CN103154203B

CN103154203B - The integration method of steam cracking

Info

Publication number: CN103154203B
Application number: CN201180033756.0A
Authority: CN
Inventors: S·M·戴维斯; R·C·斯特尔; 刘俊贤; S·H·布朗; P·F·柯森科思恩; A·R·迪尼克兰托尼奥; J·J·瓦尔德洛普
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2010-07-09
Filing date: 2011-06-09
Publication date: 2015-11-25
Anticipated expiration: 2031-06-09
Also published as: SG186124A1; WO2012005861A1; CN103154203A

Abstract

The present invention relates to the method and the alkene that comprise the hydrocarbon feed of vacuum residuum for cracking, comprising: (a) makes vacuum residuum at thermal conversion reaction device (such as delay coking device, fluid coker, Flexicoker ^tM, viscosity breaking and shortening viscosity breaking) in carry out the first thermal transition, wherein at least the vacuum residuum of 30wt% is converted into the material of boiling under 1050 ℉ (566 DEG C); B the residual oil of described thermal transition is incorporated into gas/liquid separation by (), described separator is integrated into steam cracker furnace, to form gas phase and liquid phase; C described gas phase is sent in the radiant-type furnace of described steam cracker furnace by (); (d) from the material leaving radiant-type furnace, reclaim the alkene (weight of total hydrocarbon material based on leaving radiant-type furnace) of at least 30wt%.

Description

The integration method of steam cracking

Contriver: SM Davis, RC Si Teer, Liu Junxian, SH Blang, Ke PF Sen Kesien, AR Di Nike Lantonio, and JJ Grindelwald Lip river is general

Priority application

The application advocates the USSN12/833 that on July 9th, 2010 submits to, and the EP submitted on September 17th, 556 and 2010 applies for the right of priority of No.10177302.6, and its disclosure is incorporated to by reference with its entirety.

Quoting of related application

The application relates to the application USSN12/833 that simultaneously there is submission, 485 (lawyer's Docket Number 2010EM008) (submission on July 9th, 2010).The application also relates to the USSN12/692 of submission on January 22nd, 2010,222 (lawyer's Docket Number 20/10EM009).

Technical field

The present invention relates in steam cracker furnace or pyrolysis oven by crude oil or the method preparing alkene containing the crude oil fractions of residual oil.

Background technology

The thermally splitting of hydrocarbon is that one is widely used in the petrochemical process producing alkene (such as ethene, propylene, butylene, divinyl) and aromatic hydrocarbon (such as benzene, toluene and dimethylbenzene).These each is because itself being all valuable industrial goods.Such as, described alkene can oligomeric (such as, form lubricant base), polymerization (such as, form polyethylene, polypropylene and other plastics), and/or functionalization (such as, forming acid, alcohol, aldehyde etc.), all these have well-known intermediate and/or end-use.

Steam cracking (also referred to as pyrolysis), already for various hydrocarbon feed is cracked into alkene, preferred light olefin is ethene, propylene and butylene such as.Usually, the raw material for steam cracking is such as petroleum naphtha, gas oil or other is containing the whole crude cut of residual oil, its can such as by distillation or otherwise fractionation whole crude obtain.Conventional steam cracking uses the steam cracker furnace with two major sections: convection zone and radiation section.Described hydrocarbon feed typically enters the convection zone (lightweight material except entering as steam) of this stove as liquid, wherein this hydrocarbon feed is usually by being heated with the hot flue gases indirect contact from radiation section with by directly contacting with steam and gasify.Then, raw material (with the optional steam) mixture of gasification is sent to the radiation section that cracking occurs.Usually, the mixture of gasification is incorporated into radiation section by cross manifold, wherein the mixture of this gasification is heated to harsh hydrocarbon cracking temperature rapidly under the pressure of usual about 10 to about 50psig (69-345kPa) scope, the scope of such as about 1450 ℉ (788 DEG C) to about 1650 ℉ (900 DEG C), with the thorough thermally splitting of stream of supplying raw materials.The product comprising the gained of alkene leaves steam cracker furnace to carry out further Downstream processing.

After cracking, the effluent from pyrolysis oven comprises multiple hydrocarbon gas, such as, and saturated, cholesterol and polyunsaturated hydrocarbon, and can be aliphatics and/or aromatic hydrocarbon, and the molecular hydrogen of significant quantity.The product of cracking such as is further processed to produce the individual stream of multiple highly purified separation subsequently as equipment product, i.e. hydrogen, light olefin ethene, propylene, butylene and aromatic compound and other product such as pressure gasoline in olefin production plant.

Along with the exhaustion to the increase of light olefin widespread demand and the operability of favourable crude oil origin, therefore be necessary to utilize the crude oil of more heavy (namely, there are those of residual oil more at high proportion), it requires that the capital investment that increases is with the by product of processing and process refining.Wish very much to adopt more low cost, more heavy crude oil and more effectively produce the method for the Product mix of more favourable light olefin.But the process for steam cracking of known conventional is easy to by the raw material serious scale containing the even residual oil of small concentration, and described residual oil exists usually in inferior quality heavy feedstocks.Therefore, most of steam cracker furnace is restricted to the processing of more high quality raw material, and described more high quality raw material has substantially made all residue oil fractions remove in other refining process.These extra processes add the cost of holistic approach.Similarly, residue oil fraction remove the total transformation efficiency reducing refining process because most of residue oil fraction and low-value fuel oil mixes, instead of change into the material of more high value.

The patent application No.2007/0090018 of U.S. Patent Publication, is incorporated to by reference herein, discloses the integration of hydrotreatment and steam cracking.Crude oil or its charging containing residue oil fraction hydrotreatment and pass into steam cracker to obtain olefin product harshly will be comprised.

Describe the cracking of heavy hydrocarbon charge in fluid coker.Such as, U.S. Patent No. 3,671,424, is incorporated to herein by reference, discloses a kind of two-stage fluidized coking process, and wherein the first step is the transfer line of short contacting time and the second stage is transfer line or fluidized-bed.

The use of the separating tank integrated with steam cracker furnace has developed into the important extension of this platform to allow to process the raw material such as long residuum of more heavy.Described separating tank provides a kind of means with from being separated the heaviest component in cracked gas oil molecule and preventing the heaviest cut fouling in steam cracker furnace comprising pitch type molecule.Unfortunately, by using this method, most of heavy vacuum residual oil molecule (its due to lower cost be favourable as raw material), still in the liquid phase and do not transform in the radiation section of steam cracker furnace.

Other important patent comprises US7,097,758; US7,138,047; US7,193,123; US3,487,006; US3,617,493; US4,257,871; US4,065,379; US4,180,453; US4,210,520; US3,898,299; US5,024,751; US5,413,702; US6,210,561; US7,220,887; US2007/023845; WO01/66672; WO2007/117920; US6,632,351; US4,975,181; WO2009/025640;

US2007/0090018 and WO2007/117919.Other important document comprises: " Tutorial:DelayedCokingFundamentals. " P.J.Ellis and C.A.Paul, article 29a, TopicalConferenceonRefineryProcessing, 1998GreatLakesCarbonCorporation (it can be downloaded from http://www.coking.com/DECOKTUT.pdf).

