CN87100848A - Improved hydroconversion process - Google Patents
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- CN87100848A CN87100848A CN198787100848A CN87100848A CN87100848A CN 87100848 A CN87100848 A CN 87100848A CN 198787100848 A CN198787100848 A CN 198787100848A CN 87100848 A CN87100848 A CN 87100848A CN 87100848 A CN87100848 A CN 87100848A
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- revivifier
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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Abstract
A kind of improved thermal equilibrium hydrocarbon conversion process that between riser reactor (contactor) and revivifier (burner), adopts solid circle, improve solid circle and hydrocarbon charge ratio (C/O or agent-oil ratio), that is: the firm regenerated contactant of directly cooling part heat makes the regrowth of part heat feed the steam stripped device; The regeneration contactant of cooling heat and be added in the downstream riser of uncooled regrowth adding place (the hydrocarbon charging is added to the riser tube bottom with promoting gas or steam) or at heat regeneration contactant with after the hydrocarbon that sprays in the riser tube higher position contacts, but the lifting gas of usefulness carbonization rises to the heat contactant of regenerating in the riser tube.
Description
The present invention relates to a kind of heavy hydrocarbon oil is converted into the method and system of lighter fraction, comprise that the heavy hydrocarbon that will contain high density coke precursors and heavy metal is converted into the method for gasoline and other liquid hydrocarbon.The best of the present invention is embodied in the fluid catalytic cracking of hydrocarbon, to obtain the product in the vehicle fuel boiling spread.
Along with the appearance of highly active zeolite type catalyzer, fluidized catalytic cracking method has moved towards general consistent way, even the hydrocarbon gas and levigated catalyzer are in the pipe reaction section of the industrial length that is called riser tube and flow up.Though the reaction times generally was about about 10 seconds or less than 10 seconds very brief like that, still have sedimentation of coke on catalyzer, when catalyst recirculation is used, can make its active decline like this, the yield distribution of product becomes and is not inconsistent requirement simultaneously.Therefore, generally all follow such method, promptly catalyzer is separated from the logistics of riser tube, by the revivifier return course, revivifier can be used to reach dual order ground, promptly burns coke contaminants and heatable catalyst then.So that in reaction time, recycle.
According to present technology, isolate catalyzer from crackene, be in a so-called separate chamber that includes stripping stage, to carry out.The separate chamber is the container of a sealing.It or partly form a huge cover cap around the riser tube downstream end.Or it is be placed on the outside of riser tube, and coaxial with it.For the setting of this a kind of pattern of back, catalyzer and the hydrocarbon stream that has transformed directly are discharged into the separate chamber by a lateral openings or hole from riser tube.But, to above-mentioned cap style setting, generally preferably the riser tube effluent is at first entered the separate chamber by a single stage cyclone separator again from this lateral openings or hole: the remarkable reduction of apparent space velocity is entrained under the catalyst sedimentation in the riser tube effluent quite a few above-mentioned two kinds of operating method because in the separate chamber, and accumulates in the bottom, separate chamber.Air-flow passes through the cyclonic separator that is arranged in the separate chamber with stripped vapor from the separate chamber, enter separation column, and the effect of this cyclonic separator mainly is to collect all catalyzer of carrying secretly.
In view of the granularity of present new zeolite cracking catalyst is about 5～100 microns, wherein major part is about 40～80 microns, and it is very effective separating with above-mentioned prior art.Even now is clipped in more a spot of catalyzer in the cracked-stream because its accumulative total throughput is very big, still becomes a problem.In some cases, main problem is the entrained catalyst of separating from cracked-stream, must reclaim from separation column with the form of slurry oil, circulates, thereby has reduced the material quantity that cracking unit can be processed.Like this, just can't obtain the optimal process efficient of cracking unit.
And, in the technology catalyzer is separated rapidly with reaction product now, take place thereby reduce undesirable reaction as far as possible, because from integral body, this reaction can make the total efficiency of whole process reduce.
The professional in present technique field can both understand well, and revivifier is that necessary integral part is put in the fluid catalyst makeup, because reclaimable catalyst will recover its activity at revivifier.The regeneration of reclaimable catalyst is generally carried out after it is separated from reaction product, reclaimable catalyst is separated from conversion zone, contact with stripping medium (being generally steam) at stripping stage later on, so as from catalyzer, to remove vaporized and carry secretly and (or) hydrocarbon of sorption.Come out by stripping stage through steam stripped catalyzer, and enter RS Regenerator Section, in RS Regenerator Section, burn the coke that is deposited on the catalyzer, make regenerated catalyst regeneration with oxygen-containing gas (being generally air).Then, make the hot regenerated catalyst of gained be circulated back to conversion zone, contact with the hydrocarbon charging that replenishes.Steam stripping efficiency influences liberated heat in the revivifier.In fact, the stripper of full scale plant is not very effective, and the catalyzer of emitting from stripper still contains remaining hydrocarbon.The temperature of revivifier improves along with the reduction of steam stripping efficiency.
