CN85106455A - The original adoption dry gas is made the slag oil cracking method of lift gas in riser reactor - Google Patents

Abstract

With containing minute quantity C ₃ ⁺And contain C hardly ₅ ⁺Humid gas replace generally containing C ₃ ⁺And C ₅ ⁺Humid gas make lift gas and transform riser tube such as metal separation system, fluid catalytic cracking device and RCC mink cell focus cracking technology catalyzer is sent hydrocarbon.Be preferably in the acceleration of for some time, mix and the impurity passivation after hydrocarbon feed is contacted with catalyzer one lifting gas mixture, be about 0.01～2 its duration of contact, better 0.05～1.5, best 0.15～1 second.Preferred hydrogen content in optimized hoisting gas is at least about 10, and is better 15, best 20 moles of %.Advantage is that aerogenesis is few, the low and better product selectivity of coke formation amount.

Description

The original adoption dry gas is made the slag oil cracking method of lift gas in riser reactor

The relevant a kind of realization crude oil fraction of the present invention, new the improving one's methods of the catalytic cracking of the residual oil part of particularly forming by gas oil (gas oils) in the crude oil, this cracking stock can contain also can not contain decompression residual oil, comprise asphaltene, pitch, a great deal of metallic impurity nickel and vanadium, stream and nitrogen compound.Hydrocarbon feed can be the heavy oil feed of 343 ℃ (650) above carbon containing metal (carbometallic), and this raw material contains or contain the Ramsbottom coke or the Kang Laxun carbon residue dispersed substance of a great deal of hardly.Used crude oil fraction can be an air distillation heavy oil in the cracking process of the present invention, topped oil, vacuum residuum, the heavy oils that extracts from oil-sand, gelatin liquefaction product, resinous shale high temperature pyrolysis gained oil product and composition thereof.Typical its boiling point of oily raw material can be from 343 ℃ (650 °F) to up to 566 ℃ (1050 °F), perhaps, when containing the VACUUM TOWER BOTTOM product, can be up to 816 ℃ (1500 °F).

Be on the one hand more specifically, the present invention relates to improvement and using active catalyst, particularly contain the method for the catalyzer of activated crystalline zeolite catalyst activity value required under resulting selectivity of product in this class heavy oil feed cracked process and the assurance equilibrium state.Reaching of essence of the present invention is by at the beginning, that is to say, with send into before oily raw material that riser tube goes to carry out catalytic cracking contacts, just in lift gas, use and reach the suspensoid that desired pyritous regenerated catalyst particles forms a kind of upper reaches, lift gas comprises the dry gas composition, coke was existed, and this lift gas also can be distributed to coke in the catalyst suspension hardly and go.

The present invention relates to and relevant technical field is the conversion of hydrocarbon, this technical field is disclosed in (file number 6034AUS) USSN288952, and the applying date is on May 13rd, 1981, and present United States Patent (USP) 4432863 belongs to Meyer this (Meyers ') or the like; (file number 6049JUS) USSN373599, the applying date is April 30 nineteen eighty-two, present United States Patent (USP) 4419223; And USSN411719, the applying date is August 19 nineteen eighty-two, among the present United States Patent (USP) 4435279.More particularly, the present invention is also relevant before residual oil is carried out catalytic cracking, residual oil raw material is handled with part taken off the synthetic operation method that charcoal and part remove metal, and this technical field has been disclosed in USSN550985, the applying date is November 10 nineteen eighty-three, (file number 6107CUS); USSN355661, the applying date is March 12 nineteen eighty-two, (file number 6107MUS); USSN524813, the applying date is August 19 nineteen eighty-three, (file number 6107NUS); And USSN567487, the applying date is on January 3rd, 1984, among (file number 6107OUS).The relevant technical field of the present invention also comprises the technical field that is disclosed in the following invention, i.e. USSN94216, the applying date is on November 14th, 1979, present United States Patent (USP) 4341624, (file number 6049AUS), belong to Meyer this or the like; USSN94217, the applying date is on November 14th, 1979, present United States Patent (USP) 4347122, (file number 6049BUS), belong to Meyer this or the like; USSN94091, the applying date is on November 14th, 1979, present United States Patent (USP) 4299687, (file number 6049CUS), belong to Meyer this or the like; USSN94227, the applying date is on November 14th, 1979, present United States Patent (USP) 4354923, (file number 6049DUS), belong to Meyer this or the like; USSN94092, the applying date is on November 14th, 1979, present United States Patent (USP) 4332673, (file number, 6049EUS), belong to Meyer this or the like; United States Patent (USP) 4419223, (file number 6049JUS) belong to Meyer this or the like; USSN411719, the applying date is August 19 nineteen eighty-two, present United States Patent (USP) 4435279, (file number 6168AUS) belongs to Bush (Busch) or the like; And USSN304992, the applying date is on May 13rd, 1981, present United States Patent (USP) 4434044 belongs to Bush (Busch) or the like.

In confirming process of the present invention disclosed herein, also think the prior art of having considered the simple discussion of following institute.

Gilmore(Phillips) United States Patent (USP) 2900326 has been discussed the method for processing gas oil in a kind of fluid catalytic cracking (FCC) device, the light gas that contains hydrogen that wherein will produce with circulated after the fresh feed of sending into mixes, thereby suppress C ₁～C ₄The generation of composition.

Rice(Gulf) United States Patent (USP) 2904504 has been discussed before with oily raw material injecting lift pipe, with C ₁～C ₅The hot regenerated catalyst blended method of riser cracking section is delivered in hydrocarbon and circulation, and the speed that this light hydrocarbon is sent into is about 35.6～89.0 cubic metres of every cubic metre of raw material (being about 200～500 cubic feet of every barrel of raw material).(except clearly being illustrated separately, said among the present invention " bucket " all refers to the raw material barrelage).

What United States Patent (USP) 3849932 Owen(Mobil) was discussed is the bottom of light hydrocarbon being delivered to the riser cracking district.The contriver of this patent also further upwards introduces gas oil along riser tube, still upwards further injects hydrocarbon along riser tube then.By these decanting points, suspended catalyst upwards flows, and by hydrocarbon steam and the light hydrocarbon sent into it is raised up.

Henny(UOP) it is being under the condition that exists of pure hydrogen basically in the riser tube that United States Patent (USP) 2888395 has been discussed, the method that heavy hydrocarbon is contacted with catalyzer.Beyond cracking unit, produce hydrogen.It is said that hydrogen and oily raw material together use formation that can reduce coke and the generation that can reduce unsaturated product.

What discuss in the United States Patent (USP) 4268416 Stine(UOP) is, before the zone of cracking of catalyzer being sent in the riser tube, catalyzer can be reduced catalyzer and is polluted by nickel and vanadium with being contacted by water saturated hydrogen.

What United States Patent (USP) 4280895 Stuntz(Exxon) and United States Patent (USP) 4280896 related to is that the cracking catalyst that is contaminated with metals is delivered to the breeding blanket from the zone of cracking in the riser tube, coke is wherein fired, then before the zone of cracking of regenerated catalyst being sent in the riser tube, it is used hydrogen, and carbon monoxide or hydrogen-carbon oxide mixture are handled in the reduction zone.

United States Patent (USP) 4345992(Phillips) be that regenerated catalyst is delivered to the reduction zone, catalyzer contacts with hydrogen therein.Reducing catalyst is sent into the zone of cracking in the riser tube with not used up hydrogen then.

Castillo(UOP) United States Patent (USP) 4361496 is spoken of with a kind of by three carbon atoms or be less than the hydrocarbon of three carbon atoms or appropriate hydrocarbon gas that its mixture is formed is handled the catalyzer that metallic impurity are arranged that was reproduced, thereby foreign metal is reduced fully, these foreign metals are being carbonized in the dipleg between the reaction zone in revivifier and the riser tube, and this dipleg is used for catalyzer is sent into reaction zone in the riser tube from revivifier.

Castillo(UOP) United States Patent (USP) 4364848 is similar to above-mentioned United States Patent (USP) 4361496, and promptly used reducing gas is the mixture of 1,2,3 carbon atom hydrocarbon, thereby makes metal passivation before its carbonization become metallic state.

The patent 2937988(Esso Res.﹠amp of Polack; Eng.Co.) disclosed is a kind of riser reactor system, be used for the cracked oil raw material, the residual oil that for example contains heavy hydrocarbon, oil plant at the bottom of decompression or the atmospheric tower, tar-bitumen, pitch or its mixture, hot coke granule wherein is dispersed at first and dissolves among the gas, this fluidizing agent for example has steam, light hydrocarbon gas, rare gas element or its mixture.

The patent 3406112(Mobil of Bowles) disclosed is the method that reclaims hydrocarbon product stream, the boiling point of this product hydrocarbon is lower than the boiling point of about 6 carbon atoms or 5 carbon atom hydrocarbon, the latter's consumption be enough to make in the bottom of riser reaction zone zeolite catalyst particle its with form a suspensoid before the oily raw material of sending into contacts.

What the patent 3849291(Mobil of Owen) relate to is with the resulting dry gas product of cracking or the humid gas product method as diluted material in disclosed riser cracking operating process.

The patent 3894932(Mobil of Owen) speaks of and use C ₃～C ₄Hydrocarbon gas mixture make in the bottom of riser tube zeolite catalyst particle its with form a suspensoid to the upper reaches before oily raw material contacts.

What the patent 2684931(Union oil of Berg) relate to is a kind of method that adopts fluidized solids, wherein uses by hydrogen the gaseous product of the cracking gained that methane, unsaturated and normally saturated hydrocarbon gas are formed.

The patent 4431515(Ashland Oil of this grade of Meyer, Inc.) disclosed is to use hydrogen and the high catalyzer of metal content to transform the method for the oil plant of carbon containing metal (carbome-tallic) in riser reactor.This patent is also spoken of hydrogen is added riser reaction zone to reduce the growing amount of conjugated diene.So just be considered to, the concentration of diolefine has reduced, and the amount of coke that generates with the catalyzer that contains metal has also reduced.This patent has been discussed hydrogen the method for using has been provided with the hydrocarbon feed that provides with gas stream, and the hydrogen content of this gas stream is 60% and 80% or higher.This patent does not relate to the disclosed invention essence of present patent application.

The prior art of above-mentioned concise and to the point discussion does not all provide or demonstrates the significant and beat all improvement effect that is obtained by applicant's inventive concept, these inventions all adopt a special dry gas composition and a cooling fluid to combine a kind of suspensoid to the upper reaches that reaches required pyritous regenerated catalyst of formation separately, more particularly, this suspensoid it is believed that and can make the product selectivity optimization that shows in the catalyzer conversion process of given hydrocarbon feed.