Still exist in this area economically process heavy containing residual oil charging so that produce alkene,

The demand of aromatic hydrocarbons and the new tool of other valuable petrochemicals and the method for improvement.Similarly, still exist in this area and residual oil is upgraded to demand that is more useful and/or more compositions useful.

The invention discloses a kind of method of being produced chemical preparations in the following manner by heavy feed stock,

Wherein the vacuum residuum of signal portion is converted into the molecule of more lightweight, described lighter molecule easierly can gasify and is subsequently converted to fuels and chemicals in separating tank.

Summary of the invention

The present invention relates to the method that cracking comprises the hydrocarbon feed of residual oil, the method comprises:

A hydrocarbon feed containing vacuum residuum is sent to the first thermal transition district by (), wherein by described heating raw materials to the temperature being less than 649 DEG C (1200 ℉), wherein at least the vacuum residuum of 30wt% is converted into the material seethed with excitement below at 566 DEG C (1050 ℉);

B the residual oil of described thermal transition is incorporated into form gas phase and liquid phase in gas/liquid separation (such as separating tank) by (), described separator is connected with steam cracker furnace fluid (such as, being incorporated into steam cracker furnace);

C described gas phase is sent to the radiant-type furnace in described steam cracker furnace by (); With

D () is by the alkene (weight of total hydrocarbon material based on leaving radiant-type furnace) of the salvage material leaving radiant-type furnace at least 30wt%.

In another embodiment, the present invention relates to the method for the hydrocarbon feed comprising residual oil for cracking, the method comprises:

A () heat packs is containing the hydrocarbon feed of residual oil;

B the hydrocarbon feed of described heating is sent to gas/liquid separation (such as separating tank) by ();

C hydrocarbon feed that () heats described in flash distillation in described separator is to form gas phase and the liquid phase comprising described residual oil;

D () to operate from comprising being sent at least partially of the liquid phase of residual oil described in described separator below at 649 DEG C (1200 ℉) and optionally to comprise the thermal conversion reaction device of coke granule;

E the liquid phase comprising residual oil of described thermal transition is sent to gas/liquid separation (such as separating tank) to form the second gas phase and second liquid phase by (), described separator is connected with steam cracker furnace fluid (such as, being incorporated into steam cracker furnace);

F described second gas phase is sent to the radiant-type furnace in described steam cracker furnace by (); With

G () is by the alkene (weight of total hydrocarbon material based on leaving radiant-type furnace) of the salvage material leaving radiant-type furnace at least 30wt%.

In another embodiment, the liquid phase leaving the first gas/liquid separation is further heated the temperature to such as 1000-1200 ℉ (538-649 DEG C), usually in the lower coil pipe of the convection zone of steam cracker, the material of usual part heating is usually by viscosity breaking, thereafter the material of water (such as steam) quenching viscosity breaking in gasification reaction is used, the viscosity breaking material of described gasification is sent to the second gas/liquid separation subsequently, wherein the material separation of viscosity breaking is become liquid and gas.Subsequently gas phase is incorporated into steam cracker (at convection zone or at radiation section) and wherein at least the alkene of 30wt% reclaim from the material leaving radiant-type furnace (weight of total hydrocarbon material based on leaving radiant-type furnace).

Favourable, initial hydrocarbon feedstock usually comprise between 10wt% and 50wt% at 566 DEG C ⁺the residual oil of boiling, preferably about 20-40wt%, and method described herein enables this residual oil of height ratio be converted into chemical.

In preferred embodiments, the liquid comprising residual oil from the second gas/liquid separation is not processed further with production of chemicals.Replace, this material be preferably used as the blending stock that adds oil fuel or for further refining processing to produce fuel.

In preferred embodiments, the present invention relates to the method for the hydrocarbon feed comprising vacuum residuum for cracking, comprising:

A the vacuum residuum of at least 10wt%, containing the hydrocarbon feed of at least 1wt% vacuum residuum, based on the weight of hydrocarbon feed, and is converted into the material seethed with excitement 566 DEG C below by () heat packs;

B the hydrocarbon feed of described heating is sent to gas/liquid separation (preferably by the liquid bottom heat phase from gas/liquid separation to the temperature of 593-649 DEG C) by ();

(d) by from described separator at least partially described in comprise residual oil liquid phase be sent to the first thermal transition district and (preferably comprise coke granule, preferred described district has coke granule/fresh feed ratio (wt/wt) (preferably at least 3:1 of at least 1:1, preferred at least 5:1, or from 1:1 to 50:1, preferably from 3:1 to 30:1), based on recycle coke solid and the weight of fresh feed entering described district), to comprise the liquid phase of residual oil described in thermal transition at least partially;

E the liquid phase of described thermal transition is sent to gas/liquid separation by (), to form the second gas phase and second liquid phase, described separator is connected with steam cracker furnace fluid;

F described second gas phase is sent to described steam cracker furnace with thermal transition described second gas phase (or the second gas phase can be used as fuel or blending stock) at least partially by (); With

(g) from leave described steam cracker furnace radiant-type furnace material reclaim the alkene (weight of total hydrocarbon material based on leaving radiant-type furnace) of at least 30wt%.

Brief Description Of Drawings

In the following figure, similar equipment and/or the same numeral of method steps are determined.

Fig. 1 is the schema of an embodiment of the inventive method.

Fig. 2 is the schema of an embodiment of the inventive method.

Fig. 3 is the schema of an embodiment of the inventive method.

Fig. 4 is the schema of an embodiment of the inventive method.

Detailed Description Of The Invention

The present invention relates to heavy feedstocks steam cracker and thermal transition unit (such as, delay coking device, fluid coker, the Flexicoker of the vacuum residuum gas/liquid separation (such as, separating tank) comprising integration ^tM, visbreaker, shortening visbreaker) comprehensive, wherein vacuum residuum is converted into the component being suitable for steam cracking of more lightweight.(" being suitable for steam cracking " refer to can the material of cracking in steam cracker).By closely integrating two kinds of conversion processes, the heavy feedstocks of more wide region can be changed into the chemical of high value by total process effectively, makes fouling minimize simultaneously.For the purposes of the present invention, steam cracker furnace (also referred to as " steam cracker ") is the pyrolysis oven with two major sections or stove: convection zone and radiation section, wherein hydrocarbon feed enters the convection zone of the stove of lower harshness using liquid (lightweight material except entering as gas), and wherein usual by indirect contact from the high-temperature gas heating of radiation section and gasified raw material, and optionally raw material to be contacted with steam.Subsequently, the raw material of gasification and vapour mixture are sent in radiation section, wherein under the pressure of usual about 10 to about 50psig, (69 to 345kPa-gauge pressure) is rapidly heated to harsh hydrocarbon cracking temperature, such as in the scope of about 1450 ℉ (788 DEG C) to about 1650 ℉ (900 DEG C), with the thorough thermally splitting of stream of supplying raw materials.The product obtained generally includes alkene, aromatic hydrocarbons and diolefine.