The ratio of cyclic regeneration catalyzer and hydrocarbon charging, so-called C/O(agent-oil ratio) the common FCC(fluid catalytic cracking of the influence) selectivity of device, this influence is particularly evident for the heavy oil FCC device.C/O is big more, and selectivity is good more, and duration of contact can be short more.When adopting zeolitic cracking catalyst, weak point will cause hydrogen transference to weaken duration of contact.Hydrogen transference weakens the octane value cause having improved gasoline again under certain transformation efficiency, has increased the alkene as raw material for alkylation, has improved the hydrogen richness of producing the light cycle oil LCO that distillate uses.In industrial FCC apparatus, catalyst circulation rate (CCR) and agent-oil ratio C/O are not the independent variable(s) that can change arbitrarily.For full scale plant, the C/O that operation is adopted determines according to thermal equilibrium.Generally speaking, unique independent regulated variable is the preheating temperature of cracking temperature (particularly riser reactor temperature out) and raw material.
Select vapourizing unit similar to FCC apparatus.But,, do not play the cracking catalyzer fully as the fluidized solids contact substance.Selecting vaporization is to carry out in a riser tube that is called contactor.The burning of carbon deposits is to carry out in burner.For example see United States Patent (USP) the 4th, 263, No. 128 (Bartholic) quotes for referencial use herein.This technology is in the industrial ART process that is called.
This term of coke poor (△ coke) is meant that the weight of coke percentage ratio of reclaimable catalyst deducts the difference of the weight of coke percentage ratio gained of regenerated catalyst.In other words, the △ coke is that amount of coke on the reclaimable catalyst deducts weight of coke on the regenerated catalyst again divided by the value of catalyst circulation rate (CCR) gained.The relation of △ coke and C/O can be represented by the formula:
C/O=(coke of generation)/(△ coke)
New process of the present invention provides the method for operating thermally equilibrated FCC apparatus or selective evaporation device under high C/O ratio.These methods can be used separately, also can unite use.
According to one aspect of the present invention, FCC apparatus, the CCR of heavy oil FCC device or selection vaporescence controls (raising) by the round-robin fluidized solids contact substance of direct cooling heat.The hydrocarbon charging preferably with lift gas and (or) steam directly is added to the bottom of riser, if necessary, also can contact with heat regeneration fluidisation solid contactant matter with the upstream of refrigerative fluidized solids contact substance contact position, so that can make revivifier/burner system of the no cooling apparatus of operating by thermal equilibrium improve C/O at this gas shape mixture.This working method can reduce the thermal response of FCC apparatus and strengthen needed catalyzed reaction.When FCC apparatus or the raw material of selecting vapourizing unit to process contain bituminous matter, when basic nitrogen and metal, this working method also is favourable.According to this method, be to remove above-mentioned impurity with minimum hot fertile absorber preheating material, and then refrigerative solid contactant matter is sent into the downstream of the solid contactant matter inlet of heat, because the active centre on the contact substance is not covered by bituminous matter (coke) settling, do not neutralized, so can keep high selectivity by basic nitrogen yet.And, the deleterious especially new metal refining of activity is also removed when contacting with the regeneration contact substance of heat already.
On the other hand, the present invention includes a FCC apparatus, heavy oil FCC device or the Controlling System of selecting vaporescence to operate, to improve the C/O ratio and to cross the steam that thermal reactor/contactor is used, its method is that hot fertile absorber and contact substance to be generated are merged, directly enter contact substance stripper to be generated, or adopt equipment hereinafter described.Its method is that hot fertile absorber and reactor/contactor product are merged between the inlet of preseparator outlet and efficient cyclone separator, and the dipleg by efficient cyclone separator returns into stripper hot fertile absorber then.Can reduce the △ coke on the recycled material like this, and the reduction of △ coke can make the temperature of revivifier reduce, thereby make C/O than improving.Consequently, further vaporize, thereby the carbon for the treatment of on the biomass is reduced owing in stripper, treat the hydrocarbon on the biomass.Also having a favourable side effect is in stripper and the hydrocarbon vapour of efficient cyclone separator inlet all is heated to more than the high temperature of generalized case.Because these steams may be in its dew point, cooling all can make its hjeavu ends condensation usually a little, thereby makes in container, cyclonic separator and vapour line, generates undesirable coke.These steam of reheat just can reduce the coke that generates because of condensation reaction.