In general, the boiling spread of gasoline and other liquid hydrocarbon fuels oil is about 38 ℃ (100)～about 343 ℃ (about 650), and a kind of mixture of forming by hydrocarbon and other compound from the crude oil that wherein extracts these oil fuel, the molecular weight difference of each component is very big in the mixture, so the variation range of its boiling point will be wideer.For example, in the known crude oil 30%～60% of cumulative volume or more component be higher than by boiling point that the compound of 343 ℃ (650) forms.Also comprise some crude oil like this in these crude oil, its cumulative volume about 10%～about 30% or more by molecular weight so high compound form so that its boiling point is higher than 552 ℃ (1025 °F), perhaps at least under normal pressure these compounds be lower than under the temperature of 552 ℃ (1025) and can seething with excitement.

Because these quite abundant high boiling components are unsuitable for being included in gasoline and other liquid hydrocarbon fuels in the crude oil, so worked out fluid catalytic cracking (FCC) method so that molecular weight is big, the compound molecule cracking that boiling point is high or to fragment into molecular weight less, the molecule of boiling point in suitable scope.Though fluid catalytic cracking (FCC) method has reached quite high state of the art, and many improving one's methods or modification method proposed, but the consistent factor that these methods are considered is, it is big to contain molecular weight, the hydrocarbon feed that is evaporated that boiling point is high, at high temperature by be suspended in raw material steam among the method that contacts of cracking catalyst make its cracking, reach the desired molecule amount and make after its boiling point lowering, again catalyst system therefor is separated from the desired product that obtains.

Employed hydrocarbon feed and commonly used fluid catalytic cracking (FCC) raw material wherein have the great Lan Shi carboloy residue of possibility that generates coke by comparison in the method that the present invention relates to.With regard to common fluid catalytic cracking (FCC) method, the Lan Shi carboloy residue is all thought adaptable raw material in about scope of 0.1～about 1.0.A kind of like this fraction in common fluid catalytic cracking (FCC) the method employing crude oil is as raw material, be that boiling point is about 343 ℃ (650)～about 538 ℃ (1000), and do not contain the material of meeting formation coke and the fraction of beavy metal impurity comparatively speaking.This charging is called " decompression gas oil " (VGO), in general make with crude oil, its preparation process is, the fraction that the crude oil mid-boiling point is lower than about 343 ℃ (650) under normal pressure distills, separate then, to carry out underpressure distillation than heavy fraction again, obtain at last boiling point between about 343 ℃ (650 °F) and about 482 ℃ (900 °F) to the fraction of 552 ℃ (1025) as charging.

Because each heavy metal species is unequal to the middle cytotoxic activity of catalyzer in the oil plant of carbon containing metal, therefore the middle cytotoxic activity of representing to contain the oil plant of a kind of metal or several metal like this is very easily, promptly has the poison amount of active a kind of metal of equivalent with estimation and represents.Like this, heavy metal content in the oil plant just can be represented by the formula (the Oil and Gas Journal that form and W.L.Nelson published on October 23rd, 1961, the formula of listing on the 143rd page is similar), wherein be that benchmark calculates with the raw material weight, percent umber (calculating by weight) the when content of every kind of metal all is expressed as this metal and exists with metallic state in the oil plant.

Nickel equivalent=Ni+(V/4.8)+(Fe/7.1)+(Cu/1.23)

Above-mentioned formula also can be used for representing the deposition of heavy metal on cracking catalyst, and just used amount of metal is the weight (butt) with catalyzer rather than is that benchmark calculates with the raw material weight in the formula.

The present invention relates to contain the working method of such heavy metal raw material, promptly heavy metal content substantially exceeds heavy metal content in fluid catalytic cracking commonly used (FCC) method in the raw material, thereby might deposit on the catalyzer and make poisoning of catalyst.

Distinguishing feature of the present invention is to have proposed a kind of simply, and operating quite is easy to and productivity is high that oily feedstock conversion is become various than light hydrocarbon, as the method for gasoline.Raw material is made up of the oil plant that boiling point is higher than 343 ℃ (650).This class oil plant, boiling point wherein is at least the fraction of 343 ℃ (650) in other words, it is characterized by, calculate by weight, heavy metal content wherein is for about at least 4ppm, preferably greater than 5ppm, be more preferably at least approximately nickel equivalent of the heavy metal of 5.5ppm, and calculate by weight, the carbon residue content of high temperature pyrolysis is more preferably about at least 2% or higher for about at least 1%.

The metal that contains about 1000～70000ppm, as nickel, the iron of increment, the catalyzer of copper and (perhaps) vanadium or its oxide compound, below be referred to as impure catalyzer, because in cracking process, if the not passivation of this catalyzer just tends to promote the formation of coke.Like this, in most of the cases, will replace catalyzer continuously,, promptly be up to the Ni+V of 2000ppm so that these metals keep lower concentration on catalyzer.

The preferred in the present invention practice is to adopt to contain these metals, the particularly catalyzer of its concentration in above-mentioned scope, because according to the study, when hydrogen was introduced the cracking system, these metals had the ability of activation hydrogen.

The explanation that has proposed a kind of mechanism of coke generation type in catalytic cracking process is such, and the alkene that contains in raw material passes through

The ionization principle perhaps forms conjugated diene by cracking reaction, as divinyl through dehydrogenation in cracking process.This class diolefine can form carbonaceous material after it is believed that condensation, and these electrodeposition substances lose activity it to catalyzer.Wherein total chemical reaction can be represented by the formula:

In the presence of the catalyzer of containing metal impurity, as coking and other dehydrogenation reaction, the above-mentioned reaction phase of giving will quicken.But according to reining in the summer row principle (Le Chatalier ' s principle) of making a mistake, having of hydrogen may make reaction carry out to the reversed reaction direction in the system, thereby reduces the growing amount of conjugated diene.Conjugated diene forms the carrying out that the reduction of speed has stoped the incrustation reaction, accelerates simultaneously or has improved other

The ionic effect, thus obtain being worth bigger product.

Equally based on reining in the summer row principle of making a mistake, hydrogen is added behind the catalytic cracking system and make second reaction also obtain stoping.Many metals above-mentioned all turn back in the reactor with oxide form, and in reactor, because the elimination of the hydrogen that above-mentioned reaction produces, these metal oxides can very fast reduction become metallic state or metal oxide more at a low price far and away.Therefore, to right-hand, so this impellent also just might be impelled the formation of conjugated diene to the impellent of this reaction at above-mentioned reaction formula middle finger.

So, be not bound by theory although do not want, but will be understood that, when hydrogen is fed containing metal, as nickel, copper, during the catalytic-cracking reaction system of the catalyzer of iron and vanadium or its oxide impurity, the conjugated diolefine hydrocarbon reaction can carry out to the reversed reaction direction, thereby reduced the concentration of diolefine, and coke formation amount has reduced similarly.In addition, will be converted into diolefine usually and the alkene that is removed can remain with the alkene form from the cracking system, then can be freely and protonic acid (Bronsted acid) reaction, thus improved transformation efficiency and selectivity.With raw material, the mixture of catalyzer and gas is introduced continuously streamed reactor (progressive flow type reacter).

Terminal point at predetermined lifting intraductal retention time, on by elongated riser reaction zone or the determined direction of its extension area, catalyzer is sprayed, make steam product change direction thus again with less momentum, separate (ballistic separation) thereby product and catalyzer are carried out trajectory, so just avoided the secondary cracking of product.

With the catalyst stripping separated to remove high boiling component hydrocarbon that carry secretly or that absorb with other, with oxygen containing combustion-supporting gas coke burning is wherein made its regeneration at least one breeding blanket then, regeneration condition is, time, temperature and regenerative environ-ment should be enough to the carbon content on the regenerated catalyst is reduced to about 0.05% or lower (calculating by weight).CO in the coke combustion zone: CO ₂Mole ratio remain on about at least 0.20～about 0.25, and, be more preferably about at least 0.5 with about at least 0.3 for well.

Removing the air of deentrainment, and then circulation is sent into reactor and is gone to contact with fresh feed with the catalyst stripping of regenerating.

The present invention also is the operating parameters in the hydrocarbon feed catalytic cracking step is being kept a specific relation, can change a severity of the catalyst regeneration that requires and use thus.So, because this active catalyst is sent in the cracking process of oily raw material, reduced coke formation amount, thereby made its selectivity that significant improvement arranged hydrocarbon product.Working method of the present invention provides a kind of like this catalyzer, and the activity that the catalyzer before its specific activity can reach is higher.

With regard to another feature aspect, the present invention also is to have realized the crystalline zeolite catalyst cracking method of residual oil fraction in the higher crude oil of selectivity, such residual oil fraction in the cracking crude oil particularly, wherein contain nickel and vanadium metal impurity, content range is 1000～20000ppm, and have the big polynuclear hydrocarbon material of molecular weight, in its cracking process, dispersive Lan Shi carboloy residue is up to about 8.

More special aspect of the present invention is to use the method for the dry gas stream that comprises hydrogen, under the condition that forms catalyst suspension, the generation that contains some certain limit in the dry gas stream contains the composition of the above hydrocarbon of three carbon atoms, cooling fluid with one or more regenerated catalysts, as steam, water and composition thereof is used in combination with dry gas stream to form and promotes the gas suspension body, wherein be distributed with the hot regenerated catalyst particle, its temperature is adjusted to the catalytic cracking that is particularly suitable for realizing the residual oil raw material be made up of gas oil, contains or do not contain the higher VACUUM TOWER BOTTOM product that boiling point in general is higher than about 552 ℃ (1025) in this residual oil raw material.Be suitable for realizing dry gas stream such as commercially available refining product dry gas stream above-mentioned purpose of the present invention and substantial improvements, the above hydro carbons of three carbon atoms that wherein contain is less than 10 volume %, and the amounts of hydrogen that contains is preferably at least 10 volume %.From economic angle, this hydrogen-containing gas streams can be recycled from one or more refinery streams again.

The present invention adopts dry gas stream to replace petroleum naphtha in conjunction with steam and (perhaps) water, light hydrocarbon, the series of advantages that scheme obtained that contains the synthetic operation of the high-purity hydrogen of a large amount of three above hydro carbons compositions of carbon atom or wet gas current is unexpected and unpredictable.In fact, have quite a few disclosed prior art proposal to think, the cracking catalyst of containing metal impurity should comprise the hydrogenation or the dehydrogenation functionality of residual coke to suppress these metallic impurity of a great deal of in its surface.But applicant's operational aspect has obtained unexpected product liquid selection result among the present invention, uses quite cheap dry gas product in the operating process, has greatly reduced coke formation amount.

Specificity of catalyst

Used catalyzer can be in fact any fluidized crystallization zeolitic cracking catalyst used in the prior art proposal in the operating process that catalytic cracking of the present invention transforms, and wherein contains rare earth metal and (perhaps) hydrogen ion in the crystalline structure of zeolite.Zeolite is scattered among the siliceous clay substrate material, and this substrate material can have also can not have cracking activity.That is to say that this substrate material is selected from silica-alumina, silicon-dioxide-zirconium or silicon-dioxide-chromium mixture, this class material can make the additive of sedimentary metallic impurity passivation help catalysis with one or more more effectively.More applicable interpolation materials comprise the rare earth metal that contains excessive lanthanum, the compound of antimony and titanium.The active crystalline zeolite that the used cracking catalyst of the inventive method can contain becomes deal to be lower than about 40 weight % or lower, and for equilibrium catalyst commonly used, content range more commonly used is 5～20 weight %.