Residual oil used herein refers to the complex mixture of heavy crude compound, otherwise known in the art be Residual oil (residuum) or residue (residual).Nominally long residuum is the bottoms generated in air distillation when the terminal of the heaviest distillage is 650 ℉ (343 DEG C), and is called as 650 ℉ ⁺(343 DEG C ⁺) residual oil.Nominally vacuum residuum is when final product of distillation is 1050 ℉ (566 DEG C) under reduced pressure from the bottoms of tower, and is called as 1050 ℉ ⁺(566 DEG C ⁺) residual oil.(term " nominally " this refers to rational expert and may not agree to for these terms point of contact really, but may no more than +/-50 ℉ or +/-100 ℉ at most).This 1050 ℉ ⁺(566 DEG C ⁺) part comprises bituminous matter, it is considered to traditionally for steam cracker is problematic, causes serious fouling and potential corrosion of equipment or erosion.Except as otherwise noted, term used herein " residual oil " refers to 650 ℉ ⁺(343 DEG C ⁺) residual oil and 1050 ℉ ⁺(566 DEG C ⁺) residual oil; Note 650 ℉ ⁺residual oil comprises 1050 ℉ ⁺residual oil.According to the present invention, gasified 650 ℉ at least partially ⁺residual oil, until at least 1050 ℉ ⁺boiling point fraction, such as when with steam in conjunction with time, and/or when pressure reduces or in decomposition tank at steam cracker during flash distillation.Term " comprises the hydrocarbon feed of vacuum residuum ", " comprising the hydrocarbon feed of long residuum ", " comprising the hydrocarbon feed of residual oil " etc. refer to weight based on hydrocarbon feed, (preferably at least 1wt% is there is in the residual oil determined with at least 0.1wt%, preferred at least 10wt%, preferably at least 15wt%, preferably at least 20wt%).

Term " flash tank ", " flash distillation pot ", " separating tank " are used interchangeably in this article with " being separated pot "; They are known in the art, are commonly referred to as the container or the system (" gas/liquid separation ") that go out liquid phase from gas phase separation.Term " flash distillation " is commonly referred to as by the material in reduction pressure and/or increase temperature realization container at least partially by the phase transformation of liquid phase to gas phase.The separating tank integrated is the gas/liquid separation be connected with steam cracker fluid.Particularly, the separating tank of described integration and the convection zone fluid communication of steam cracker, its Raw is heated (optionally with overheated vapor mixing) and be sent in the described separating tank operated as gas/liquid separation, thereafter in the future the gas of self-separation tank turns back to described steam cracker, preferably to convection zone or radiation section or the two.Adding of steam helps flash separation further by reducing hydrocarbon partial pressure, helps 750 ℉ ⁺(399 DEG C ⁺) to 1050 ℉ ⁺(566 DEG C ⁺) (preferably even most 1100 ℉ ⁺(593 DEG C ⁺)) conversion of residue oil fraction and gasification, and prevent fouling.

Preferred flash tank or gas/liquid separating device and their integration with pyrolysis unit previously at United States Patent(USP) Nos. 7,090,765,7,097,758, and 7,138, description in 047, it is incorporated into herein by reference.For the purposes of the present invention, another kind of effective equipment as flash tank is described in U.S. Patent No. 6 as " gas/liquid separation ", 632, in 351.

Described gas/liquid separation those parts cause coker feedstock material to remain on liquid temperature and pressure under operate, operate at temperature preferably between about 375 to 525 DEG C, preferred 400-500 DEG C, preferably by 800 ℉ (about 425 DEG C) and about 870 ℉ (about 465 DEG C), but be usually no more than about 900 ℉ (about 482 DEG C).

According to the present invention, comprise the raw material that the crude oil of residual oil or its cut are applied steam cracker furnace.The charging of suitable more low value can comprise the crude oil of more heavy usually, and the crude oil of described more heavy is defined as due to high 650 ℉ ⁺(343 DEG C ⁺) residual oil concentration, high-sulfur, high total acid value (TAN), high naphthenic hydrocarbon, high aromatic hydrocarbons, and/or the result of low hydrogen richness those there is the hydrocarbon feed of low api gravity.

As used herein crude oil refers to the whole crude when it is produced by well head, production site facility, traffic facilities or other initial fields treatment facility, optionally comprise by the step of desalination, process, and/or other can be necessary to make its conventional distil-lation for refinery be the crude oil of acceptable step processing.Assuming that as used herein crude oil comprises residual oil.

Crude oil fractions is obtained by refinery pipe still usually.Although obtaining crude oil fractions any by refinery pipe still and can be used for the present invention, is still comprise all or part of original 1050 ℉ existed in the whole crude that obtained by well head by significant advantage provided by the invention ⁺(566 DEG C ⁺) crude oil of residual oil or crude oil fractions can be used as the charging of steam cracker.In one embodiment, enter the crude oil of native system or other raw material and can comprise 1050 ℉ at least about 1wt% ⁺(566 DEG C ⁺) residual oil, preferably at least about 1050 ℉ of 5wt% ⁺(566 DEG C ⁺) residual oil, and more preferably at least about 1050 ℉ of 10wt% ⁺(566 DEG C ⁺) residual oil, be up to 1050 ℉ of about 50wt% ⁺(566 DEG C ⁺) residual oil.

Usual residual oil comprises the naphthenic acid (measure according to TAN according to ASTMD-664, TAN refers to the total acid value represented with milligram (" mg ") KOH every gram (" g ") sample) of a high proportion of undesirable impurity such as metal, sulphur and nitrogen and high molecular (C12+).Still, another advantage of the present invention is that the charging of being rich in one or more these impurity can easily be processed.In some embodiments, the present invention can have 566 DEG C of one or more (preferably two kinds, three kinds, four kinds, five kinds, six kinds or seven kinds) following character ⁺residual oil is put into practice: 1) based on 566 DEG C ⁺the weight of residual oil, Ni of 50ppm or more, or 100ppm or more, or 125ppm or more; And/or 2) based on 566 DEG C ⁺the weight of residual oil, 200ppm vanadium or more, or 500ppm or more, or 900ppm or more; And/or 3) based on 566 DEG C ⁺the weight of residual oil, sulphur of 4wt% or more, or 5wt% or more, or 6wt% or more; And/or 4) TAN of at least 0.1, or at least 0.3, or from about 0.1 to about 20, about 0.3 to about 10, or about 0.4 to about 5; And/or 5) 19 or less api gravity (ASTMD6822,15.5 DEG C); And/or 6) at least 0.04 gram of C ₅the C of bituminous matter every gram residual oil ₅asphalt content (" C ₅bituminous matter " refer to bituminous matter insoluble in pentane, as measured by ASTM method D2007); And/or 7) kinematic viscosity (as measured by ASTMD445) of at least 10cSt at 37.8 DEG C.It can be 566 DEG C that are obtained by crude oil at example residual oil used herein ⁺residual oil, described crude oil includes but not limited to the crude oil from following world region: United States Gulf is littoral, Southern California, Alaska north slope, Canada's Tar sands, Transport Model for Alberta area, Gulfian Campeche, Argentina Sheng Haoerhe basin, Brazil Sang Tuosi and Kan Bosi basin, Egyptian the Gulf of Suez, Chad, U.K. North Sea, Angola coastal waters, China Bohai Sea Gulf, Xinjiang, China Kelamayi, Iraq's Zagros, Kazakhstan the Caspian Sea, Nigeria coastal waters, the Madagascar northwestward, Oman, Holland Schoonebek, the Su Liya state of Venezuela, the Su Mendala of Malaysia and Indonesia.Residual oil useful in addition herein comprises by US7,678, the crude oil described with " disadvantageous " in 264 obtain 566 ⁺dEG C ⁺residual oil, is incorporated to herein by reference.