Another aspect of the present invention is by utilizing a kind of lift gas to promote regenerated catalyst, improving the FCC apparatus of employing zeolitic cracking catalyst or the C/O ratio of heavy oil FCC device, to control duration of contact.Described lift gas be regenerated catalyst with can cracked in riser tube before the raw material that enters in the riser tube downstream contacts.Used lift gas acid sites at catalyzer before adding raw material generates coke.The result makes the acid sites of catalyzer by the carbon institute deactivation that generates when thermocatalyst contacts with lift gas.Best lift gas or from the moisture of king-tower cat head receiver or in the gas concentration unit, reclaim C
3And C
4Any gas behind the cut.The active centre of zeolite is can deactivation, can be used for the cracking coarse diesel charging.Coke is reduced, and yield structure is improved.The result causes not only having improved the C/O ratio, and the output of octane value and alkene is increased.
A best embodiment of the new process of the present invention is that reactor (contactor) and revivifier (burner) are adopted new control method, so that the round-robin solid matter is controlled fully.At first, it is in dilute phase when contacting when recycled material and products of combustion (revivifier/burner) or hydrocarbon vapour (reactor/contactor).At recycled material and steam or products of combustion after separating, recycled material is got back in another container.General other technology of great majority that adopts all has a dense-phase bed that contacts with products of combustion or hydrocarbon steam, and utilizes cyclonic separator to make recycled material get back to the same container that it came out originally therefrom.This container always contains the dense-phase bed of recycled material.In new process of the present invention, dilute phase system directly links to each other with a preseparator, links to each other with several efficient cyclone separators (as multicyclone) then, makes recycled material always enter another container, separates with steam.This recycled material forms dense-phase bed in further receptacle, further receptacle is neither reactor/contactor neither revivifier.The feature of this new process is, it is a complete equilibrated system, and the separation efficiency of its reactor/contactor and revivifier/burner is identical, thereby makes these two systems hold identical size range.In this process, all contact substances that enter reactor/contactor and revivifier/burner all remain in dilute phase, and all pass through preseparator, promptly all do not have the dense fluidized bed in reactor/contactor or in revivifier/burner.New process provides handiness to the composition of hydrocarbon charging, the distribution and the working ability of all prods.In addition, new process can also keep more particulate, makes average degree of particulate less, and surface-area is bigger, keeps higher activity and fluidizing performance preferably.
That describes in detail from below implements to see significantly other characteristics and the advantage of method of the present invention with the best of hydrocarbon catalytic cracking process.
Accompanying drawing is the graphic extension that is suitable for implementing the best apparatus-form of process of the present invention.
With reference to the accompanying drawing that the best of catalyzer cracking of the present invention system is implemented, can see that it mainly is fast fluidization system in the dilute phase operation that this system comprises one, all substances all are that the bottom from revivifier (B) is transported to the top.The difference of native system and General System is: (1) can be controlled all catalyzer fully and flow into system, and (2) all catalyzer that flow into systems all are to be carried by air, at last by products of combustion warp let-off revivifier, enters cyclonic separator (E) and (F).So not only controlled the total flow rate of air and products of combustion, and controlled and enter cyclone system (E) and catalytic amount (F).Control catalyst will be controlled exactly and enter the cyclone system (E) and (F) poundage of per 1 cubic feet of catalyzer, thereby makes the loading capacity of cyclonic separator controlled, makes the unlikely overload of system.For example, the air from gas blower enters through pipeline (A) revivifier (B) bottom of wanting the regenerated catalyzer is housed, and dominant discharge makes it keep dilute phase.Catalyzer separates rapidly with the efficient more than 80% in preseparator (E) with steam, and catalyst substance enters revivifier buffering bucket (C) by the bottom of preseparator (E) through pipeline (R) then.Vapor species is come out from (E), enters multicyclone (F), gets rid of by pipeline (G) in this place's stack gas, and catalyzer enters revivifier buffering bucket (C) by pipeline (R) again.The effect of regeneration system rapidly obviously is to burn carbon all on the reclaimable catalyst.Therefore this system will be designed to have certain temperature, pressure and flow rate, so that can burn carbon in required time.The products of combustion of the revivifier of discharging through flue gas line (G) is mainly nitrogen, CO
2(contain a small amount of CO, generally be lower than 500ppm), SO
xThe steam that contained steam and combustion reactions are produced in (sulphur content that depends on raw material), the combustion air.Also has minor N O
x, the service temperature of it and revivifier (B) has confidential relation.Most of the nitrogen in the coke is emitted with the form of ammonia or nitrogen from nitrogen contained in the raw material.Native system also can stay on the regenerated catalyst carbon by the amount that restriction enters the air of revivifier.This will cause, and CO content improves in the stack gas.Oxygen-supplying amount when the amount of CO depends on the temperature of revivifier, the carbon amount on the fertile absorber and burning.