More particularly, catalyst system therefor can be selected from the catalyzer of being introduced among United States Patent (USP) 4440868 or the United States Patent (USP) 4435515.Preferred catalyzer is optional from patent application case USSN483061, and the applying date is April 7 nineteen eighty-three, a kind of catalyzer of being introduced among (file number 6193AUS).Here every kind of catalyzer mentioning all only as a reference.

Particularly preferred one group of catalyzer be for can activating hydrogen and those catalyzer of cavernous structure are arranged, and raw molecule can enter these holes in so that in the hole or be convenient to raw molecule by the absorption of activity of such catalysts point with (perhaps) in the place of closing on the hole and contact with the activity of such catalysts position.A class catalyzer can obtain various catalyzer like this, for example comprises the laminated silicate material, as the catalyzer on green.

Used zeolite containing catalyst can comprise any zeolite among the present invention, no matter be natural, still the synthetic of half synthetic all can be separately or with other and the material mixing of the suitability that reduces catalyzer indistinctively use, as long as the final catalyzer that forms has following activity and has pore structure just passable.For example, if catalyzer is a mixture, the porose refractory inorganic oxide support that catalyzer can comprise zeolite and be used in combination with it perhaps is dispersed in zeolite in the porose refractory inorganic oxide support; In this case, catalyzer for example can contain about 1 weight %～about 60 weight %, and it is better with about 1 weight %～about 40 weight %, more typical is that the zeolite of about 5 weight %～about 40 weight % is scattered among the carrier, above-mentioned per-cent is that the total catalyst weight (butt) when being used in combination when using separately with porose refractory inorganic oxide or with any other known auxiliary serves as that calculate on the basis, used auxiliary is in order to promote various desired reactions or suppress various the reactions that take place do not expected that wherein some auxiliary will be discussed below.

For the kind to the used zeolite [molecular sieve of the present invention has a understanding roughly, can be " Refinery Catalysts Are a Fluid Business " and " Making Cat Crackers Work on Varied Diet " these two pieces of disclosed contents of article with reference to title, these two pieces of articles be published respectively on " the Chemical Week magazine " of on July 26th, 1978 and publication on September 13rd, 1978.Here the narration in the above-mentioned article of mentioning is only for reference.

In general, the overall size range of the catalyzer of employing is about 5 * 10 ^-6Rice～about 160 * 10 ^-6Rice (about 5～about 160 microns) is more preferably about 40 * 10 ^-6Rice～about 120 * 10 ^-6Rice (about 40～about 120 microns), and in proportion, the size range of its chief component is 40 * 10 ^-6Rice～about 80 * 10 ^-6Rice (40～about 80 microns).

The catalyzer that is adopted preferably has quite high cracking activity and selectivity at the very start, and just reaches high conversion and high yield in the very short residence time.The conversion capability of catalyzer can be represented or measures out with the standard catalyst activity test with the transformation efficiency that obtains in the actual mechanical process.[consult classical works: Shankland and Schmitkons work " Determination of Activity and Selectivity of Cracking Catalyst ", Proc, API27(III), 1947, pp.57～77].For example, the catalyzer of preferentially selecting for use in the operating process of the inventive method, should have enough activity to keep about at least 50% or be more preferably about at least 60% transformation efficiency.In this respect, transformation efficiency is benchmark with the fresh feed and represents with liquid volume percent.

Preferred catalyst of the present invention also can define like this, and promptly at it under the fresh or equilibrium state, this catalyzer shows with the little activity test of MAT[(micro-activity test)] given activity of deriving and coming out and represent with volume percent.(operating process and these tests of MAT ' S) can be consulted United States Patent (USP) 4299687 to importance of the present invention for relevant various little activity tests.

When being that the basis is when coming representation feature with the MAT activation analysis, MAT activation analysis when MAT activation analysis in the time of can " just introducing " operating process of the present invention based on these catalyzer to the description of preferred catalyst of the present invention or equilibrium state is perhaps based on the two MAT activation analysis.

It is about 60% that preferred MAT activity value during fresh and non-live catalyst " just introduce " operating process of the present invention is at least, but should be noted that particularly and adding under the situation of non-live catalyst at a high speed, and lower MAT activity value also allows.

For the catalyzer that the present invention has adopted, the MAT activity value during acceptable equilibrium state is more than 20%, preferably about at least 40% or higher, and better activity value is about 60% or higher.

Add catalyzer

In general, the weight ratio scope of catalyst system therefor of the present invention and fresh feed (not being exposed to the raw material in the cracking catalyst environment promptly under cracking conditions) is about 3～18.It is about 4～12 that preferred ratio can reach, and this depends on that the possibility that forms coke in the crude oil is few greatly.Limiting under the condition that quality product requires, catalyzer and oil plant ratio are being controlled at the productive rate (is benchmark with the fresh feed) that quite low value in the above-mentioned scope just might reduce coke in the oil plant.

As embodiment, catalyzer can add the regular loss that also can intermittently add with catalyzer in the replenishment system continuously.For example, the adding of catalyzer can be connected with the discharge of catalyzer, to keep or to increase the average activity value of catalyzer in the device or make the amount of metal on the catalyzer remain constant.

As embodiment, the speed range that live catalyst adds operating gear can be 0.285 kilogram of about every cubic metre of raw material (0.1～about 3 pounds/barrel) to 8.55 kilograms of about every cubic metre of raw materials or higher (about 0.03～1 weight % of charging) or higher, and this will decide according to metal content in the raw material and the amount of metal that allows to deposit on the equilibrium state catalyzer.On the other hand, if adopt the equilibrium state catalyzer, can reach up to 14.25 kilograms of about every cubic metre of raw materials (about 5 pounds every barrel) or higher replacement speed.If the operational condition in the operating gear might make catalyzer lose activity quickly, just can adopt the catalyzer that is higher than above-mentioned value to add speed; And under opposite condition, can adopt lower interpolation speed again.

Metal on the catalyzer

The present invention operates with allowing heavy metal deposition catalyzer thereon to carry out cracking, and up to now, in the operating process of common fluid catalytic cracking (FCC) decompression gas oil (VGO), has thought that this does not allow fully.Adopt allowing heavy metal is that value in about 1000～approximately 20000ppmNi+V scopes deposits to the catalyzer on it with mean vol, and this is possible.Deposition value scope also can be about 4000～50000ppm, and that more likely realize is 5000～approximately 30000ppm.

Aforementioned high value is by weight to be calculated and based on 1,000,000/umber of heavy metal, these heavy metals comprise the iron (sedimentary extra iron when being application) and the copper of nickel, vanadium, increment, metal wherein is with the equilibrium catalyst of regenerating, and metal promptly that record on the used catalyst and that calculated by weight is based on this represented.People also can adopt from another device, the equilibrium catalyst of another fluid catalytic cracking (FCC) device for example, this device has been used for cracking decompression gas oil, and the carboloy residue that wherein has during high temperature pyrolysis is less than 1 and contain the heavy metal that is less than about 4ppm nickel equivalent.

The catalyzer ignition dope

Also can comprise one or more burning ignition dopes in the catalyst composition, this is of great use in follow-up process catalyst regeneration step.In order to recover activity of such catalysts, in regenerative process, coke to be burnt, coke wherein is converted into the burning gas that comprises carbon monoxide and (perhaps) carbonic acid gas.Know, when with various materials, Pt for example, Pd, rare earth metal (perhaps adding with charging), might quicken the conversion of coke to carbon monoxide and (perhaps) carbonic acid gas when joining cracking catalyst on a small quantity.Ignition dope when coke is converted into carbon monoxide might reduce the temperature that specified rate is removed the coke degree, so just reduces catalyzer deactivated possibility when high temperature.

The common effective usage quantity scope of these ignition dopes for trace to calculating with catalyst weight up to about 10%～20%(), for example can be any ignition dope that under regeneration condition, can promote carbon burning general.

Additional materials

The additional materials amount that can contain in the raw material can change as required; But the additional materials amount that adds preferably can be enough to keep basically the thermal equilibrium in the operating process of the inventive method.These materials that add reaction zone can be up to for example about 0.4 with respect to the weight ratio of raw material, preferred range be about 0.02～about 0.4, be more preferably about 0.03～about 0.3, and best be about 0.05～about 0.25.

The liquid water that will come when circulating from regenerative process is as a kind of additional materials, perhaps mixed with raw material or when adding reaction zone individually, embodiment preferred is will be in the above-mentioned scope calculated of benchmark hydrogen sulfide to be dissolved in wherein in the gross weight with raw material.In other words, should there be the hydrogen sulfide of about 500ppm～about 5000ppm to be dissolved in the liquid water of sending here that circulates.Also the hydrogen sulfide in above-mentioned weight ratio scope can be added as additional materials, thereby replacement is dissolved in the hydrogen sulfide in the liquid water of sending here that circulates.

The inventive method adopts the trajectory separation method at the dirty end of continuously streamed riser tube (progressive flow type riser) catalyzer and steam to be separated, this is disclosed in United States Patent (USP) 4066533 and United States Patent (USP) 4070159 as Meyer this (Myers) etc., and the disclosure of two pieces of patents mentioning here is only for reference.

But according to whether having slippage between riser tube inner catalyst and the hydrocarbon steam, the residence time of catalyzer in riser tube can be identical with the residence time of steam, also can be different.So, the ratio of catalyzer residence time in reactor at mean residence time in the reactor and hydrocarbon steam, that is to say that the slippage scope can be about 1～about 5, preferred range is about 1～about 4, preferred scope be about 1.1～about 3, and most preferred range about 1.2～about 2.

If about at least 80% for riser tube length, steam is essentially identical words promoting intraductal retention time and the duration of contact of steam-catalyzer in riser tube, will be understood that this is favourable.

The regeneration of catalyzer

The regenerative operation process of catalyzer can be carried out in the temperature range of about 593 ℃ (1100)～about 871 ℃ (1600), and this is the temperature that records in the exit of catalyst regenerator.This temperature range can be about 649 ℃ (1200)～about 816 ℃ (1500), better temperature range is about 677 ℃ (1250)～about 774 ℃ (1425), and most preferred scope is about 704 ℃ (1300)～746 ℃ (1375) or about 760 ℃ (1400).

In order to reduce regeneration temperature to greatest extent and to the requirement of regenerated capacity, the time that just requires in the stripper to be adopted, temperature and envrionment conditions should be enough to make the volatile hydrocarbon species content that catalyzer had after the stripping to be reduced to about 10% or lower (calculating by the weight that is brought to revivifier) as much as possible.This stripping operating process can comprise for example reheat of catalyzer, carry out stripping more completely with steam, and adopt temperature in general to be higher than the gas of the normal running temperature of fluid catalytic cracking decompression gas oil (FCC/VGO), for example from the next stack gas of revivifier, and other refinery's air-flow, (contain H as the discharge air-flow of hydrotreater ₂S), hydrogen and other gas carry out stripping.Stripper can be operated under the temperature that is higher than about 482 ℃ (900).The stripping operation that temperature when handling used catalyst reaches higher temperature range also should be thought and comprises within the scope of the invention.

