPa.
Downstriker reactor for catalytic conversion of hydrocarbon oil provided by the invention has no particular limits stock oil character, any hydrocarbon feed of catalytic cracking unit that is applicable to all can be used as the raw material of this reactor, for example, the mixture of long residuum, vacuum residuum, decompressed wax oil, deasphalted oil, wax tailings, hydrogenation tail oil, gasoline fraction, diesel oil distillate and above-mentioned two or more hydrocarbon ils.
Further specify the workflow of reactor provided by the present invention below in conjunction with accompanying drawing 13.
As shown in figure 13, the pyritous regenerated catalyst enters catalyzer pre-riser tube 14 by catalyst transport 1 through the flowrate control valve dominant discharge from revivifier.The pre-medium (water vapor or dry gas) that promotes feeds pre-riser tube bottom by sparger 8, regulates the pre-flow that promotes gas, and catalyzer is controlled at 100～500kg/m in the density of pre-riser tube beds
3By nozzle 3 ejections, the dense-phase bed surface that is sprayed onto pre-riser tube outlet contacts also vaporization rapidly catalytic cracking reaction takes place with catalyzer adverse current or cross-flow behind the fuel oil preheating.Product, catalyzer and still uncracked hydrocarbon ils oil gas, the atomized water steam that reaction back generates, promote medium in advance and enter descending reaction tubes 9 by the annular cavity between pre-riser tube of catalyzer and the outer cylinder body 6 together.Thereby uncracked hydrocarbon oil crude material can continue to contact with catalyzer in annular cavity and down pipe and is cracked into light-end products.Under certain reaction temperature, agent-oil ratio (being the ratio of the inlet amount of the flow of unit time inner catalyst in the reactor and hydrocarbon oil crude material) and reaction pressure, (according to the requirement of processing condition, reaction pressure＜gauge pressure in the down pipe reactor〉can between 0.05～0.3MPa, select, agent-oil ratio can be selected between 3～40, and the temperature in down pipe exit can be selected between 450～750 ℃.) oil gas carries out 0.25～10 second catalytic cracking reaction in down pipe 9 after, arrive the down pipe outlet and flow in the gas-solid Quick Separation System 10, separate rapidly with catalyzer, in order to avoid the catalytic cracking product because of contacting with catalyst excess cracking reaction took place.Isolated catalyzer is stripping in the stripper 11 of settling vessel bottom, and wherein entrained oil gas stripping comes out, and enters in the catalyst regeneration system 13 recycle behind the coke burning regeneration through reclaimable catalyst line of pipes 12 and flowrate control valve.Process isolated oil gas of gas solid separation system and stripping medium enter the fractionation and the absorbing-stabilizing system (not drawing among the figure) at rear portion together by pipeline, fractionate out product streams such as dry gas, liquefied gas, gasoline, diesel oil, heavy oil.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Comparative Examples
The resulting test-results of the disclosed down-flow reactor of CN1205028A is adopted in this Comparative Examples explanation on the catalyst cracker middle-scale device.
The treatment capacity of the middle-scale device that this Comparative Examples adopted is 0.24t/d.Testing sequence is as follows: stock oil is after the process furnace preheating, in high-efficient atomizing nozzle injecting reactor, contact with high temperature catalyst and react from revivifier, oil gas and catalyzer separate rapidly after by reactor, oil gas is sent into subsequent separation system through transfer line and is carried out product separation, the long-pending catalyzer that coke is arranged is sent into the revivifier coke burning regeneration after the reaction behind the water vapour stripping, and the catalyzer after the regeneration is delivered to reactor cycles and used.Various products are measured, analyze.
The used three kinds of raw material oil propertiess of 3 Comparative Examples are referring to table 1.Comparative Examples 1,2,3 catalyst system therefors are respectively to be MLC-500, CRP-1 and CEP catalyzer by the industrial trade names of Sinopec Qilu Petrochemical branch office catalyst plant, and its character sees Table 2.3 main operational conditions of Comparative Examples, product distribute and main products character sees Table 3, table 4 and table 5.
Present embodiment explanation: adopt down-flow reactor provided by the present invention resulting test-results under conventional catalytic cracking reaction condition.