Because the temperature lower (800 °～1100) of reclaimable catalyst will be difficult at the carbon on the dilute phase burning-off reclaimable catalyst of general time (3～15 seconds) the inherent revivifier that adopts, therefore used the recycling valve (O) of a heat, made the hot material cycle of drawing from revivifier buffering bucket (C) get back to the bottom of revivifier (B).The purpose of this pipeline is the temperature in control revivifier (B), and carbon on the reclaimable catalyst or coke can be burnt in the time that dilute phase carries in the riser regenerator to be allowed.Generally, the cycling rate by valve (O) was at least 1: 1 with the ratio of cycling rate by guiding valve to be generated (JJ), in most of the cases was 2: 1 or bigger, making burning carry out fully so that the temperature in this system can be brought up to foot, generation CO
2, and burn carbon all on the catalyzer.(though not being absolutely necessary) concrete enforcement that novel method of the present invention is recommended also is shown among the figure, be catalyst cooler (N), its flow is controlled by guiding valve (P), the use of this valve is when regenerator temperature reaches on the metallurgy greatest limit, the equipment that prevents is badly damaged, or keeping activity of such catalysts and considering to obtain the highest temperature on the basis of C/O ratio.In other words, operate under the temperature about 1600 if make revivifier, when this intrasystem temperature during near this temperature, just begin to have substance flow to cross guiding valve (P), making has more material to flow out by catalyst cooler (N) and valve (P) from revivifier buffering bucket (C).Obviously, its effect is opposite with valve (O), because it removes heat by produce steam in catalyst cooler (N), thereby the temperature of whole regenerator system is reduced.
Be appreciated that (P) and (O) two control valves all can adopt.If produce steam, just valve (P) can be kept the state that open, to produce quantitative steam so that for the refinery provides energy.Owing to the proportionlity that will keep activity of such catalysts and maintenance catalyzer and oil in reactor or contactor (K) or owing to desired reaction kinetics, revivifier is worked under lower temperature.As noted before, all catalyzer and combustion air all carry the top of revivifier to enter preseparator (E) by riser tube.The design of preseparator (E), its minimum efficiency must be reached can remove contained solid in the gas more than 80%, preferably can remove more than 90%.The solid of removing is discharged from separator (E), enters revivifier buffering bucket (C) by regeneration solid lines (R).Material returns the charge level that should be lower than the bottom of buffering bucket (C) into the position of buffering bucket (C) from preseparator (E), therefore, pipeline is immersed under the actual charge level, upwards blows back into preseparator (E) to prevent gas along pipeline, thereby preseparator (E) is broken down.The stack gas of coming out from preseparator (E) only take away therewith enter preseparator (E) catalyzer total amount 20% or less than 20% catalyzer.Enter efficient cyclone separation system (F) after coming out and carry out final purification.The purification rate of native system is greater than 99.0% more preferably greater than 99.99% gas that does not contain catalyzer basically that comes out from efficient cyclone separator (F), by pipeline (G), go to carry out flue gas treatment and (or) enter atmosphere.The catalyzer of separating from efficient cyclone separator (F) returns under the normal catalytic agent charge level of revivifier buffering bucket (C), so that seal dipleg again.
Make revivifier buffering bucket (C) fluidizing method be control from the little air of gas blower, enter system by air distributor, make that material remains on the speed that is not less than about 1.5 feet per seconds and is not more than 3.3 feet per seconds in the container.The gas that carries a part of catalyzer comes out from revivifier buffering bucket (C), returns revivifier (B) by pipeline (L).Pipeline (L) is the vapor pipe of buffering bucket, also is an equaler line, and this is a very important feature of present method.This pipeline guarantees that the pressure of preseparator (E) inlet equates with the pressure of buffering bucket C, and the pressure that the pressure of buffering bucket (C) will never surpass preseparator is a lot.If the pressure of buffering bucket (C) surpasses the pressure of preseparator (E), isolated material just might not can flow into buffering bucket (C) downwards along pipeline (R) in preseparator (E), thereby makes preseparator (E) inoperative.Also same pressure reduction or pressure equalization must be arranged between efficient cyclone separator (F) and the buffering bucket (C).As long as the charge level in the return pipe (R) is not high enough to degree that preseparator (E) and efficient cyclone separator (F) are broken down, the pressure of buffering bucket (C) can be a little more than (E) or (F).As shown in the figure, vapor pipe (L) links to each other with dilute phase revivifier (B).But from the vent line (L) that revivifier material stock buffering bucket (C) is drawn also can be connected on (E) and (F) between, the speed of revivifier buffering bucket C is depended in this selection.In any case, the purpose of vent line (L) is that the pressure that guarantees preseparator (E) inlet equates with the pressure of buffering bucket C.