For zeolite catalyst is remained in the desired activity value scope, just require the regenerative operation of catalyzer under such condition, to carry out, it is the time of regenerative operation, the weight percentage that temperature and envrionment conditions all should be enough to make regeneration to be retained in the carbon on the catalyzer after this is reduced to about 0.05% or lower, and this is not consider whether catalyzer has heavy metal that a large amount of depositions get off.Coke one speech is understood to include any material that can not evaporate that residues in after the catalyst stripping on the catalyzer or the material of hydrocarbon-containiproducts.

Caused quite a large amount of coke to produce with the quite high transformation efficiency that the inventive method obtained, for example based on fresh feed and calculate by weight, that coke yield reaches is about 4%～about 17%, more commonly about 6%～about 14%, and modal be about 6%～about 12%.

In the scope of catalyzer that suggestion is used and the ratio of raw material, formed sedimentation of coke amount is benchmark and calculates by weight by the fresh or regenerated catalyst of water content not, can surpass about 3%, more commonly surpass about 0.5%, and the most common about 1%.Though more common sedimentation of coke amount is 0.5～about 1.5%, such sedimentation of coke amount also can be up to about 2%, and is perhaps about 3%, perhaps higher.

According to the preferred embodiments of the invention, just in fact whole, available oxygen reaches above-mentioned low levels value with the coke content that regenerated auxiliary treatment process proceeds on the regenerated catalyst, and oxidation is to generate H by hydrogen all in the coke is all burnt ₂O, carbon all in the coke all burnt generates CO and (perhaps) CO ₂And sulphur all in the coke all burnt generate SO ₂Needed stoichiometry is sent to one or more regenerative operation stages.If also contain other combustiblesubstance in the coke, just can adjust above-mentioned stoichiometry so that it comprises the required amount of oxygen of these combustiblesubstances of burning.

Multistage regenerative operation provides with oxygen regenerative operation and to CO: CO ₂The operative technique that combines of the control of mole ratio, also provide the coke content on the catalyzer is reduced to be preferably 0.05% or lower method.So, to the CO in the first step regenerative operation process: CO ₂Mole ratio just control and can in this operating process, calculate by weight, remove the coke on about catalyzer of 65%～about 80%.

Combine with abovementioned steps, last coke content accounts for the percentage ratio that is present in weight of coke on the catalyzer at first, i.e. the total coke that left behind after the abovementioned steps can feed more oxygen and removes in follow-up regeneration step.

Particularly preferred embodiment of the present invention is a branch two-stage regenerated catalyst, and top temperature wherein is about 816 ℃ (1500 °F), but preferably operates under the temperature that is not higher than 760 ℃ (1400).Partial service temperature and the identical of the first step or lower than the first step, like this can be in breeding blanket, the second stage with the carbon content on the catalyzer, calculate by weight, be reduced to about 0.05% or lower or even low to about 0.025% or lower, in fact, even the carbon content before the regeneration on the catalyzer is high to about 1% or higher, can at an easy rate catalyst regeneration be reached carbon content and be low to moderate 0.01% but use this technology.

Another particularly preferred technical scheme is control or limits the regenerative heat of passing to fresh feed through recycling catalyst, wherein a part of dissipation of heat that recycling catalyst had passed to the additional materials of discussing in the present patent application.The catalyzer of discharging from revivifier with suitable stripping gas stripping to remove oxygen-containing gas.This stripping for example can carry out as stripping gas with steam nitrogen or rare gas element under quite high temperature, catalyzer deactivated viewpoint under the water vapor heat effect when avoiding using water vapor, and it is favourable using nitrogen or other rare gas element.

Charging

The present invention is suitable for catalytic cracking lightweight gas oil feed or heavy oil residue raw material, comprise VACUUM TOWER BOTTOM product and component wherein, these raw materials were before handled through partial hydrogenation, sulphur and nitrogen compound have therefrom been removed, (perhaps) through the part carbonization treatment and remove the processing of metal, treatment process is under the hot visbreaking condition that contains hydrogen or do not have the thinner of hydrogen to exist it to be contacted with absorbing material or sorbing material.Used absorbing material or sorbing material can be suitable inert material in the visbreaking operation, or its catalytic activity is quite low, no longer is applicable to the material of Hydrocarbon Content by Catalytic Cracking Operation process.So, operation of the present invention also is quite useful for disclosed synthetic operation scheme in United States Patent (USP) 4434044 such as Busch, and the content of the United States Patent (USP) of mentioning here is only for reference.

Operational condition will change with the composition and the boiling spread of the raw material of being sent in the Hydrocarbon Content by Catalytic Cracking Operation process of the present invention.In general, the temperature range of sending into the regenerated catalyst of riser cracking operating process is 649 ℃ (1200)～816 ℃ (1500), and the temperature of more frequent employing is about 704 ℃ (1300)～760 ℃ (1400).The dividing potential drop of the hydrocarbon feed when of catalyzer and oil plant changes with the boiling spread of raw material and the volume of used gaseous diluent, each parameter should be determined like this so that comprise the suspension cracking catalyst, the temperature range of the vapour shape hydrocarbon converted product that promotes gas and atomizing raw materials diluted material when discharge the zone of cracking of riser reactor is 482 ℃ (900)～598 ℃ (1100), and more common temperature range is about 510 ℃ (950)～about 566 ℃ (1050).

Among the present invention relevant in the hydrocarbon processing process, reduce coke formation amount and improve the present general inventive concept of product selectivity just can be used for the course of processing set forth in the above-mentioned United States Patent (USP) of indicating 4434044 as long as make an amendment slightly, said modification is as the oil plant raw material that removes metal is desired, fluidized particles with absorption agent or sorbent material carries out the operation of decarburization visbreaking earlier, and then with technical scheme of the present invention the heavy oil feed that partly remove metal and part decarburization is carried out catalysis upgrading processing.Here an importance of the described synthetic operation scheme of the referenced patent of being mentioned is the separation of the lightweight gaseous product shown in the relevant figure I, and wherein, fuel gas will separate from the component of three carbon atoms and four carbon atom.This fuel gas that comprises hydrogen when separating, is specially adapted to the course of processing of the present invention from the hydrocarbon component of three carbon atoms and four carbon atom.Therefore, specially United States Patent (USP) 4434044 described product separation methods are incorporated in this, only for reference.Working method of the present invention to the described cracking method of this referenced patent as such correction, promptly adopt the dry gas do not contain petroleum naphtha but to contain steam to make the hot regenerated catalyst particle form a upflowing suspensoid in the bottom of riser tube, and then contact with oily raw material, wherein improve the quality of oil plant with crystalline zeolite catalyst cracking method provided by the invention.

With regard on the other hand, equipment in the United States Patent (USP) 4434044 in the figure V is arranged and has been comprised the catalytic cracking zone that adjoins with two-stage catalyst regeneration flow process, arrange so that cooling is delivered to the said second stage from the said first step like this and remove the regenerated catalyzer, but modification is preferably done some in this arrangement, so that make the upper diameter of riser reactor bigger than its underpart diameter, be equipped with in the riser reactor and want cracked oil raw material, these oily raw materials are to be admitted to from the downstream part than major diameter riser tube partly.This design is the United States Patent (USP) 4435279(file number 6168AUS of Busch etc.) a part, therefore quote this patent here, only for reference.

Of the present invention simple but effectively working method be suitable for to reaching any gas oil that crystalline zeolite catalyzer that various cracking purposes get up in latest developments carried out or than the operating process of light-weight residual oil catalytic cracking.Therefore, applicable catalyzer comprises the described catalyzer of following document, and promptly United States Patent (USP) 4377470, USSN258265, and the applying date is on April 28th, 1981, (file number 6117BUS); United States Patent (USP) 4407714, USSN263391, the applying date is on May 13rd, 1981, (file number 6038AUS); United States Patent (USP) 4431749, USSN318186, the applying date is on April 10th, 1981, (file number 4078BUS); United States Patent (USP) 4432890, USSN277751, the applying date is on March 19th, 1981, (file number 6125AUS); And United States Patent (USP) 4440868, USSN328354, the applying date is on December 7th, 1981, (file number 6148AUS).

More particularly, the present invention and Meyer this (Myers) etc. in United States Patent (USP) 4431515 and working method disclosed and required for protection in United States Patent (USP) 4435279 such as Busch be different, its reason is as described below.So and since these patents relevant technical field identical with the application's case (file number 6224AUS), all be that it is only for reference to quote from these patents here about the catalyzed conversion of oily raw material.

Working method of the present invention is following different aspect with the difference of above-mentioned patent, comprising:

A) the product gas of refinery, being commonly referred to dry gas (generally is from common gas concentration unit, as Busch, Walters and Zandona are represented in the figure III in United States Patent (USP) 4434044), be used as the lift gas that makes hot fresh regenerated catalyzer under the temperature of 704 ℃ (1300), form suspensoid at least, contain the hydrogen of at least 10 volume % in the employed dry gas, but the above material (C of three carbon atoms that contain ₃-plus) be less than 10 volume %.Dry gas is used as the steam of heat exchange material and (perhaps) water is replenished, and its usage quantity should be enough to just that regenerated catalyst temperature is reduced to the desired low temperature of oily feedstock conversion.The hydrogen that preferred dry gas contains is about 15～40%, more preferably 20～35%, and the above material of three carbon atoms that contain is 2～8%, is more preferably 0～6%.

B) dry gas-steam-catalyst suspension is that the bottom of zone of transformation in riser tube oils riser tube below the raw material decanting point forms, and will keep certain residence time to guarantee being no more than about 0.20 weight % or 0.25 weight % contact the amount of coke that deposits on the catalyzer before with oily raw material that the boiling point of sending into is higher than 343 ℃ (650).Therefore, formed dry gas-steam in riser tube-regenerated catalyst suspensoid, with before the oily raw material of sending into contacts, the residence time in riser tube should be no less than one second number/one, but should be enough to make the metal oxide on the catalyzer to be reduced into oxide form at a low price or to be reduced into metallic state.

C) the above material of three carbon atoms that contain is less than 10 volume % and the hydrogen that contains is that refinery's product dry gas stream of 10～40 volume % can be separated from the desulfurizer of aromatic hydrocarbon, and consider from economic angle, be very attractive, thereby impel it to be used for the cracking operating process of oily raw material of the present invention.The hydrogen sulfide that is present in this dry gas stream is a kind of composition of great use, and it can generate sulfide with the metallic impurity reaction.

D) use the Ni+V metallic impurity that deposit on it to be up to the available dry gas of the present invention of operation of the catalyzer processing carbon containing metal oil raw material of 20000ppm, and finish, thereby can improve product selectivity for depositing under the condition that nickel on the catalyzer and vanadium provide one or more metal passivators or compound.