Used down pipe structure of reactor form as shown in Figure 1 among this embodiment.
The raw materials used oil of embodiment, catalyzer and testing sequence are all identical with Comparative Examples 1, and main operational condition, product distribute and main products character sees Table 3.
As can be seen from Table 3, compare with Comparative Examples, heavy oil content has reduced percentage point more than 10 in the product of embodiment, the lighter hydrocarbons productive rate has improved percentage point more than 10, dry gas yied and Comparative Examples remain basically stable, though the absolute yield of coke rises to some extent, this causes because of there being more heavy oil to obtain transforming, if calculate by relative productive rate (dry gas yied/heavy oil conversion rate or coke yield/heavy oil conversion rate), dry gas yied of the present invention and liquefied gas yield are all obviously low than Comparative Examples.As seen adopt down-flow reactor provided by the invention to transform the heavy hydrocarbon oil raw material, can obviously improve the transformation efficiency of heavy oil and increase the yield of lighter hydrocarbons.
Present embodiment explanation: the test-results that adopts down-flow reactor provided by the present invention under harsh reaction conditions, to obtain.
The structure of used down-flow reactor as shown in Figure 7 among this embodiment.
The raw materials used oil of embodiment, catalyzer and testing sequence are all identical with Comparative Examples 2, and main operational condition, product distribute and main products character sees Table 4.
As can be seen from Table 4, compare with Comparative Examples, heavy oil content has reduced percentage point more than 8 in the product of embodiment, and the lighter hydrocarbons productive rate has improved nearly 9 percentage points, and the productive rate of dry gas yied and coke and Comparative Examples remain basically stable.The productive rate of propylene has improved percentage point more than 3 in the product.As seen adopt down-flow reactor provided by the invention to transform hydrocarbon oil crude material, can obviously improve the yield of lighter hydrocarbons and increase the productive rate of propylene.
Present embodiment explanation: the test-results that adopts down-flow reactor provided by the present invention under the reaction conditions of high severity, to obtain.
The structure of used down-flow reactor as shown in figure 11 among this embodiment.
The raw materials used oil of embodiment, catalyzer and testing sequence are all identical with Comparative Examples 3, and main operational condition, product distribute and main products character sees Table 5.
As can be seen from Table 5, compare with Comparative Examples, heavy oil content has reduced percentage point more than 6 in the product of embodiment, and ethylene yield and productivity of propylene have all improved percentage point more than 3, and the productive rate of coke has reduced nearly 1 percentage point.As seen adopt down-flow reactor provided by the invention to transform hydrocarbon oil crude material, can obviously improve the transformation efficiency of heavy oil and increase the productive rate of low-carbon alkene.
Table 1
| Raw material type | A | B | C |
| Density (20 ℃)/gcm -3 | 0.9005 | 0.8648 | 0.9012 |
| Carbon residue/% | 6.9 | 1.29 | 4.8 |
| Elementary composition/% | |||
| C | 86.00 | 85.65 | 86.53 |
| H | 12.59 | 13.56 | 12.84 |
| Metal content, ppm | |||
| Ni | 6.3 | 0.48 | 6.3 |
| V | 3.4 | ＜0.01 | 0.05 |
| Boiling range/℃ | |||
| Initial boiling point | 279 | 274 | 284 |
| 10％ | 363 | 365 | 388 |
| 30％ | 425 | 407 | 429 |
| 50％ | 484 | 465 | 492 |
Table 2
| Physical properties | MLC-500 | CRP-1 | CEP |
| Specific surface area m 2/g | 298 | 160 | 152 |
| Pore volume, ml/g | 0.40 | 0.26 | 0.24 |
| Tap density, g/cm 3 | 0.69 | 0.86 | 0.91 |
| Size composition, heavy % | |||
| 0～40μm | 17.4 | 26.0 | 16.6 |
| 40～80μm | 44.1 | 60.8 | 42 |
| ＞80μm | 38.5 | 13.2 | 41.4 |
Table 3