Same consideration also is applicable to reactor/contactor (K).Introduce the lifting steam by reactor/contactor (K) by pipeline (J), introduce hot regenerated catalyst by guiding valve (Q), introduce charging by pipeline (HH), and it is the same with the situation of foregoing revivifier (B), also make all products and catalyzer all enter preseparator (E), enter (F) then.And to there be an equaler line just the same between revivifier material stock buffering bucket (C) and the revivifier (B), an equaler line (M) also must be arranged here, return cyclonic separator (E) and (F) from catalyst vapor stripper (D).Therefore, the effect of the effect of pipeline (M) and pipeline (L) is identical on the figure.
In general, the operating parameters of revivifier (B) is: 1100 °～2000 of temperature are lower than 1400 °F concerning the FCC operation, speed must be greater than 3.5 feet per seconds, with the operation of assurance dilute phase, but must generally keep 5～15 feet per seconds less than 100 feet per seconds.The pressure of revivifier is generally 5～50 pounds/square inch (gauge pressures), is preferably 10～30 pounds/square inch (gauge pressures), and gas residence time (gastime) was generally 3～15 seconds.
The design of revivifier is closely similar among the design of reactor assembly and the figure, this shows that it also is by two separators (E) and (F) and a stripping tower (D) that plays the buffering bucket effect, and a riser tube/contactor (K) is formed.Regenerated catalyst is drawn by revivifier buffering bucket C, enters riser tube contactor (K) by valve (Q).It can with thinner (as lift gas), steam, freshening hydrocarbon or water, or the contact of the charging by pipeline J.Also prepared alternative feed points (HH) in addition, with the residence time in control contactor or the reactor.Regenerated catalyst and any thinner and any recycle hydrocarbons and charging will contact the necessary time, to obtain desired product yield in contactor/reactor (K).This point is selected vaporescence to FCC, heavy oil FCC, fluid coking or to ART() (as United States Patent (USP) the 4th, 263, No. 128 are disclosed) all be the same.With foregoing the same, all steam that produced in reactor/contactor (K) and all catalyzer but enter preseparator (E).Similar to the situation of revivifier (B), control the catalyzer and the steam that enter preseparator (E), make the unlikely overload of system.The efficient of separator (E) and (F) is identical with regenerator system.The catalyzer of separating from steam also is to return in the reclaimable catalyst stripper (D) by the pipeline under the charge level that is connected in dense-phase bed (R).Reclaimable catalyst stripper (D) the steam fluidisation that feeds wherein.The vent line (M) of stripper (D) with separator (E) and the pipeline (F) be connected.Because the material of carrying secretly seldom, so the same with the situation of revivifier, enter the inlet of (E) easily.
Then, reclaimable catalyst leaves catalyst stripping equipment again by valve (JJ) under the situation of control charge level.So basically the steam that does not contain catalyzer leaves native system by pipeline (H), carries out fractionation and separates, if the ART device will carry out chilling herein.If fluid coking, FCC or heavy oil FCC, steam then carries out fractionating system, and chilling is not essential.
From as can be seen above-mentioned, a key distinction between system shown in the drawings and the prior art system is not to be catalyzer dense-phase bed balance contained with container (C) or (D) or to contact from the steam that regeneration system rapidly (B) or contactor (K) come out.And before this, most of system all has such characteristics, and promptly steam is isolating in container, and always contacts with dense-phase bed.
The condition of contactor (K) is to be 10～100 feet per seconds in speed basically, and the speed in exit is reached about 70 feet per seconds.Time depends on whether be the ART device, and when being the ART device, the time generally was less than 3 seconds most preferably less than 1 second, and FCC apparatus is operation down in 1～5 second in the steam time (Vaportime) generally in this way, and the temperature in the contactor is generally 800～1000 °F.
Requirement to preseparator is not strict at all, and only requiring can be with rapid round-robin solid and vapor removal.The equipment of this type is at United States Patent (USP) the 4th, 285, and No. 706, open in the 4th, 348, No. 215 and the 4th, 398, No. 932, all disclosures are drawn at this for referencial use.Efficient cyclone separator is general cyclonic separator, and can be one also can be a plurality of cyclonic separators.Separator (F) is a United States Patent (USP) the 4th, 285 preferably, No. 706 described the sort of multicyclones, and the content of this patent disclosure is drawn at this for referencial use.