E) improvement that working method of the present invention reached product selectivity and make the temperature severity in the catalyst regeneration operating process reduce to significantly reducing of slurry oil amount and coke formation amount, with regard to the operating process of two-stage catalyst regeneration, the original temperature that surpasses 760 ℃ (1400) in each grade regeneration step is decreased.Therefore, when steam being added in the dry gas forming when promoting catalyst suspension, because of the heat effect of water vapor makes the deactivated condition of catalyzer be reduced to acceptable limit to a great extent.

When Fig. 1 makes the lift gas of catalyzer for using wet circulation gas and dried circulation gas at the comparison line chart that oily feedstock conversion is lower than the hydrogen yield that the product of 221 ℃ (430) obtained before as boiling point.

Fig. 2 is for being that the boiling point that boiling point is lower than five carbon atoms that obtained when using wet recycle gas and dried recycle gas as the lift gas of catalyzer before the product of 221 ℃ (430) is the comparison line chart of the gasoline yield of 221 ℃ (430) with oily feedstock conversion.

Fig. 3 is for oily feedstock conversion being the comparison line chart that boiling point is lower than the gasoline selective that is obtained when using wet recycle gas and dried recycle gas as the lift gas of catalyzer before the product of 221 ℃ (430).

The comparison line chart of resultant coke yield when Fig. 4 is lower than the product of 221 ℃ (430) with oily feedstock conversion as boiling point as the lift gas of catalyzer for using wet recycle gas and dried recycle gas.

Fig. 5 is for oily feedstock conversion being the comparison line chart that two following amount of by-products of carbon atom reduce that shows that is obtained when using wet recycle gas and dried recycle gas as the lift gas of catalyzer before boiling point is lower than the product of 221 ℃ (430).

Fig. 6 is the schema of slag oil cracking device-gas concentration section, has schematically expressed the process that reclaims by the used suitable dry gas of the present invention.The more detailed description of this figure can be with reference to belonging to Busch, in the United States Patent (USP) 4434044 of Walters and Zandona to the explanation of corresponding figure III.

Fig. 7 has expressed the reactor-regenerator in the another kind of slag oil cracking device, more detailed description can with reference in the United States Patent (USP) 4434044 to the explanation of corresponding figure V.

Fig. 8 arranges the longitudinal section synoptic diagram for two-stage regenerative operation flow process with the equipment that the riser cracking district adjoins mutually.

Working method of the present invention and the improvement effect that is reached will be described in more detail with embodiment described below, and used operational condition and the result that obtained present in diagrammatic form out among the embodiment.

The table I has shown the analytical results that the humid gas that obtains from the market that cracking process of the present invention is adopted carries out.Should be noted that three above materials until five carbon atoms of carbon atom comprise that the hydrocarbon materials of five carbon atoms amounts to about 45%.

The table I

Compound mol %

Hydrogen 19.74

Methane 17.72

Nitrogen 3.97

Carbon monoxide 0.72

Ethene 5.93

Ethane 6.97

Oxygen+argon gas 0.03

Hydrogen sulfide is not found

Propylene 12.48

Propane 4.16

Carbonic acid gas 1.13

The 1,3-butadiene trace

1-butylene+iso-butylene 5.07

Anti-(formula)-2-butylene 2.59

Along (formula)-2-butylene 1.98

Trimethylmethane 3.81

Normal butane 1.08

The carbon oxysulfide trace

Iso-pentane 2.27

Skellysolve A 0.28

After Skellysolve A, flow out 10.05

The table II has shown the analytical results that the dry gas that obtains from the market used in the cracking process of the present invention is done, and should be noted that, three carbon atoms are above up to Skellysolve A and comprise that the content of Skellysolve A is about 8.68%.Therefore, should admit, refinery's gaseous product to be carried out industrial processing and be lower than 8 or 10% cheap dry gas product with three substances content more than the carbon atom that obtain wherein, consider from economic angle, be difficult to accomplish, therefore, concerning the refining of petroleum merchant, this is not almost had no interests in other words conj.or perhaps can say.On the other hand, the fluidized catalyst zone of cracking in riser tube is upwards transmitted a suspensoid and is contacted with the heavy oil feed of sending into, and this conforms with wishes and necessity.With regard to one aspect of the present invention, the lightweight gaseous product in the cracking process is separable to come out, and circulation is delivered in the cracking process then, as what the application discussed, can be applied once more therein.

The table II

Compound mol %

Hydrogen 20.01

Methane 33.10

Nitrogen 9.94

Carbon monoxide 4.03

Ethene 12.70

Ethane 11.40

Oxygen+argon gas 0.13

Propylene 4.24

Propane 0.51

Carbonic acid gas 0.01

1-butylene+iso-butylene 0.62

Anti-(formula)-2-butylene 0.17

Along (formula)-2-butylene 0.11

Trimethylmethane 0.69

Normal butane 0.12

Iso-pentane 0.02

After Skellysolve A, flow out 2.19

By the experimental sequence that helps to confirm special working method of the present invention, to comprise Lan Shi carbon residue, sulphur, the residual oil raw material of the carbon containing metal of nickel and vanadium is sent to earlier with the fluid cracking catalyst that typically comprises rare earth metal and is contacted, catalyst changeout more then, replace previous cracking catalyst with the cracking catalyst that contains crystal aluminosilicate [faujusite (fauja-site)], at high temperature catalyzer is carried out manipulation of regeneration at last, what use in this process is that three substances content more than the carbon atom obtaining in by catalytic cracking process are lower than about 10% the dry gas product that is rich in hydrogen and the content of four carbon atom and five carbon atom hydrocarbon reaches the humid gas product that is rich in hydrogen that can play substantial role.

To collect a large amount of experimental datas that obtain by experimental sequence and make the comparison line chart,, will go through these figure below as Fig. 1 to Fig. 5.Thermocatalyst with mix to form catalyst suspension with dried recycle gas or wet recycle gas before residual oil raw material contacts as lift gas, this operation is enough to represent the feature of cracking operating process in the riser tube discussed below.

The hydrogen of Fig. 1-generation

Referring now to Fig. 1, wherein be under the temperature of about 704 ℃ (1300), used cracking catalyst has been carried out pre-treatment with the humid gas product that is rich in the dry gas product of hydrogen or is rich in hydrogen after, be used in and residual oil raw material is converted into boiling point is lower than the line chart that resulting data are depicted as in the process of product of 221 ℃ (430).As can be seen from Figure 1, when top curve representation is handled catalyzer with humid gas, transforming the hydrogen that produces in the process of residual oil raw material with the catalyst suspension that obtains after handling subsequently, when transforming with the high temperature catalyst suspensoid that adopts dry gas to be at least about 704 ℃ (1300) as the lift gas formation temperature resulting amounts of hydrogen by comparison, the amounts of hydrogen that produces during with humid gas is more.

Fig. 2-five carbon atom is the productive rate of the gasoline of 221 ℃ (430) to boiling point

On the other hand, Fig. 2 has expressed the gasoline yield of five carbon atoms to 221 ℃ of boiling points (430), and this is to use the experimental data that obtains when using dry gas or humid gas as the catalyzer lift gas before hot regenerated catalyst contacted with the residual oil raw material of sending into to draw to form.Can be clear that very much the gasoline yield height that the gasoline products productive rate that obtains during as lift gas with dry gas obtains when using humid gas as lift gas from this figure.So, the selectivity of gasoline products has obtained improving greatly.

Fig. 3-gasoline selective

Fig. 3 draws the comparison line chart that forms with gained through improved gasoline selective experimental data, as can be seen from the figure, initial be higher than the selectivity curve that obtains when the wet recycle gas of hydrogen is rich in use with dry gas and the improvement gasoline selective curve that obtains after hot regenerated catalyst contact, this is to obtain with testing before the residual oil raw material conversion that will send into.

The coke of Fig. 4-generation

Fig. 4 is another line chart of drawing with experimental data, represented under the condition that catalyzer exists, residual oil is converted into the amount of coke that is produced when boiling point is lower than the product of 221 ℃ (430), and catalyzer dried recycle gas or wet recycle gas initial and as the lift gas use contact in riser cracking district for example.From the figure line of Fig. 4 as can be seen, the amount of coke that in catalyzer, produces during with the dried recycle gas that uses hydrogen rich gas by comparison, use wherein four carbon atom and five carbon atom hydrocarbon reach the content that can play substantial role be rich in the wet recycle gas of hydrogen the time coke that in catalyzer, produced more.High sedimentation of coke amount helps to obtain to surpass the catalyst regeneration temperature of 760 ℃ (1400).

The following by product of Fig. 5-two carbon atom

On the other hand, Fig. 5 has shown the improvement result of two products below the carbon atom of resulting reduction to the dried recycle gas product of the application definition and wet recycle gas product the time.This figure shows that when using the defined dried circulating current of the application to contact with hot regenerated catalyst at first, by-product yields is much lower.

Data analysis among Fig. 1-5

The self-evident data line chart of simple discussion is estimated some conclusions that draw to be shown without doubt, three above hydrocarbon of carbon atom wherein reach the wet recycle gas of the content that can play substantial role will give cracking catalyst with coke distribution, thereby reduced the cracking activity and the selectivity of catalyzer, these by obtaining five more than the carbon atom gasoline and the productive rate difference of light cycle oil very clearly showed.And on the other hand, use and contain three hardly more than the carbon atom, when comprising the dry gas of four carbon atom and five carbon atom products, can improve productive rate wherein widely, in addition, be to be further noted that if the dry gas mixture that uses the application to propose, then with respect to the raw material of a certain given riser cracking operation, the lift gas content of use can reach about 12～15 weight % or higher.When three materials more than the carbon atom that contain in the lift gas, comprise when the amount of hydrocarbon of five carbon atoms is quite high, these materials that contain, at catalyzer with before residual oil raw material contacts, cracking reaction can take place and with sedimentation of coke on the hot regenerated catalyst of just having sent into, thereby the cracking activity and the selectivity of catalyzer have been reduced, shown in the figure as discussed above, this has further caused the reduction of five above products of carbon atom again, according to estimates, the desired product that can form gasoline that obtains can reduce at least 3～5 volume %.Have found that the catalyzer that has deposited coke in advance of Xing Chenging can improve the formation amount of by product and coke like this, shown in the comparison line chart of expressing in self-evident mode.

Therefore, can find out from the line chart that is depicted as with the gained experimental data discussed above with removing, to in riser tube, oily raw material be carried out more effective cracking, contacting with the hot regenerated catalyst of just having sent into lift gas at first with regard to necessary, this catalyzer with will carry out before cracked oil raw material contacts, even when having coke to exist, lift gas also can make sedimentation of coke hardly on hot catalyst particles.The essence of this operation imagination is that the experimental data that provides with the application is confirmed, these experimental datas be with get on the market and from considering worthwhile refinery's operating process economically, for example the dry gas product in the cracking operation obtains, and contains hydrogen in the dry gas product and the above hydrocarbon of three carbon atoms that contains had better not surpass about 10%.The dry gas that another kind is suitable for doing lift gas is by hydrogen, and methane and ethane are formed.But, the recycle gas product stream that a kind of like this cracking process that promotes usefulness or refinery's operating process produce be difficult to economically reasonably cost obtain from industrial.The aromatic oil product that obtains in the coal course of processing is carried out the hydrogen-containing gas streams that desulfurization produced,, just can use as long as the above hydrocarbon content of three carbon atoms wherein is no more than 10 volume %.