| Project | Comparative Examples 1 | |
| Raw material type | A | A |
| Catalyzer | MLC-500 | MLC-500 |
| Main operational condition: | ||
| Temperature of reaction, ℃ | 500 | 500 |
| Reaction pressure (table), kPa | 100 | 100 |
| Raw material preheating temperature, ℃ | 220 | 220 |
| The regenerator temperature, ℃ | 712 | 713 |
| Agent-oil ratio | 10.2 | 10.7 |
| Reaction times, s | 0.5 | 0.5 |
| Product distributes, heavy % | ||
| Dry gas | 2.37 | 2.45 |
| Liquefied gas | 10.25 | 11.67 |
| Gasoline | 28.53 | 32.72 |
| Diesel oil | 33.75 | 38.43 |
| Heavy oil | 15.34 | 4.26 |
| Coke | 9.13 | 9.76 |
| Loss | 0.63 | 0.71 |
| The heavy oil conversion rate, heavy % | 84.66 | 95.74 |
| Gasoline+diesel oil+liquefied gas | 72.53 | 82.82 |
| Dry gas yied/heavy oil conversion rate | 0.0280 | 0.0258 |
| Coke yield/heavy oil conversion rate | 0.1078 | 0.1026 |
| Main products character: | ||
| Gasoline density, g/cm 3 | 0.71 | 0.71 |
| Gasoline RON | 90 | 91 |
| MON | 77 | 78 |
| Diesel oil density, g/cm 3 | 0.86 | 0.91 |
| Condensation point of diesel oil, ℃ | 0 | -13 |
Table 4
| Project | Comparative Examples 2 | |
| Raw material type | B | B |
| Catalyzer | CRP-1 | CRP-1 |
| Main operational condition: | ||
| Temperature of reaction, ℃ | 560 | 560 |
| Reaction pressure (table), kPa | 100 | 100 |
| Raw material preheating temperature, ℃ | 260 | 260 |
| The regenerator temperature, ℃ | 710 | 695 |
| Agent-oil ratio | 18.6 | 18.3 |
| Reaction times, s | 0.6 | 0.6 |
| Product distributes, heavy % | ||
| Dry gas | 6.77 | 6.86 |
| Liquefied gas | 43.13 | 48.42 |
| Gasoline | 22.31 | 24.47 |
| Diesel oil | 11.25 | 12.83 |
| Heavy oil | 9.70 | 0.74 |
| Coke | 6.11 | 6.03 |
| Loss | 0.73 | 0.65 |
| Wherein the light olefin productive rate weighs % | ||
| Ethene | 3.28 | 3.65 |
| Propylene | 20.67 | 24.37 |
| Main products character: | ||
| Gasoline density, g/cm 3 | 0.75 | 0.75 |
| Gasoline RON | 96 | 95 |
| MON | 82 | 81 |
| Diesel oil density, g/cm 3 | 0.88 | 0.94 |
| Condensation point of diesel oil, ℃ | -8 | -19 |
Table 5
| Project | Comparative Examples 3 | |
| Raw material type | C | C |
| Catalyzer | CEP | CEP |
| Main operational condition: | ||
| Temperature of reaction, ℃ | 650 | 650 |
| Reaction pressure (table), kPa | 100 | 100 |
| Raw material preheating temperature, ℃ | 320 | 320 |
| The regenerator temperature, ℃ | 745 | 740 |
| Agent-oil ratio | 23.2 | 22.7 |
| Reaction times, s | 0.8 | 0.8 |
| Product distributes, heavy % | ||
| H 2～C 2 | 28.76 | 33.61 |
| C 3～C 4 | 29.17 | 34.35 |
| C + 5Cracking naphtha | 1 8.24 | 16.25 |
| Cracking light oil | 7.13 | 6.46 |
| Heavy oil | 6.64 | 0.37 |
| Coke | 9.25 | 8.33 |
| Loss | 0.81 | 0.63 |
| Wherein the light olefin productive rate weighs % | ||
| Ethene | 15.73 | 18.87 |
| Propylene | 18.43 | 21.66 |
| Main products character: | ||
| Gasoline density, g/cm 3 | 0.81 | 0.83 |
| Gasoline RON | 97 | 100 |
| MON | 84 | 86 |
| Diesel oil density, g/cm 3 | 0.90 | 0.98 |
| Condensation point of diesel oil, ℃ | -12 | -25 |
Claims (11)
1, a kind of Desending catalytic cracking reactor is characterized in that this reactor comprises with lower member: regenerated catalyst (1), top cover (2), raw material nozzles (3), outer cylinder body (6), promote dielectric distribution device (8), descending reaction tubes (9), the pre-riser tube of catalyzer (14) in advance; Wherein, the top exit end of the pre-riser tube of catalyzer (14) is positioned at outer cylinder body (6) inside, and its underpart is communicated with regenerated catalyst (1); The pre-dielectric distribution device (8) that promotes is positioned at the pre-riser tube of catalyzer (14) bottom; The outer cylinder body upper end is connected with top cover is along the circumferential direction airtight; Descending reaction tubes (9) is fixedlyed connected with the sidewall or the bottom of outer cylinder body, or makes the two connection by symmetrically arranged arm; Raw material nozzles is arranged on the outer cylinder body sidewall of the pre-riser tube of catalyzer outlet top and/or on the top cover.