In preferred embodiments, wherein charging comprises 1050 ℉ comprising appreciable amount ⁺(566 DEG C ⁺) crude oil of residual oil or long residuum, such as, 1050 ℉ of 10wt% or more ⁺(566 DEG C ⁺) residual oil, or 1050 ℉ of 20wt% or more ⁺(566 DEG C ⁺) residual oil, or 1050 ℉ of 30wt% or more ⁺(566 DEG C ⁺) residual oil, 1050 ℉ of 40wt% or more ⁺(566 DEG C ⁺) residual oil, or even up to 1050 ℉ of 50wt% or more ⁺(566 DEG C ⁺) residual oil, make the charging comprising residual oil first be sent to the steam cracker furnace of the separating tank with integration.

Subsequently, the bottom material from the first separating tank is made to be sent to thermal transition unit, such as delay coking device, fluid coker, Flexicoker ^tM, visbreaker, or shortening visbreaker, wherein heat bottom material and at least the vacuum residuum of 30wt% (weight based on charging) is converted into 1050 ℉ ^-(566 DEG C ^-) fraction.As used herein 1050 ℉ ^-(566 DEG C ^-) fraction is defined as usually 1050 ^f-(566 DEG C ^-) hydrocarbon that seethes with excitement below.The residual oil of thermal transition is incorporated into separating tank to form top gas phase and phase of the liquid end, described tank is integrated in steam cracker furnace.Described gas phase is sent to the radiant-type furnace in described steam cracker furnace.At least the alkene of 30wt% reclaims (weight of total hydrocarbon material based on leaving radiant-type furnace) from the material leaving radiant-type furnace.Add steam and help flash separation further by reducing hydrocarbon partial pressure, help 750 ℉ ⁺(399 DEG C ⁺) to 1150 ℉ ⁺(621 DEG C ⁺) conversion of residue oil fraction and gasification, and prevent fouling.

Described fluid coker preferably includes the air gasification device (or partial oxidation reactor) of integration, and it is used to coke be fuel gas by steam/air gasification lower between about 1400-1800 ℉ (760-982 DEG C) and burning.Can by co-fed oxygen or by using the air of oxygen enrichment to promote gasification.The coke of the partial gasification of the heat from this gasification reaction continuous print from gasifier is taken out, and be fed to one or more solid transmission line, wherein it contacts with by the base material being equipped with one or more steam cracker furnace of the gas/liquid separation of integration (such as separating tank) to reclaim.This residual oil fractions is converted to the mixture of the more light hydrocarbon comprising high concentration ethylene and propylene at 1300-1800 ℉ (704-982 DEG C).Although transfer line reactor can be arranged in several ways, preferred to arrange to for fluid catalytic cracking unit similar; Such as, transfer line operates as vertical-lift pipe reactor, solid and the feed contacts close to the bottom of riser tube of wherein said heat, solid and steam upwards transmit along riser tube, and described solid and steam use the swirler of one or more series connection to be separated.Or transfer line can as " downtake " or downflow reactor operation.No matter specifically arrange, for making the coke of heat contact with oil residues, transfer tube reactor is very effective.

Or, the vacuum residuum (fractionating out from crude oil) from refinery directly can be sent to crude conversion units and subsequently as the raw material of steam cracker furnace of separating tank being equipped with integration.

Preferably, flash tank preferably operates at the temperature of about 800 ℉ (about 425 DEG C) to about 870 ℉ (about 465 DEG C), but also usually not higher than about 900 ℉ (about 482 DEG C).By flash tank flash distillation material to obtain top gas and liquid bed material further promotes 650 ℉ ⁺(343 DEG C ⁺) slag oil gasification.

Independent steam cracking provides ethene, propylene, butylene, C except needing ₅alkene and diene, and beyond mononuclear aromatics product, also comprise the oil fuel of remarkable productive rate, tar and SCN (petroleum naphtha of steam cracking).It is effective especially and favourable that method of the present invention is integrated for steam cracker, because the crude conversion that described method achieves significantly higher level is chemical, and non-scaling, and its demand making cooling and reheat midbody product stream minimizes.

The product liquid produced in thermal cracking residue can in steam cracker the chemical of production high yield and the tendency showing the fouling steam cracker furnace of reduction (to 1050 ℉ ⁺(566 DEG C ⁺) residual oil).

The present invention relates to for the method for production of chemicals from heavy feed stock in one way, wherein more vacuum residuum is converted into fuels and chemicals in large quantities.Usually, described method relates to the heavy feedstocks steam cracker of the vacuum residuum separating tank comprising integration and the integration of the second thermal conversion reaction device, and in the second thermal conversion reaction device, vacuum residuum is converted into the lighter component being suitable for steam cracking.Second thermal conversion reaction device is usually at the time/temp window operation similar with coking process to conventional viscosity breaking, although operation can be favourable under the condition of the milder a little of the condition than the production fuel usually adopted.In one embodiment, in method described herein, operation under 25 DEG C or more (or 50 DEG C or more, or 75 DEG C or more) below the service temperature of the stove section of the steam cracker of thermal conversion reaction device after thermal conversion reaction device.In some embodiments, lighter liquid described in preferred cascade and gas not condensation by the radiation section of steam cracker.By closely integrating two kinds of method for transformation, a kind of operation under relatively mild severity operates under high severity with a kind of, and wide multiextent heavy feedstocks can be converted into the chemical of high value by described method.(when specifying reactor or reaction zone for " operating in " a certain temperature, the material that it refers in reactor or district has been heated to that temperature).

In the following drawings and specification sheets, any gas/liquid separation device can be often referred to reference to separating tank.