Also can draw such conclusion further from the experimental data that relates to working method design of the present invention that obtains, promptly the residual coke content of regenerated catalyst should be reduced at least 0.10 weight %, preferably reduce at least 0.05 weight %.Form the catalyst suspension that contains hydrogen with dry gas, with before needs cracked oil raw material contacts, coke content in the catalyzer should be restricted to about 0.20 weight %, and preferably should not surpass about 0.15 weight %, so just from the operating process of the application's narration, obtain bigger interests.

The formation thought of relevant regenerated catalyst-dry gas suspensoid is applicable to the contact system of fluidized catalyst in riser tube among the present invention, as the contact system that Busch etc. proposes in United States Patent (USP) 4434044 at United States Patent (USP) 4435279 and Busch etc., two pieces of patents mentioning here are only for reference.Reach operation thought of the present invention thereby these patent disclosures are done suitable correction, will working method wherein is improved in best mode.

Riser tube equipment

Particular device in the illustrations 7 is arranged figure I in the United States Patent (USP) 4435279 that is equivalent to Busch etc. basically and the figure V in the United States Patent (USP) 4434044.In equipment another kind of of the same type shown in Figure 8, comprise riser reactor 1, a cross section expansion arc is arranged at reactor top, is the bigger part of a diameter in this transition section upper end of riser tube.Will be through the oily raw material of an input in opening for feed 5,7 or 9, for example to carry out cracking effective especially for residual oil raw material.The transition section of riser tube 2 or larger diameter partly have a plurality of feed-pipe devices 6, the upper limb of feed-pipe 6 contiguous transition sections, and in embodiment preferred, these feed-pipes are used for sending into oily raw material.Cracking discussed here operation is formed by hydrocarbon product steam, before the suspensoid that catalyzer and lift gas are formed separates, just control raw material and dry gas-catalyst suspension duration of contact in riser reactor, vertical direction feeding unit 5 spaced apart from each other, 7 and 9 provide bigger degree of freedom to operator, therefore, but the suitable high zeolite catalyst of the riser tube use temperature of using 1～2 this structure as shown in Figure 8 with oily raw material catalytic cracking to improve its quality, the bottom in riser cracking district is delivered in cracking with oily raw material, middle part or top, but, count/one second extremely up to 1 in order to be limited in the duration of contact with oily raw material and catalyzer, within 2 or 3 seconds, also oily raw material can be delivered to the downstream of formed dry gas-regenerated catalyst suspensoid.

In this riser tube arrangement mode, hot regenerated catalyst mixes with dry gas or fluidizing agent at first, thereby form the suspensoid at upper reaches at the qualification diameter parts of riser tube, the temperature range of hot regenerated catalyst is that 649 ℃ (1200 °F) are to 816 ℃ (1500 °F), that dry gas or fluidizing agent propose for the present invention and be added with steam and (perhaps) water as heat sink material, the temperature of the upper reaches suspensoid that forms is suitable for being implemented in the catalytic cracking of the residual oil raw material of sending into through feeding unit 7 or 9 in the downstream.Therefore, material inlet device 5,7 and 9 uses together together with diluent inlet pipe 6,8 and 10, just can substantially change atomizing raw materials situation and dividing potential drop and as above-mentioned oily raw material and the duration of contact between dry gas-steam suspensoid granules of catalyst.In addition, add as the steam of heat sink material and (perhaps) water by dried lift gas with composition of the present invention, just can be in the temperature of the bottom of riser reactor adjusting regenerated catalyst.

In general, difference according to raw material composition and source, when with oily raw material when being in 704 ℃ (1300) catalyzer to 760 ℃ of (1400) temperature ranges and contacting, can be with residual oil raw material and catalyzer the duration of contact in riser tube be limited in 0.5～about 2 or 3 seconds scope in, thereby the temperature out scope that makes riser tube reaches 510 ℃ (950 °F) to 593 ℃ (1100 °F), more usually is not higher than 566 ℃ (1050 °F).In essence, riser reactor can be got desired any vertical height, just the height of this riser tube will with the catalyst regeneration device of adjoining, stripper plant and catalyst transport pipeline that this combine operations is essential are coordinated, as shown in the figure, the catalyst regeneration device of adjoining can adopt the single-stage regeneration operation, also can adopt multistage regenerative operation.

Stripping

The top of riser tube 2 is upward through a stripping zone 16, enters the top of a larger-diameter catalyst separation zone thereby form an annular stripping zone thus, and catalyst separation zone directly is communicated with said annular release district 16.Stripping gas, for example the suitable gas of steam or other is sent into the bottom of stripping zone through pipeline 17, makes it upwards flow through this stripping zone, and becomes adverse current with dirty granules of catalyst.

Regeneration

Catalyzer after the stripping is sent into catalyst regeneration device through pipeline 19 then, illustrated regenerating unit has catalyst regeneration bed 20 and 36 in order, catalyzer obtains regeneration in separated breeding blanket by combustion processes, thereby remove the carbon deposits that forms in the cracking process, the temperature that improves during burning does not surpass the high temperature of about 816 ℃ (1500), preferably temperature limit is fixed on about 649 ℃ (1200 °F) to the scope of 816 ℃ (1500), be more typically and be limited to 704 ℃ (1300 °F) to 760 ℃ (1400 °F).

Catalyst separating

Relate in riser tube system of the present invention one important aspect particularly about separate the method and apparatus of the suspensoid at upper reaches in the riser tube upper, open end.That is to say, will be by hydrocarbon steam, catalyzer, the suspensoid of lift gas and vapor composition is discharged from the riser tube upper, open end, speed should reach such speed during discharge, the momentum of promptly distributing to granules of catalyst is bigger than the momentum of distributing to vapour shape component, sets up a upflowing track therefrom, thereby granules of catalyst and vapour shape material are separated.This vapour shape substance mixture usually is called gaseous state (gasiform) material in prior art proposal, this vapour shape material feeds the discharge-channel of annular cup 11, the annular cup top is an opening, then by to around the expansion plumbing installation, the outer end of the outside expansion line that each is so all directly is communicated with cyclone separator 12.In cyclonic separator 12, steam is separated from the fine powder of catalyst entrainment, and the pipeline through being communicated with collection chamber 13 and product line road 14 obtains reclaiming then, sends into product fractionation and tripping device at last, does not show among the figure.The catalyst fines of separating in cyclonic separator 12 is discharged through dipleg, catalyst stripping and the regenerative operation flow process discussed below sending into then.

Catalyzer

Finish in the riser reaction zone that the conversion operation of hydrocarbon is estimated here to discuss, the key of conversion is to use the granules of catalyst of fluidized, and the granularity of granules of catalyst is greater than 10 * 10 ^-6Come (10 microns), general mean particle size is 60～100 * 10 ^-6Come to be less than about 85 * 10 and be more typically granularity in the scope of (60～100 microns) ^-6Come (85 microns).The composition of catalyzer preferably includes crystal aluminosilicate or crystalline zeolite, zeolite has used rare earth metal and (perhaps) ammonia to carry out ion-exchange, to obtain material with catalytic activity, dispersion of materials with catalytic activity is in fertile material, fertile material can have catalytic activity, also can not possess catalytic activity.The catalyzer that is particularly suitable for being used in operating process of the present invention is a kind of octahedra crystalline zeolite of rare earth ion exchange, this zeolite has the perforate of catalyst pore volume and parent size, these perforates will be collected the metallic impurity that gather a great deal of with (perhaps), simultaneously can also keep suitable catalyzer cracking activity and selectivity, discussed herein as the present invention.

Raw material

The oil raw material, the residual oil part in the crude oil that opening for feed 5 or 7 is sent into for example, can with steam and (perhaps) water, for example mix through the acid product water that pipeline 6 or 8 is sent into.On the other hand, if sent into from opening for feed 9 by raw material, then steam-water mixture can add through pipeline 10.Dried lift gas inlet duct 4 is equipped with in the bottom of riser tube 2, and the hot regenerated catalyst particle of the lift gas of sending into deliver to riser tube through pipeline 3 bottom forms the suspensoid at upper reaches.Dried lift gas can be sent into riser tube separately, also can send into the steam of sending here through pipeline 43 and (perhaps) water.

Except forming desired granules of catalyst concentration range for 16～44 kilograms every cubic metre the upper reaches suspensoid, several different effects also can be brought into play in the bottom of the qualification diameter parts of riser tube.That is to say, the dry gas that therein indicated here contains hydrogen except being used as lift gas, can also be used as the passivating material of foreign metal, as long as just can make Ni and V passivation to wherein adding the metal passivation compound.Can add antimony and make the nickel deposit passivation of gathering.But barium oxide becomes than the lower oxyde form in conjunction with the reduction passivation of hydrogen concentration, as long as provide its dystectic oxide compound or knot containing the adding titanium separately, alumina can reach with the rare earth metal that is rich in lanthanum.Therefore, before oily atomizing raw materials sprays into, the bottom of this riser tube is no matter make any purposes, the most substantially concerning inventive concept of the present invention, be, the applied composition that contains the product circulation dry gas of hydrogen should be such, promptly should in addition strict restriction to the content of three components more than the carbon atom in the dry gas, make its with will the cracked heavy oils contact before, can suppress these components deposit significant quantity on catalyzer coke.As what gone through here, the content that will contain in the dry gas of hydrogen the above component of three carbon atoms is restricted to and is lower than 10%, preferably be lower than 8%, be lower than 6% level and be more preferably, just can improve gasoline yield, reduce hydrogen yield, improve the productive rate of light cycle oil productive rate and reduction slurry oil and coke.Be unexpected and be unpredictable through these discoveries that obtain after experimental results show that.The one side that has more economic worth in the operation scheme of the present invention is to have used the refinery's product gas that is easy to obtain or the gas in other sources, and hydrogen content is 10～40 volume % from the gas that obtains like this and the dry gas that forms.

In special a kind of operation scheme of considering, the hydrogen that used dry labor thing gas contains in the cracking operating process is at least 15 volume %, the above hydrocarbon of three carbon atoms that contain is lower than 10 volume %, the water yield that is blended into wherein should be at catalyzer with before the atomizing residual oil of sending into the preheating that promotes dry gas-steam-catalyst suspension that operation forms contact, also be enough to this regenerated catalyst portion cooled off so that oily raw material at this moment transformation efficiency reach desired low-level.It is to carry out under riser tube pressure is higher than the condition of barometric point that the hydrocarbon of sending into is carried out fluid catalytic cracking, carries out catalysis among the present invention in riser tube, and cracked pressure is about 172 * 10 ³To 1137 * 10 ³Pascal's (about 10～150 pounds/English inch ², gauge pressure), still, the dividing potential drop of hydrocarbon materials can reduce widely because of the atomizing thinner material of lift gas-vapour mixture and oily raw material in the oily raw material after the atomizing.Therefore, the dividing potential drop scope of oily raw material can reach 27.6 to 172 * 10 ³Pascal, it is about 5～15 that the ratio range of catalyzer and oily raw material can reach, more preferably 6～12, so just make between the oily raw material of granules of catalyst and atomizing contact tightr.