Fig. 1 also illustrates and is used for the Controlling System that FCC apparatus, heavy oil FCC device or ART process improve the C/O ratio.Its method is with water cooler (V) and guiding valve (W) recycling catalyst directly to be cooled off; (in the catalyst A RT device or the carbon on the non-catalytic contact substance, this can reduce the temperature of revivifier owing to the material in reactor heating/contactor stripper once again again to improve the C/O ratio to reduce recycled material.This makes hot fertile absorber directly enter stripping tower by guiding valve (S) and heating riser tube (U) and realizes.Promoting medium (T) can be gas or steam.So not only reduce, and make the so favourable side effect of CX/RX steam superheating in addition, thereby the amount of coke that generates by condensation reaction is reduced owing to the more hydrocarbon of vaporizing from the stripping tower material makes the carbon for the treatment of on the biomass.Because the CX/RX steam in heavy oil FCC or the ART device may be in its dew point, cooling all can make the condensation of heavy afterbody a little, generates coke in container, cyclonic separator and the vapour line thereby make, and steam overheated enables to eliminate this problem.As shown in the figure, also have another pipeline (U ') also to can be used for, thereby overheated CX/RX steam improve the temperature of stripping tower with hot fertile absorber and the outlet that promotes medium (T) injection preseparator (E).
Another characteristics shown in the figure are, with before charging (HH) contacts, promote regenerated catalyst with lift gas (J) at regenerated catalyst.Charging system sprays into the higher position of carrying into pipe, to be controlled at the time in contactor or the riser reactor.This lift gas feeds before tying up to and adding charging, generates coke on acid sites, with generation and the improvement product structure that reduces coke.In traditional catalyst system, the active of acid sites obviously improved when the content that is reproduced carbon when catalyzer was lower than 0.3.The active raising of acid sites, the coke that hydrocarbon feed is generated increase and selectivity are reduced.Therefore, contact with gas, can make acid sites because gas generates carbon and passivation by before spraying into raw material, making catalyzer.The active centre of zeolite is to have optionally to can be used for cracking coarse diesel.The result increases octane value and alkene, and C/O improves.
The further feature that still has shown in the figure is to select such method for use, being about to hydrocarbon feed locates with the bottom (J) that lift gas or steam directly are added to riser tube, and make its with contact with hot regenerated catalyst before the refrigerative catalyzer contacts so that in not carrying out the operation of refrigerative thermal equilibrium, improve the C/O ratio.This working method is containing bituminous matter with FCC system processing, be favourable during the charging of basic nitrogen and metal.When adopting this method, the operator can be earlier with trying one's best few hot fertile absorber preheating material to remove the most of bituminous matter in the raw material, basic nitrogen and metal, make the cooled catalyst that enters just in the downstream of thermocatalyst, with the highly selective that keeps cooled catalyst to have, because its active centre is covered by bituminous matter (coke) settling, also do not neutralized by basic nitrogen (or) competition of new metal active run into.
The technician who is familiar with fluidized solids operation is easy to understand, illustrated delivery system can reduce the investment of erecting equipment, and can utilize present container, not carry out under the situation of material alteration, the ability of existing FCC apparatus, heavy oil FCC device, fluid coker or ART device is doubled, because the superfacial velocity restriction that is present in the present dense bed stratotype revivifier has been eliminated by this system.And but the design philosophy of this fluidizer also is applicable to other fluidized solids system that is subjected to apparent bed speed limit at present.
Certainly, the detailed process that is adopted is obviously depended in one or more concrete fluidized solidss.
Be used for the cracked typical solid and comprise that those have the solid of microvoid structure, the molecular energy of charging enter micropore in case absorption with (or) contact with catalytic active center in micropore or near the micropore.The various catalyzer that belong to this class for example, comprise some layered silicates (as terre verte), though what extensively adopt in this class catalyzer is the well-known catalyzer that contains zeolite, the nonzeolite catalyzer is also at the row of consideration.
The catalyzer that contains zeolite preferably can comprise various zeolites, (no matter be natural, semisynthetic or synthetic), it can be independent zeolite, it also can be zeolite and the use that mixes of other material, but can not damage the suitability of catalyzer significantly with zeolite blended material, the catalyzer that mixes and obtain should have activity above-mentioned and microvoid structure, for example, if live catalyst is a mixture, it can comprise and combines with the heatproof inorganic oxide carrier of micropore or be dispersed in zeolite constituent in this carrier, in this case, zeolite can account for about 1～60% of total catalyst weight (moisture-free basis), be about 15～50% preferably, most typical is 20～45%(weight) about, the rest part of catalyzer entirely for porous refractory inorganic oxide or its with reaction various needs or unwanted is played promotion or inhibiting arbitrary known auxiliary.Be applicable to molecular sieve catalyst of the present invention with regard to the zeolite genus, please note two pieces of articles of being entitled as on the Chemical Week magazine that is published on July 26th, 1978 and on September 13rd, 1978 respectively " Refinery Cafalysfs Are a Fluid Business " and " Making Cat.Crackers Work on Varied Diet ".Its described content is drawn at this and is reference.