Basic flow sheet of the present invention shows in FIG, wherein hydrocarbon feed (comprising long residuum) 100 is introduced the first thermal conversion reaction device 600, wherein at least the crude conversion of 30wt% (preferably at least 50%, preferably at least 70%, preferably about 90%) is 1050 ℉ ^-(566 DEG C ^-) fraction and/or petroleum coke.Subsequently whole liquids and gases product is introduced (207) to separating tank 205 (usually operating under 800-900 ℉ (423 to 482 DEG C)), described tank is connected (such as with steam cracker furnace 200 (having convection furnace 206 and radiant-type furnace 250) fluid, be incorporated into steam cracker furnace 200), to form top gas phase 210 and liquid bottom phase 220.Directly or by well heater gas phase 210 is sent to the radiant-type furnace 250 in described steam cracker furnace 200 subsequently, described well heater is such as the convection zone 206 of dispatch tube well heater or steam cracker 200, wherein radiation section operates usually at 750 to 900 DEG C, and at least the radiation section charging of 30wt% (preferably 40% or more) is converted to light olefin (such as C ₂, C ₃, C ₄), described light olefin reclaims from the material 221 leaving radiant-type furnace (weight of total hydrocarbon material based on leaving radiant-type furnace).

Another basic flow sheet of the inventive method shows in fig. 2, wherein heat packs containing residual oil hydrocarbon feed 100 (usually in the convection furnace 206 of steam cracker furnace) and, preferably at least 10wt% (preferably at least 20wt%, preferably at least 25wt%, or from about 20-30%) vacuum residuum be converted into 1050 ℉ ^-(566 DEG C ^-) cut.Whole charging is heated to about 750-850 ℉ (399-454 DEG C).Subsequently the raw material of heating is transmitted 207 to separating tank 205 (being preferably incorporated in steam cracker furnace), usually operate under 800-900 ℉ (423-482 DEG C).Subsequently the raw material of heating is separated (being usually separated in flash tank by the gravity settling of centrifugal force with coalescent drop) to form top gas phase 210 and the liquid bottom phase 220 comprising described residual oil.Subsequently, liquid bottom 220 is sent to thermal conversion reaction device 300 mutually, and optionally comprise coke granule, wherein it is changed into the molecule 223 seethed with excitement below at 1050 ℉ (566 DEG C) of more lightweight higher.Subsequently, the molecule 223 of described more lightweight is sent to separating tank 205 ^*(usually operating at 800-900 DEG C), described tank is preferably incorporated in steam cracker furnace, to form the second top gas phase 210 ^*with phase 220 bottom second liquid ^*.Subsequently by top gas phase 210 ^*be sent to the radiant-type furnace 250 in steam cracker furnace ^*(usually operating at 750-900 DEG C), is preferably separating tank 205 ^*the steam cracker furnace integrated with it.Afterwards, light olefin (such as, the C of at least 30wt% (preferably at least 40%) ₂, C ₃, C ₄alkene) by reclaiming in the material leaving radiant-type furnace 225 (weight of total hydrocarbon material based on leaving radiant-type furnace).

Another basic flow sheet of the inventive method shows in figure 3.By heavy feed stock crude oil or vacuum residuum 101 (preferably comprise about 10-50% at vacuum residuum scope (1050 ℉ ⁺(566 DEG C ⁺) in the molecule of boiling) 100 be fed in the first steam cracker furnace 200, described first steam cracker furnace 200 comprises the separating tank 205 of integration.Whole charging is heated to about 750-850 ℉ (399-455 DEG C) in the convection zone 206 of stove.Whole charging transmits 207 and enters separating tank tripping device 205, the molecule wherein seethed with excitement below at about 1000-1100 ℉ (538-593 DEG C) is evaporated (or keep evaporation) and with the compound separation of more heavy remaining on liquid phase.Material usually enters described tank and promotes evaporation by using steam stripped or extracting with light hydrocarbon at the temperature of about 800-850 ℉ (427-454 DEG C).Gas enters the radiation section 250 of the first steam cracker furnace by top 210, but heavy liquid is taken out from the bottom of separating tank 220.Joined in the second conversion reactor 300 by heavy liquid molecule subsequently, wherein heavy liquid is thermally cracked into the molecule of more lightweight.Subsequently, lighter molecules is entered into by 221 and is incorporated into steam cracker furnace (not shown) tank separating device 400, wherein below about 538-593 DEG C, the molecule of boiling is evaporated (or keep evaporation) and is separated from the compound of still more heavy in the liquid phase.Material usually enters described tank and promotes evaporation by using steam stripped or extracting with light hydrocarbon at the temperature of about 427-470 DEG C.Steam enters the radiation section (not shown) of steam cracker furnace by top by pipeline 410, but bottom stream is taken out by the bottom of separating tank by pipeline 420.Steam can be incorporated into (not shown) in steam cracker furnace.Bottom stream 420 from separating tank may be used for oil fuel among other things.In preferred embodiments, the material leaving thermal conversion reaction device can not be introduced in the first steam cracker again.

Preferably combine from several heavy liquid of the stove of separating tank that is equipped with to realize better scale economics in the second vacuum residuum conversion reactor.Second conversion reactor directly can be combined with steam cracker furnace and can adopt the form that this coker of delay coking device, fluid coker, Fick (flexicoker), visbreaker, shortening visbreaker or other suitable conversion reactor design.Optionally, before entering coking reactor, can by reheating in reboiler or stove or making feeding preheating to about 800-900 ℉ (427-482 DEG C) further by contacting with high-temperature gas such as steam or hydrogen.In the second conversion reactor, a high proportion of vacuum residuum molecule (such as, about more than 50%) is thermally cracked into the molecule of the more lightweight of seething with excitement below at 1050 ℉ (566 DEG C).Vacuum residuum molecule usually be once the scope of 30-60% in viscosity breaking by transforming, or once reach most 95% or more by shortening viscosity breaking or coking.This is by balanced reaction time and the residence time, and extracts lighter product liquid realization in the conversion vessel operated under thermal insulation.In order under remaining on high-level crude conversion or the hydrogen balance of more low hydrogen content charging, most heavy vacuum residual oil molecule is converted into the solid coke product of low hydrogen content or the heavier tarry bottom fraction of transferring to.In shortening visbreaker, except producing the heavier tarry bottom fraction of low hydrogen content, add hydrogen with feed heteroatoms to produce H ₂s, NH ₃and H ₂o, and the olefinic fragment adding to cracking is to prevent coking.When delay coking device, continue reaction until described tank fills solid coke gradually.Subsequently charging is switched to the second tank, coke is reclaimed from the first tank simultaneously, and continue the method in a circulating manner.In preferred embodiments, the second steam cracker furnace being incorporated to and integrating separating tank will be fed to from the gas of pyrogenic reaction and product liquid.Compare with the first stove (or for supplying the stove group of coker feed), this stove can operate at slightly lower separating tank temperature or cut point, preferably the second separating tank operation under 25 DEG C or more (preferably 50 DEG C or more, preferably 75 DEG C or more) below the service temperature of the first separating tank.The molecule of the more lightweight produced in coking (or second transform) reactor keeps evaporation and is sent to the radiation section of steam cracker, and more vacuum gas oil (VGO) molecule of heavy and the material that do not transform in coker take out from the bottom of the second separating tank.In preferred embodiments, these molecules are disposed by other means, such as, be mixed into oil fuel, and as usually put into practice in fuel coking method, recycle back is not to coker.In another preferred embodiment, the hot gas from coker top partly can use the distillment stream quenching between the outlet of water cooler VGO or coker and separating tank entrance, to promote the further condensation of the heavier VGO component of more low hydrogen content.