Combustion unit among Fig. 8 is a kind of regeneration system rapidly of very special granules of catalyst, this system can effectively control temperature of combustion, thereby especially can granules of catalyst reduce to minimum degree because of hydrothermal and deactivated possibility in the process of deposits of coke with removing by burning, this also helps the catalyzed conversion of the higher component in the catalyzed conversion of gas oil and the residual oil that (perhaps) comprises vacuum residuum especially.

Now special reference catalyst regenerating unit with and application method, device has wherein carried out special arrangement, that is to say, the diameter of the chamber that gathers materials on its top is greater than the gather materials diameter of chamber of its underpart, separate mutually by being positioned at its intermediary regeneration gas distributing chamber 24 these 2 chambers that gather materials, top gathers materials the chamber by 40 supportings of ring baffle element, and this baffle element has gas channel 41.It is a plurality of that 24 abducent arm-type devices 25 are used for regeneration gas is imported the lower curtate of the catalyst bed 20 carrying out regenerative operation from the gas distribution chamber.Combustion-supporting gas during regeneration, for example air or the gas that contains oxygen in pipeline 22 with vapor mixing from pipeline 23, thereby oxygen concentration can be controlled at desired value, its content can be removed the required content of carbon-containing sediment greater than part from the granules of catalyst of sending into, also can be less than this content, temperature of combustion in the operating process can be limited in the desired scope thus, required regeneration combustion-supporting gas is sent into by collection chamber 24 and abducent arm-type element 25.This fs of catalyst regeneration comprises burning hydrocarbonaceous throw out, burning is at desired oxygen, carry out under the condition that carbonic acid gas and steam exist, the regeneration temperature of this moment be controlled in 593 ℃ (1100)～871 ℃ (1600) scope than low value for well, preferably be controlled at 649 ℃ (1200 °F) to the scope of 815 ℃ (1500), more generally be to be controlled at about 690 ℃ (1275)～760(1400 °F) scope in.

Partly remove carbonaceous material and carry out in catalyst bed 20, the condition of operation is to produce the product stack gas that is rich in carbon monoxide in this process, also comprises carbonic acid gas, sulphur, nitrogen and water vapor.So, the stack gas that is produced by by a group shown in the cyclonic separator among the figure 26 or organize cyclonic separator more, thereby remove the fine powder of catalyst entrainment, fine powder reclaims with the dipleg of settling then, the stack gas of Chan Shenging enters collection chamber 27 from cyclonic separator 26 then like this, after pipeline 28 therefrom reclaim.Industrially usually such stack gas that is rich in carbon monoxide is fed CO (carbon monoxide converter) boiler to produce process steam, do not express this CO (carbon monoxide converter) boiler among the figure.

Catalyzer after the partial regeneration is discharged from its bottom in catalyst bed 20 like this, dirty in then external catalyst cooling zone 29, carry out indirect heat exchange with plug-in type (bayonnet type) heat exchanger tube 30 therein, these heat exchanger tubes are that positioned vertical is in above-mentioned cooling zone basically.If oiler feed is sent into the distributing chamber that is positioned at water cooler 29 bottoms and is communicated with said heat exchanger tube 30 through pipeline 31, just can form high pressure steam, its pressure range about 3.1 * 10 ⁶Pascal's (450 pounds), this high pressure steam can obtain recycling after pipeline 34 outputs.Catalyzer part refrigerative temperature range in cooling room 29 is 28 ℃～111 ℃ (50 °F～200 °F), scope more commonly used is 55～83 ℃ (100～150 °F), cooling is after pipeline 35 is discharged and delivered to catalyst bed 36, and catalyst bed 36 is clamped among the second stage catalyst regeneration section 37.The vertical tubes 42 that catalyst bed 20 and 36 is communicated with can be used as the direct channel of catalyzer, just catalyzer can be sent into the bottom bed from the top bed without cooling in needs.But the main flow that catalyzer flows between two should be through supercooler 29, so that as required the temperature of catalyzer in the subsequent catalyst regeneration system rapidly is controlled.Temperature in second stage catalyst regeneration bed 36 should be limited in the scope of 649 ℃ (1200)～816 ℃ (1500), is more typically in the scope that is limited to 704 ℃ (1300)～760 ℃ (1400).The temperature of the regenerated catalyst in the fluidized-bed 36 of close phase can equal, and is higher than or is lower than the temperature of being kept in the dense fluidized catalyst bed 20 in the first step catalyst regeneration operation.With regard to an embodiment, can be equal to, or greater than to make the carbon residue perfect combustion on the partial regeneration catalyzer later and produce through pipeline 38 and through the amount that grid 39 is sent into the air of catalyst bed 36 or oxygen-containing gas and be rich in CO ₂The needed amount of flue gas product, the stack gas that is produced can contain also can not contain the oxygen that part does not consume.Preferably, closely knit stack gas of discharging does not mutually contain the CO that reaches combustion-supporting metering from the top of catalyst bed 36, to prevent that subsequent combustion takes place in stack gas.What produce in the catalyst regeneration process of the second stage is rich in CO ₂High-temperature flue gas product, enter the bottom of catalyst bed 20 after the opening 41 on the baffle plate 40 of flowing through, mixes with the regeneration gas of sending into through the arm-type element 25 of sparger then, provide heat thereby operate for first step catalyst regeneration.In the catalyst regeneration process of the second stage.In order the carbon residue content on the regenerated catalyst particles to be reduced to about 0.05 weight % or to reduce about 0.01 weight % and all stack gas products of combustion of obtaining are all flowed through the catalyst bed 20 in the first step catalyst regeneration process.As mentioned above, the regenerated catalyst that obtains is like this discharged from the top of catalyst bed 36, send into the bottom of riser tube 1 then through pipeline 3, to be used to promote operation and Hydrocarbon Content by Catalytic Cracking Operation flow process subsequently once more.

With regard to equipment arrangement mode disclosed in relevant Fig. 8 and that discuss, can consider to adopt vertical height to be approximately the riser reaction zone of 49 meters (about 160 English Foot), catalyst suspension is 18～31 meter per seconds (60～100 English Foot/second) by the velocity range of this reaction zone.With regard to employing speed is the specific embodiments of about 24.5 meter per seconds (80 English Foot/second), and the time that catalyst suspension is passed riser tube is about 2 seconds.In such operating process, initial dry gas-steam-the catalyst suspension that forms before the oil plant raw material with atomizing contact residence time of riser tube internal consumption for number/a second extremely up to 0.5 second, and hydrocarbon contacts contact residence time of being exhausted up to about 1 or 1.5 second with granules of catalyst in riser tube.The residence time of specified weak point is harmless to the inventive method, and uses the short residence time also quite favourable, owing to reduced any generation transition cracked possibility, just can keep the desired product selectivity that obtains like this.

Concerning the those of ordinary skill in the technology of the present invention field, it should be noted that, it is limitation of the present invention that the foregoing description and discussion thereof not should be understood to, and that is to say, can make various revisions and can not depart from scope of the present invention these embodiments.The top patent of mentioning, in the discussion process institute's quoted passage offer and bibliography only for reference.

Claims (31)

1, use the cracking catalyst that contains crystalline zeolite to realize the method for the catalytic cracking of oily raw material fraction in the crude oil in the zone of cracking of riser tube, it is improved one's methods and comprises:

A) adopt dry gas to form the humidity hydrocarbon that reaches a high temperature and transform the lifting suspensoid of the granules of catalyst of humidity as lift gas, the above material of three carbon atoms that this dry gas comprises the hydrogen of about at least 10 moles of % and is less than 10 volume %,

B) keeping said lift gas to close the contact between the granules of catalyst of suspension and limit its duration of contact is 0.01～2 second, at catalyzer with before the said oily raw material that will transform contacts, make the sedimentation of coke amount that is deposited on the catalyzer by said lift gas not surpass 0.20 weight %

C) under the invert point condition, allow the said catalyzer that is suspended in the dry gas contact, thereby improve the selectivity of cracking reaction gasoline and light cycle oil product with said oily raw material.

2, with the method for mink cell focus fraction in the crystalline zeolite catalyzer cracking crude oil that contains add up metallic impurity Ni and V, it is improved one's methods and comprises:

A) at first temperature is reached about at least 704 ℃ regenerated catalyst that contains metallic impurity and contact the suspensoid that reaches desired reduction temperature with formation temperature with the lift gas that comprises steam and water, said lift gas comprises refinery's recycle gas product, comprise hydrogen in this recycle gas product, and the above hydrocarbon of three carbon atoms that contain in the lift gas is less than 10 volume %

B) at catalyzer with before oily raw material contacts, making duration of contact between said lift gas-vapour mixture and the said catalyzer that contains metallic impurity is enough to make said foreign metal reduction,

C) in said lift gas-catalyst suspension, provide one or more metallic compounds, thereby make said Ni of adding up and the passivation of V foreign metal that is present on the said catalyzer,

D) with the said mink cell focus fraction of said dry gas-steam-catalyst suspension cracking,

E) separate the product that catalytic cracking obtains, this catalytic cracking process has improved the selectivity of gasoline and light cycle oil productive rate,

F) said gasoline and turning oil are separated from said catalyzer.

3, according to claim 2 described methods, wherein, the mink cell focus fraction comprises decompression gas oil.

4, according to claim 2 described methods, wherein, the mink cell focus fraction is the residual oil part in the crude oil, and its boiling point is higher than 343 ℃ (650 °F).

5, according to claim 2 described methods, wherein, said refinery's circulation dry gas product is the gas-phase product of catalytic cracking process.

6, according to claim 2 described methods, wherein, said refinery recycle gas product is the vapour shape product in the sweetening process, comprising hydrogen sulfide.

7, according to claim 2 described methods, wherein, at catalyzer with before the heavy oil feed of the high atomisation state of sending into contacts, lift gas-vapour mixture keeps in touch with said high-temperature regenerated catalyst in the initial part of the zone of cracking of riser tube, and the time of its contact is for counting/one second.

8, according to claim 2 described methods, wherein, be number/one second in 0.1～0.5 second scope the duration of contact of lift gas-vapour mixture and said high-temperature regenerated catalyst.

9, according to claim 2 described methods, wherein, the metals content impurity scope that adds up that catalyzer comprises is 1000～20000ppmNi+V.

10,, wherein, promote the amounts of hydrogen that contains in the gas, and the residual coke content that temperature reaches in the regenerated catalyst of 704 ℃ (1300) at least is not more than about 0.05 weight % greater than 10 volume % according to claim 2 described methods.