The zeolite component that contains in the catalyzer of zeolite is those known components that are applicable to fluid catalytic cracking process mostly.In general, they are crystalline silico-aluminates, and being typically has four coordination aluminium atoms in the crystalline structure, and they combine by the Siliciumatom of Sauerstoffatom with vicinity.But " zeolite " this term not only refers to silico-aluminate here, also refer to those wherein materials of partly or entirely being replaced of aluminium, for example aluminium by gallium, phosphorus, boron, iron and (or) other atoms metal replaces, but also comprise wherein whole silicon or the substituted material of part silicon, (for example silicon is replaced by germanium or phosphorus, also can be replaced by titanium or zirconium).
Most of zeolite be make sodium form or natural be exactly this form, sodium cation combines with electronegativity position in the crystalline structure.Sodium cation can make the zeolite torpescence that becomes, and when being under the condition that hydrocarbon transforms, particularly at high temperature very unstable.Therefore zeolite can not carry out ion-exchange, if zeolite is a constituent in the catalyst component, zeolite can be used as the constituent of a component to carry out this ion-exchange before adding or after adding.Be suitable for replacing that the positively charged ion of sodium comprises ammonium (can be decomposed into hydrogen), hydrogen, rare earth metal, alkaline-earth metal etc. in the zeolite crystal structure.Various suitable ion-exchange techniques and can all knowing to one skilled in the art by the positively charged ion that exchange enters zeolite crystal structure.
Can be used as catalyzer of the present invention or faujusite, mordenite, clinoptilolite, chabazite, euthalite, Crionite are arranged as the example of the natural crystal silicon-aluminate zeolite of catalyst component of the present invention, and levyne, dachiardite, paulingite, black zeolite, ferrierite, heulandite, scolecite, stibiconite, harmotome, phillipsite, Caumnite, white garnet, lazurite, wernerite, mesolite, ptilolite, nepheline, needle stone, offretite, natrolite, brusterite, flarite, datolite, sarcolite.
Can be used as catalyzer of the present invention or have: X type zeolite, United States Patent (USP) the 2nd, 288, No. 244 as the example of the synthetic crystallization aluminosilicate zeolite of catalyst component of the present invention; Y-type zeolite, United States Patent (USP) the 3rd, 130, No. 007 and A type zeolite, United States Patent (USP) the 2nd, 882, No. 243, and the Type B zeolite, U.S. Patent number the 3rd, 008, No. 803; D type zeolite, No. the 661st, 981, Canadian Patent; E type zeolite, No. the 614th, 495, Canadian Patent; F type zeolite, United States Patent (USP) the 2nd, 996, No. 358; H type zeolite, United States Patent (USP) the 3rd, 010, No. 789, J type zeolite, United States Patent (USP) the 3rd, 011, No. 869, zeolite L, No. the 575th, 177, belgian patent, M type zeolite, United States Patent (USP) the 2nd, 995, No. 423; O type zeolite, United States Patent (USP) the 3rd, 140, No. 252, Q type zeolite, United States Patent (USP) the 2nd, 991, No. 151; S type zeolite, United States Patent (USP) the 3rd, 054, No. 657; T type zeolite, United States Patent (USP) the 2nd, 950, No. 925; W-type zeolite, United States Patent (USP) the 3rd, 012, No. 853; Z type zeolite, No. the 614th, 495, Canadian Patent.And zeolite omega, No. the 817th, 915, Canadian Patent.Also have ZK-4HJ, α, β and ZSM-type, zeolite also to be suitable for.In addition, United States Patent (USP) the 3rd, 140, No. 249 3,140, No. 253,3,944, No. 482 and 4,137, No. 151 described zeolites also are suitable for.The disclosed content of described patent is all drawn at this and is reference.
Crystal silicon-aluminate zeolite with faujusite crystalline structure is specially adapted to the present invention.Comprising particularly natural faujasite and X type zeolite and y-type zeolite.
The typical solid that is applicable to the ART method is the solid that is proposed in No. the 4th, 263,128, those United States Patent (USP)s.