Although vacuum residuum coking and gas oil steam cracking are well-known methods, coker is unknown with the integration of steam cracker furnace of the separating tank comprising integration.In addition, bottom material is usually preferably made to be circulated to obliteration procedure coker to maximize the productive rate of more light fuel components or fuel feedstocks.The compound of very infusibility is produced in this bottom cycle operation, and the soluble polynuclear aromatics of such as heptane, it is inappropriate as chemical charging.Unaccommodated especially raw material is the molecule comprising 4 or more thick aromatic rings.Fuel coker is equipped with large main fractionator usually, its by be mixed for preheating fresh feed with coker product and by mixed coking device raw material and coker tank gas streams for cleaning the coker gas of entrained drip.Bottom material reenters reactor with this fresh feed.In the process for steam cracking integrated, eliminate this main fractionator.

In the practice of the invention, the separating tank integrated is efficient especially and for heavy feedstocks steam cracking and coking method operation is effective and non-scaling, because it allows, the cut point between gas and heavy liquid is easily consistent with feedstock property to be changed.

A kind of particularly preferred setting is the direct integration of method for thermal cracking and steam cracker.Direct integration refers to that the heating of steam cracker convection zone enters the charging of heat conversion device and the effluent of heat conversion device is directly sent to separating tank, and is sent to radiation section subsequently and not by any intermediate heat exchanger.

Preferred thermal conversion reaction device used herein comprises delay coking device, fluid coker, Flexicokers ^tM, visbreaker and shortening visbreaker.

The preferred basic setup of thermal conversion reaction device is similar to delay coking device.Described method particularly: i) operation is (such as under slightly comparatively low severity, from 800-900 ℉ (427-482 DEG C), preferred 800-850 ℉ (427-454 DEG C)), ii) the every kg residual oil raw material of about 0.1-1.0kg steam is used, iii) under lower appropriate hydrocarbon gas dividing potential drop and/or shorter gas residence time, drum is operated, iv) in the separating tank equipment integrated, coking gas is separated by the heavy liquid of carrying secretly, and v) preferably once-through operation and do not have bottom cycle.Delayed coking is " Tutorial:DelayedCokingFundamentals. " article 29a at P.J.Ellis and C.A.Paul autograph, (it can be from for TopicalConferenceonRefineryProcessing, 1998GreatLakesCarbonCorporation http:// www.coking.com/DECOKTUT.pdfdownload) article in describe.In delay coking device, by as the tank of distillation tower directly contact product gas and the liquid carried secretly are exchanged with colder feed heat.This tank operates usually under close to 50psig (345kPa).Abrogating of the heavy coked device liquid that this technology causes the gas changing into the tank left as distillation tower completely and the Reusability of coke assembled in drum.Leave as the bottom heating liquid feeding of the tank of distillation tower and heat exchanger usually at 360-400 DEG C.The liquid of this heat is transported through a pump, liquid pressure is promoted to 300-600psig (2.1-4.1MPa) by described pump.The feed flow of heat pressurization is by coker stove, and described charging is wherein heated to close to 500 DEG C.Stove effluent close to 500 DEG C and 60psig (414kPa) flows in drum, and described drum is from steam and separate solid coke the drop carried secretly.Can volatiles be removed subsequently and send it to steam cracker (preferably there is the steam cracker integrating separating tank), and leaving coke.The material being sent to steam cracker is converted into alkene subsequently.

In another embodiment, heating is sent to coking district from the liquid phase of the first gas/liquid separation subsequently to coking temperature (being such as up to 649 DEG C) in heating zone (such as delay coking device), wherein forms coke at collected overhead volatile matter.Preferably, make the liquid phase from the first gas/liquid separation stand delayed coking, its thermolysis relating to petroleum residual oil is to produce the gas of multiple boiling range, liquid material stream and coke.In delayed coking method, in the well heater fired or tube furnace, rapid heating is from the liquid phase of the first gas/liquid separation, subsequently the liquid phase of the heating from the first gas/liquid separation is sent to drum, described drum remains on the condition that coking occurs, usually under the temperature super-atmospheric pressure power being greater than about 400 DEG C.The charging of the heating in drum also forms the volatile constituent (preferably having the steam cracker of the separating tank of integration) being removed and being sent to steam cracker, and is stayed by coke.The material being sent to steam cracker is converted to alkene subsequently.

If use shortening visbreaking reactor as thermal conversion reaction device 300, so hydrogen-containing gas (such as H of mink cell focus and catalyzer (such as metallic sulfide) and molecule ₂, synthetic gas, fuel gas) mixing, and a high proportion of vacuum residuum molecule, such as, at least about 60%, even about between 60-80%, or is even up to 95% and is converted to the lighter molecule seethed with excitement below at 1050 DEG C (566 DEG C).Usual operational condition comprises the temperature of 785-900 ℉ (418-482 DEG C), the residence time (0.1-5LHSV (liquid hourly space velocity)) of 2-100 minute, the hydrogen processing rate of 500-5000SCF/B, and the working pressure of 100-3000psig (0.689-20.7MPa).Preferred condition is about 785-860 ℉ (418-460 DEG C), 10-40 minute (0.2-2LHSV), 1000-2500SCF/B, and 500-1500psig (3.45-17.2MPa).Although other design is possible, common reactor design comprises coil reactor, in conjunction with the coil reactor of pump around cracking case, or with the slurry bubbling bed of liquid recycle.Usually, reactor condition is optimized to mate feedstock quality; Such as, lower quality charging can require that more exacting terms transforms with the height realizing 50-95% scope, preferably about 60-80%.Use conventional facility (high and light pressure separator) to remove gas and product liquid after the reactor and the untapped hydrogen that circulates to the method.The catalyzer used in shortening viscosity breaking method is usually based on sulfide transition metal.The most common metal is Mo, Ni and Co.When the method operates with slurry, catalyzer is usually based on being dispersed in carbonaceous main body (a.k.aMicrocat ) micron or the metal sulfide grain of submicron-scale.Described Microcat can based on moly-sulfide; Other transient metal sulfide such as by tungsten, vanadium, iron, nickel and cobalt produce those; Or the moly-sulfide to be combined with one or more these selectable transient metal sulfide, or the combination of selectable transient metal sulfide.Although molybdenum provides gratifying operation for many chargings separately, the use of other metal or multimetallic catalyst system can provide the performance of improvement, such as higher catalytic activity to the conversion of residual oil, hydrogen addition and desulfurization.Fresh catalyzer passes through usually by heavy VGO cut and low cost catalyst precursor, and such as ammonium molybdate or phospho-molybdic acid mix and be heated to 600-800 ℉ (316-427 DEG C) formation in 10-60 minute.The pre-formed of catalyzer is preferably carried out under hydrogen and H2S or elementary sulfur existence.The Microcat produced in like fashion in many conversions, to filter and re-use in circulation be stable.But catalyzer can deactivate within the long time.Due to this reason, from method, remove little removing stream can be favourable.This " with what cross " catalyzer can regenerate in a separate device or again form fresh catalyst precursor.When method is in fixed bed operation, adopts and be generally used for fixed bed residuum hydrodesulfurization (producing low sulphur fuel oil by the charging comprising 650+ residual oil), FCC feed pretreatment, and the conventional fixed bed catalyst of heavy feedstocks hydrocracker.