11, according to claim 10 described methods, wherein, when catalyzer contacted with the oily raw material of sending into from downstream part, riser cracking district, the coke content that is deposited on the catalyzer in the formed suspensoid of being made up of lift gas-steam and regenerated catalyst was lower than 0.2 weight %.

12, according to claim 11 described methods, wherein, when catalyzer contacted with the oily raw material of sending into, the coke content that is deposited in the suspensoid of being made up of lift gas-steam and regenerated catalyst on the catalyzer was limited in the scope of 0.1～about 0.15 weight %.

13, according to claim 12 described methods, wherein, the temperature of catalyzer is reduced to such degree by lift gas-vapour mixture, is enough to promptly make that the temperature range in the riser tube exit reaches 510～560 ℃ (950～1050 °F) after the oily feedstock conversion sent into.

14, according to claim 2 described methods, wherein, with antimony, titanium, chromium, zirconium be rich in one or more metallic impurity passivation that accumulation is got up in the rare earth element of lanthanum.

15, to transform available Lan Shi carbon range be 0～6 oily raw material comprises the method for the liquid fuel product of gasoline and light cycle oil with production with the crystalline zeolite catalyst that contains add up metallic nickel and vanadium, and it is improved one's methods and comprises:

A) the said catalyzer of regenerating makes its residual coke content be lower than about 0.05 weight %, therefrom said catalyzer is heated to the temperature of about at least 704 ℃ (1300),

B) part is cooled off said regenerated catalyst, method of cooling is that it is contacted with the lift gas that is rich in hydrogen, the content of three above hydrocarbon of carbon atom is lower than 10 volume % in the lift gas, and blending has steam and water, thereby make residual coke content on this regenerated catalyst remain below the level of 0.2 weight %, and metallic impurity make its reduction and passivation with metal additive

C) the part cooling zone of cracking of regenerated catalyst in riser tube afterwards contacted with the raw material that contains gas oil at least, should improve the temperature condition of contact and duration of contact selectivity gasoline and light cycle oil productive rate.

16, according to claim 15 described methods, wherein, the regenerative operation of catalyzer is finished in two-stage successive regeneration flow process, the temperature condition of regeneration flow process remains on 704 ℃～760 ℃ (1300～1400 °F), should be enough to make the temperature range of hydrocarbon product in the exit of riser tube of catalyzer conversion to reach 510～560 ℃ (950～1050 °F) with said lift gas-steam-water mixture to the cooling operation of regenerated catalyst.

17, with the method for crystalline zeolite cracking catalyst catalytic conversion hydrocarbon oil crude material, it is improved one's methods and comprises:

A) form fresh hot regenerated catalyst suspensoid with the dry gas that is rich in hydrogen, the above hydrocarbon gas of three carbon atoms that the dry gas of this moment contains is lower than 10 volume %, and promptly define the coke content that is deposited on the catalyzer thus and can not surpass about 0.2 weight %,

B) then the said suspensoid of being made up of dry gas and catalyzer is being contacted with oily raw material more than 343 ℃ (650) under the said oily raw material hydrocarbon conversion condition, the available Lan Shi carbon range of this oily raw material is 0～8, and said hydrocarbon conversion condition can form gaseous product in the temperature range of 482～593 ℃ (900～1100).

18, the available Lan Shi carbon range of crystalline zeolite cracking catalyst catalyzed conversion that adds vanadium for 1000ppm nickel at least with the metallic impurity that comprise is the method for 0～8 oily raw material, and it is improved one's methods and comprises:

A) from the interior catalyst regeneration zones reclaiming catalyzer of the temperature range of 649～816 ℃ (1200～1500),

B) regenerated catalyst that said recovery is obtained mixes to form the mix suspending body at its upper reaches with steam and the dry gas that is rich in hydrogen, mainly comprise three carbon atoms and low boiling hydrocarbon in the said dry gas, its consumption should satisfy the requirement that forms suspensoid, the temperature of the suspensoid that forms reaches desired hydrocarbon invert point

C) the oily raw material that said needs is changed into the lower boiling product contacts with said suspensoid, and the time of contact should limit like this, can form the gaseous state converted product in the temperature range of 482～593 ℃ (900～1100).

19, be higher than 343(650 °F with crystalline zeolite cracking catalyst cracking crude oil mid-boiling point) the method for oil plant fraction, it is improved one's methods and comprises:

A) under the temperature that is higher than 649 ℃ (1200) and counting in time of/one second, form the high temperature suspensoid with the dry gas that is rich in hydrogen with regenerated catalyst, the coke that is deposited in the suspensoid on the catalyzer is limited in the scope that is no more than 0.2 weight %

B) suspensoid with said such formation contacts with said oily raw material, and the consumption of oily raw material should be able to make hydrocarbon gas converted product temperature range reach 482～566 ℃ (900～1050 °F);

C) reclaim the said hydrocarbon converted product that the selectivity of gasoline and light cycle oil productive rate has been improved.

20, the method for the residual oil raw material of cracking carbon metal, the boiling point of the hydrocarbon component that contains in this residual oil raw material are not less than 552 ℃ (1025 °F), and the nickel that contains adds vanadium and is higher than 10ppm, and the Lan Shi carbon value that contains is at least 4, and it is improved one's methods and comprises:

A) the said residual oil raw material that will be preheating to 177～371 ℃ of (350～700) temperature ranges is that the regeneration cracking catalyst of 649～816 ℃ (1200～1500) contacts in the zone of cracking of riser tube with the initial temperature scope, be 1～4 second its duration of contact, thereby obtain residual oil and transform the hydrocarbon gas product that produces

B) feature of said cracking catalyst is, metal content wherein is higher than 1000ppm nickel and adds vanadium, be lower than 0.2 weight % with wherein carbon content before said residual oil raw material contacts, and the content of accelerating crystallization zeolite wherein is in the scope of 5～40 weight %

C) the hydrocarbon gas product that adopts the trajectory separating process will transform gained separates with catalyzer,

D) catalyzer that obtains after stripping separates to be removing the liquid state and the gaseous substance of deentrainment,

E) catalyzer behind the stripping is sent into the first step in the two-stage catalyst regeneration operating process, remove the carbonaceous material on the catalyzer of being deposited on of 20～90 weight % with combustion method at this, the temperature of catalyzer is brought up in the scope of 649～816 ℃ (1200～1500) thus

F) catalyzer of partial regeneration is sent into separated second stage catalyst regeneration zones to remove the residual coke on the catalyzer, make its content be low to moderate at least 0.05 weight % or lower, its operational condition is to fix on the temperature limit of catalyzer in the scope of 649～816 ℃ (1200～1500)

G) catalyzer that will regenerate the like this bottom of sending into the riser cracking district is gone to contact with the dry gas that is rich in hydrogen, thereby form by the two upper reaches suspensoid of forming, at suspensoid with before said residual oil raw material contacts, in up to about 1 second residence time, allow and flow through said riser cracking district on the suspensoid of said such formation

H) with the said catalyzer that has only the described feature in above-mentioned (b) lining at the said residual oil raw material of said zone of cracking catalyzed conversion, thereby form the gaseous state converted product, its temperature range is 482～566 ℃ (900～1050 °F).

21, according to claim 20 described methods, wherein, said gaseous state converted product is separated to reclaim liquid product from gaseous product, and then said gaseous product separated, thereby reclaim the dry gas product that obtains being rich in hydrogen, the content of the above hydrocarbon of three carbon atoms is lower than about 10 volume % in this dry gas product, and the dry gas product circulation of being rich in hydrogen that more said separation is obtained is at last delivered to said riser cracking district and formed said suspensoid with regenerated catalyst particles.

22,, wherein, will contain water or water-free steam and send into the riser cracking district sends into regenerated catalyst wherein with adjustment temperature with the said dry gas that is rich in hydrogen according to claim 20 described methods.

23, according to claim 20 described methods, wherein, said residual oil raw material comprises the Ni+V of 5～300ppm, and said catalyzer comprises the Ni+V in 1000～20000ppm scope.

24, conversion contains the method for the oily raw material of carbon metal, contain 343 ℃ (650) above fraction in the crude oil in this oily raw material, and the feature of this oily raw material is that wherein Lan Shi carbon range is 0～8 and contains foreign metal nickel and vanadium, the cracking catalyst of the zone of cracking of this oily raw material in riser tube with heat contacted, at least the nickel that contains 1000ppm in the cracking catalyst adds vanadium, be less than 3 seconds the duration of contact of hydrocarbon in contact process, thereby in the temperature range of 482～593 ℃ (900～1100), form the vaporous hydrocarbon converted product that catalytic cracking obtains and in cracking process, have carbonaceous settling to be deposited on the said cracking catalyst, when said hydrocarbon product is discharged from said riser cracking district, with the isolating method of trajectory cracking catalyst is separated from vaporous hydrocarbon product with its independent recycling, before regenerating, the above-mentioned catalyzer of separating is carried out stripping to remove volatile hydrocarbon, the regeneration of catalyzer is in the limiting temperature scope that is no more than about 760 ℃ (1400) and carries out with the burning carbonaceous settling of oxygen-containing gas in catalyst regeneration zones in order, then the hot regenerated catalyst circulation is delivered to said riser cracking district and gone to contact the purpose that transforms to realize with the oily raw material of sending into, it is improved one's methods and comprises:

A) form the suspensoid of said hot regenerated catalyst with steam and dry gas, contain the hydrogen that is lower than 40 volume % in the said dry gas and be lower than the above hydrocarbon of three carbon atoms of 10 volume %,

B) in the regular hour, allow the initial part of suspensoid upper reaches by hydrocarbon zone of transformation in the riser tube of said such formation under the situation that needs cracked oil raw material not sending into, in the time at such upper reaches, make the metal oxide reduction that forms in the regeneration of catalyzer and the passivating process with the interpolation material that is suitable for this operation

C) send into the oily raw material of the atomizing form that need to transform in the downstream part in said riser cracking district, it is contacted with the suspensoid that forms in the said said process.

25, according to claim 24 described methods, wherein, said dry gas comprises the hydrogen of at least 10 volume %.

26, according to claim 24 described methods, wherein, said dry gas is included in the mink cell focus aromatic hydrocarbons that will contain sulphur compound and carries out resulting dry gas product in the hydrotreated process.

27, according to claim 24 described methods, wherein, with said catalyst regeneration, make its residual coke that contains be no more than 0.05 weight %, and catalyzer is being no more than 0.2 weight % with its coke content when said oily raw material contacts in the new suspensoid that forms.

28, according to claim 27 described methods, wherein, the coke content on the regenerated catalyst is lower than 0.05 weight %.

29, according to claim 24 described methods, wherein, the oily raw material of sending into is decompression gas oil.

30, according to claim 24 described methods, wherein, the oily raw material of sending into is the residual oil fraction in the crude oil, is not less than the composition of 552 ℃ (1025) comprising boiling point.

31, according to claim 24 described methods, wherein, the nickel on the catalyzer and the accumulation amount of foreign matter of vanadium in the scope of 1000～20000ppm and the catalyst member ground of this containing metal impurity with metal content lower and active higher catalyzer replaces.

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