2, according to the reactor of claim 1, it is characterized in that the upper vertical of the pre-riser tube of described catalyzer (14) is arranged on outer cylinder body inside, the outer cylinder body bottom is connected with the outer wall of the pre-riser tube of catalyzer is airtight by base plate (16).
3,, it is characterized in that pre-riser tube of described catalyzer (14) and the coaxial setting of outer cylinder body according to the reactor of claim 2.
4, according to the reactor of claim 2, the angle that it is characterized in that described base plate (16) and horizontal direction is less than 90 °.
5,, it is characterized in that described top cover below is provided with anti-scorch steam distributor according to the reactor of claim 1.
6, according to the reactor of claim 1, the diameter of top exit end that it is characterized in that the pre-riser tube of described catalyzer is greater than the diameter of its underpart.
7,, it is characterized in that the pre-riser tube of described catalyzer is selected from: any one in U type pipe, bend pipe, tipping tube or the vertical tube according to the reactor of claim 1.
8, according to the reactor of claim 1, it is characterized in that the pre-riser tube of described catalyzer outside inner barrel vertically be provided with, it is fixedly connected with the pre-riser tube of catalyzer and be connected that catalyst transport (1) passes outer cylinder body.
9,, it is characterized in that described descending reaction tubes is connected by symmetrically arranged 2～4 arms with outer cylinder body according to the reactor of claim 1.
10, according to the reactor of claim 1, the diameter of top exit end that it is characterized in that the pre-riser tube of described catalyzer is greater than the diameter of its underpart, and near the exit end place orifice plate, packing layer or flase floor is set at an upper portion thereof.
11, according to the reactor of claim 1, it is characterized in that described catalyst transport (1) with the mode of connection of the pre-riser tube of catalyzer (14) is: the arm that the catalyst transport of an inclination is fixedlyed connected with a side of the pre-riser tube of catalyzer or vertical catalyst transport is divided into 2,3 or 4 bendings is earlier fixedlyed connected symmetrically with both sides, three sides or four sides of the pre-riser tube of catalyzer again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137924 CN1272405C (en) | 2003-05-30 | 2003-05-30 | Descending catalytic cracking reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137924 CN1272405C (en) | 2003-05-30 | 2003-05-30 | Descending catalytic cracking reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1552800A CN1552800A (en) | 2004-12-08 |
| CN1272405C true CN1272405C (en) | 2006-08-30 |
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| CN 03137924 Expired - Lifetime CN1272405C (en) | 2003-05-30 | 2003-05-30 | Descending catalytic cracking reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429451B (en) * | 2007-11-07 | 2013-01-02 | 中国科学院大连化学物理研究所 | Fluid bed reactor for producing olefin hydrocarbon and aromatic hydrocarbons with final residuum catalytic reaction, and method thereof |
| CN109666503B (en) * | 2017-10-16 | 2021-04-06 | 中国石油化工股份有限公司 | Descending reactor and catalytic conversion method |
| CN112495307A (en) * | 2020-10-27 | 2021-03-16 | 中国船舶重工集团公司第七0三研究所 | Feeding distributor for waste alkali oxidation reactor |
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| Publication number | Publication date |
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| CN1552800A (en) | 2004-12-08 |
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