In generation nineteen sixty, Exxon develops available Flexicoking herein ^tMmethod and describing in detail in first patent and the textbook about Residual cracking technology at wide region.Such as, U.S. Patent No. 3,671,424, is incorporated to herein by introducing, and describes the suitable fluid coking equipment of examples and method is used for purposes herein.

In another embodiment, the liquid phase leaving the first gas/liquid separation is heated to such as 1000-1200 ℉ (538-649 DEG C) further, preferred 1100-1200 ℉ (593-649 DEG C), the preferably temperature of about 1125-1190 ℉ (607-643 DEG C), usually carry out in the lower coil pipe of the convection zone of steam cracker, the wherein material of usually part heating normally viscosity breaking, then uses water (such as steam) quenching and evaporates the material of viscosity breaking.Subsequently the viscosity breaking material of evaporation is sent to the second gas/liquid separation, the material of wherein viscosity breaking is separated into second liquid phase and the second gas phase.Second gas phase be introduced into subsequently steam cracker (convection zone or radiation section or the two) and from the material leaving radiant-type furnace, reclaim the alkene (preferably 40% or with many, preferred 50wt% or more) (weight of total hydrocarbon material based on leaving radiant-type furnace) of at least 30wt%.

Usually, reaction kinetics and reaction heat calculate display when residual oil is exposed to 1200 ℉ (649 DEG C) 2 seconds roughly, obtain almost viscosity breaking completely and transform.But because viscosity breaking is thermo-negative reaction, it is inadequate for only quickly heating up to 1200 ℉ (649 DEG C).In viscosity breaking subsequently, residual oil is cooled to 950 ℉ occurring 60% roughly ⁺(510 DEG C ⁺) to 950 ℉ ^-(510 DEG C ^-) degree that transforms.Higher temperature adds the transformation efficiency of viscosity breaking, but the second pyrogenic reaction also occurs.Therefore, in preferred embodiments, in lower convection zone rapid heating from the bottom stream of the first separating tank to 1000-1200 ℉ (538-649 DEG C) (preferred 1100-1200 ℉ (593-649 DEG C), preferably about 1200 ℉ (649 DEG C)), wherein the hot continuous print of flue gas instead of heat absorption loss.In order to be minimized in the fouling in convection zone, bottom stream is only heated so that coke precursors is washed off from internal surface by the residual oil of high speed continuously in one way.If really there are some coking, periodic steam/air decoking is by calcination/make it peel off from pipe.

In alternate embodiments, convection tubes can be by solid outer tube around porous sintered metal, wherein steam is in anchor ring.Vapor pressure oozes out the operation pressure of pipe in sintering higher than causing steam thus prevents sedimentation of coke.

Subsequently, when leaving convection zone, the bottom of viscosity breaking is expected (such as, 1000-1200 ℉ (538-649 DEG C)) fast quench, otherwise the extra residence time can cause excessive coking.Steam and/or water are excellent quenching mediums, because they make light fractions evaporation newly-generated in a large number reduce hydrocarbon partial pressure.Note, in this quench operation, there is sufficient liquid, it prevents coking.In the gas phase, bimolecular pyrogenic reaction is not dominant (compared with liquid phase), because hydrocarbon concentration is low.In preferred embodiments, any fouling that still can occur in gas phase is avoided to ~ 840 ℉ (449 DEG C) by quenching.In optional embodiment, a part of bottom stream carrying out autonomous separating tank can contribute to quench operation.

In another embodiment, the second little separating tank is separated the light hydrocarbon of viscosity breaking from remaining residual oil.As the first separating tank, the pipeline to the second tank engages remaining liquid, and it is separated with appropriate hydrocarbon gas/vapour mixture subsequently in described tank.By operating described second tank at ~ 840 ℉ (449 DEG C), fouling in the gas phase will be very low.Therefore, gas can be sent to the overhead line of the first separating tank or the first tank.Or, the gas/liquid from quenching can be added the pipeline of the first separating tank upstream, eliminate the needs to the second separating tank.In addition, two separating tank design allows the bottom stream only once viscosity breaking intensely from the first separating tank, reduces the possibility of serious coking.Note, the second separating tank temperature so not high (hydrocarbon partial pressure is so not low yet) so that bottom stream can not flow and/or can not flow out.

Steam tracing reduces gas phase fouling usually further.Coking test display superheated coke(oven)gas makes the fouling in swirler minimize to arriving 1250 ℉ (677 DEG C), and supposition is by preventing the main coking mechanism of liquid deposition.Therefore, a preferred embodiment of the present invention is by making all containers of gas/liquid separate downstream and pipeline steam tracing with overheated steam and preventing liquid deposition.Institute's rheme hot steam (it is more remarkable than process gas hotter), if these pipelines are heat insulation, so eliminates the cold spot that may exist.Even hotter steam may be used for superheated gas to limited extent.If needed, some tracing steams can be injected directly in gas to provide further overheated.

The high usability of a significant advantage heavy feedstocks of the present invention, and there is no undue coking.

Another basic flow sheet for the inventive method shows in the diagram.By heavy feed stock crude oil or residual oil 101 (preferably comprise about 10%-50% at vacuum residuum scope (1050 ℉ ⁺(566 DEG C ⁺)) molecule that seethes with excitement) be fed in the first steam cracker furnace 200, described first steam cracker furnace 200 comprises the separating tank 205 of integration.At the convection zone 206 of described stove, whole charging is heated to about 800-900 ℉ (427-482 DEG C).Whole preheated feed is led to 207 separating tank separating devices 205, wherein evaporate the molecule that (or keep evaporation) seethes with excitement below at about 1000-1100 ℉ (538-593 DEG C), and from heavier still compound separation in the liquid phase.Material usually enters described tank in the temperature of about 800-850 ℉ (427-454 DEG C) and promotes evaporation by using steam stripped or extracting with light hydrocarbon.Gas enters the radiation section 250 of the first steam cracker furnace by 210, and heavy liquid is taken out by the bottom of separating tank 220.Subsequently, heavy liquid molecule is added the convection zone 206 (or by mix with fresh feed or by being sent to the heating plate area under control be separated) of stove, wherein heavy liquid is become lighter molecule by viscosity breaking.Water or steam 227 are introduced evaporate lighter molecule (usually outer at convection zone).Make the lighter molecules of viscosity breaking by 221 to separating tank separating device 400 subsequently, described separating tank separating device 400 is incorporated into (not shown) in steam cracker furnace and wherein evaporates the molecule that (or keep evaporation) seethe with excitement about 538-593 DEG C below, and is separated from still heavier compound in the liquid phase.Steam is entered the radiation section (not shown) of steam cracker furnace by 410, and bottom material is taken out by pipeline 420 from the bottom of separating tank.Steam can be incorporated into steam cracker furnace (not shown).Bottom material 420 from separating tank may be used for oil fuel among other things.In preferred embodiments, the material leaving thermal conversion reaction device is not reintroduced in first cracking device.