Symbol description on the figure
A. the air of air-blaster output-to regenerator system
B. revivifier/burner/stove
C. revivifier buffering bucket
D. reclaimable catalyst/ARTCAT stripper
E. preseparator
F. efficient cyclone separator
G. go the stack gas of flue or processing
H. remove isolating oil vapour
I. remove the steam of stripper
J. remove lifting steam gas (wet or do the)/H of riser tube contactor
2O/ or charging
K. riser tube contactor
L. buffering bucket vent line
M. stripper vent line
N. catalyst cooler/ARTCAT water cooler
O. thermal cycling material guiding valve
P. cold recycled material guiding valve
Q. fertile absorber guiding valve
R. from the separate substance of separator
JJ. treat the biomass guiding valve
HH. charging one is in order to the changed feed point of time in the control contactor
S. remove the hot material guiding valve of CX/RX heating riser tube
T. remove the lift gas/steam of CX/RX heating riser tube
V. control the C/O water cooler
W. remove the cold catalyzer of riser tube contactor
U.CX/RX stripper reheating pipe line
U ' .CX/RX steam superheating pipeline
Claims (6)
1, a kind of thermal balance type hydroconversion process.Wherein the hydrocarbon charging at high temperature contacts with the fluidized solids contact substance in reactor.Be converted into the lower product of boiling point; Separate from the lower reaction product of coke fluidized solids contact substance to be generated and boiling point that contains that this reactor comes out.And stripping is removed volatile hydrocarbon in stripping stage; Can in RS Regenerator Section, regenerate by means of a kind of oxygen-containing gas through steam stripped fluidized solids contact substance; Make the firm regenerated fluidized solids contact substance of heat get back to reactor, present method improvements are the firm regenerated part fluidisation with heat.Solid contactant matter imports above-mentioned stripper, and it is interior by the amount of steam stripped volatile hydrocarbon to increase this stripping stage, and the amount of superheated vapo(u)r, like this, can make the interior regenerated of RS Regenerator Section low through steam stripped material carbon content, and can reduce the temperature of revivifier.
2, method according to claim 1 has wherein reduced the temperature of revivifier, and has improved the ratio of fluidized solids contact substance and hydrocarbon ils.
3, method according to claim 1 has wherein reduced in the cyclonic separator, in the stripping stage or above the two coke growing amount.
4, method according to claim 1, wherein the fluidized solids contact substance is served as reasons and is contained the cracking catalyst that zeolite constituted of acid sites.
5, method according to claim 1, wherein the fluidized solids contact substance does not possess catalytic activity basically, at high temperature evaporate volatile hydrocarbon after, above-mentioned metallic hydrocarbon charging do not evaporate that part ofly just can be deposited on the fluidized solids contact substance.
6, method according to claim 1, wherein also be included in and finish above-mentioned conversion and regeneration step in the dilute phase, all solid contactant matter from above-mentioned reactor and RS Regenerator Section is sent into the whirlwind preseparator, separate solid and gas and solid matter sent back in the dense-phase bed in the container except that above-mentioned revivifier or reactor/contactor in this cyclonic separator.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US83190786A | 1986-02-24 | 1986-02-24 | |
| US831907 | 1986-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN87100848A true CN87100848A (en) | 1987-10-28 |
Family
ID=25260176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198787100848A Pending CN87100848A (en) | 1986-02-24 | 1987-02-14 | Improved hydroconversion process |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0234924A3 (en) |
| CN (1) | CN87100848A (en) |
| BR (1) | BR8700865A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2610638B1 (en) * | 1987-02-11 | 1990-04-13 | Total France | IMPROVEMENTS TO METHODS AND DEVICES FOR CATALYTIC CRACKING OF HYDROCARBON FEEDSTOCKS |
| US4917790A (en) * | 1989-04-10 | 1990-04-17 | Mobil Oil Corporation | Heavy oil catalytic cracking process and apparatus |
| US5000841A (en) * | 1989-04-10 | 1991-03-19 | Mobil Oil Corporation | Heavy oil catalytic cracking process and apparatus |
| US5043055A (en) * | 1990-04-27 | 1991-08-27 | Mobil Oil Corporation | Process and apparatus for hot catalyst stripping above a bubbling bed catalyst regenerator |
| CN106398759B (en) * | 2016-11-19 | 2017-12-22 | 河北天理环保科技有限公司 | Waste lubricant oil regeneration and production diesel device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL71312C (en) * | 1939-05-20 | 1952-07-15 | ||
| US2353505A (en) * | 1940-12-31 | 1944-07-11 | Standard Oil Co | Catalytic conversion system |
| US2427820A (en) * | 1941-10-27 | 1947-09-23 | Universal Oil Prod Co | Catalytic cracking process |
| US3886060A (en) * | 1973-04-30 | 1975-05-27 | Mobil Oil Corp | Method for catalytic cracking of residual oils |
| US4869879A (en) * | 1982-03-25 | 1989-09-26 | Ashland Oil, Inc. | Vented riser for stripping spent catalyst |
-
1987
- 1987-02-14 CN CN198787100848A patent/CN87100848A/en active Pending
- 1987-02-24 BR BR8700865A patent/BR8700865A/en unknown
- 1987-02-24 EP EP87301613A patent/EP0234924A3/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0234924A2 (en) | 1987-09-02 |
| BR8700865A (en) | 1987-12-22 |
| EP0234924A3 (en) | 1987-10-07 |
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