In preferred embodiments, in separating tank main conversion be separated after the residue vacuum residuum that retains not reclaim with additional conversion be chemical.This remaining material comprises the compound of very infusibility, the insoluble polynuclear aromatics of such as heptane, and it is not preferred for chemical charging.These remaining molecules are transformed to produce fuel in oil fuel or optional refinery's crude conversion device being separated obtain better utilised by being mixed into.

In another preferred embodiment, the vacuum resid feed transformed in the present invention comprises the hydrogen higher than 10.0wt%, preferably higher than 11.0wt%.

In another preferred embodiment, the charging entering thermal conversion reaction device (such as coker or delay coking device) comprises the hydrogen higher than 10.0wt%, preferably higher than 11.0wt%, preferably higher than 11.5wt%, based on the weight of charging.

In another embodiment, the temperature leaving the gas of thermal conversion reaction device (such as coker or delay coking device) is 750-900 ℉ (399-482 DEG C), preferred 780-860 ℉ (416-460 DEG C), preferred 800-850 ℉ (427-454 DEG C).In another embodiment, the most nearly 30psig (207kPa) of the pressure in thermal conversion reaction device, preferably reaches most 25psig (172kPa), preferably from 1-20psig (138kPa).

In preferred embodiments, when the convection zone by the first steam cracker furnace leads to the first separating tank of integration, uncolled hydrocarbon feed.The uncolled temperature referring to the mixture flow of preferred feedstock liquids and gases reduces and is no more than 30 DEG C (or be no more than 50 DEG C, or be no more than 100 DEG C).In another embodiment similarly, when the convection zone by the second steam cracker furnace leads to the second separating tank of integration, uncolled hydrocarbon feed.

In another embodiment of method described herein, before entering into the separating tank of integration, thermal transition material (such as residual oil or liquid bottom phase) is sent to the convection zone of steam cracker.

In another embodiment, by molecular hydrogen (usually containing the gas of molecular hydrogen), in method, any point joins in the raw material of heating.

In another embodiment, can steam be added in the raw material of heating any point in method.This is particularly useful for helping the evaporation in the separation tank field integrated.

In particularly preferred embodiments, thermal conversion reaction device is at 649 DEG C or more lowly operate, preferably 640 DEG C or lower, preferably 630 DEG C or lower.

In an especially preferred embodiment, thermal conversion reaction device be low severe condition (such as, be less than the temperature of 860 ℉ (460 DEG C) and the pressure of 30kPa or lower) under operation delay coking device, and the in the future output of self-dalay coker is directly sent to and is incorporated into separating tank on steam cracker (before being sent to the separating tank of integration, can the output of self-dalay coker in the future through the convection zone of steam cracker).In this scheme, the charging entering delay coking device is heated in the convection zone of steam cracker and effluent from delay coking device tank directly flows in separation pot, and described separation pot and steam cracker radiation section are integrated.Given drum integratedly can be fed to one or more steam cracker furnace being equipped with the separating tank of integration with supply.Also be possible with multiple drum of one or more stove with the integration being separated pot.Replace a tank, two or three tanks can be had in parallel.Tank can on steam, and other emptied coke.

In particularly preferred embodiments, vacuum residuum is passed in steam cracking convection zone, (wherein gas/liquid separation is connected with steam cracker fluid to be sent to gas/liquid separation subsequently, be connected with the convection zone fluid of steam cracker especially), thereafter crude conversion is become gas phase and liquid phase.Gas phase is sent to identical or different steam cracker, at radiation section or convection zone, or the two.Liquid phase is sent to thermal transition district, such as coker, delay coking device, this coker of Fick, catalysis visbreaker or shortening visbreaker, wherein converts it into gas or liquid stream and coke.(wherein gas/liquid separation is connected with steam cracker fluid with being sent to gas/liquid separation afterwards subsequently gas or liquid stream transmission to be entered the convection zone of steam cracker (being preferably different from the steam cracker of the first steam cracker), particularly the convection zone fluid of steam cracker is connected), afterwards the gas of heating or liquid stream are converted into gas phase and liquid phase, be sent in identical or different steam cracker with by described gas phase, at radiation or convection zone, or the two.

In another embodiment, the present invention relates to:

1. comprise the method for the hydrocarbon feed of vacuum residuum for cracking, comprising:

A the hydrocarbon feed comprising vacuum residuum is sent to the first thermal transition district by (), wherein by described heating raw materials to being less than the temperature of 649 DEG C (such as, be less than operation at 649 DEG C), wherein at least the vacuum residuum of 30wt% (at least 50wt%, at least 70wt% or at least 90wt%) is converted into the material of boiling below 566 DEG C;

B the residual oil of described thermal transition is incorporated into gas/liquid separation by (), to form gas phase and liquid phase, described separator is connected with steam cracker furnace fluid;

C described gas phase is sent to described steam cracker furnace by (); With

D () is from the alkene (weight of total hydrocarbon material based on leaving radiant-type furnace) of salvage material at least 30wt% of radiant-type furnace leaving steam cracker furnace.

2. the method for paragraph 1, wherein from the liquid bottom phase of the gas/liquid separation of step (b): be brought to (such as, heating or cooling) temperature (or, be less than 649 DEG C) of 538-649 DEG C is with viscosity breaking liquid bottom phase at least partially; Afterwards the liquid bottom phase quenching of viscosity breaking is sent to the second gas/liquid separation subsequently, wherein viscosity breaking liquid bottom is separated into second liquid phase and the second gas phase mutually; Thereafter then the second gas phase is incorporated into the steam cracker furnace of step (c).

3. comprise the method for the hydrocarbon feed of vacuum residuum for cracking, comprising:

A () heat packs becomes containing the hydrocarbon feed of vacuum residuum the material seethed with excitement below 566 DEG C with the vacuum residuum transforming at least 10wt%;

B the hydrocarbon feed of described heating is sent to gas/liquid separation by ();

D () will be sent to the first thermal transition district from the liquid phase containing residual oil described in described separator at least partially;

E the liquid phase of described thermal transition is sent to gas/liquid separation to form the second gas phase and second liquid phase by (), described separator is connected with steam cracker furnace fluid;

F described second gas phase is sent to described steam cracker furnace with described second gas phase of thermal transition (at least partially) by (); With

G () is from the alkene (weight of total hydrocarbon material based on leaving radiant-type furnace) of salvage material at least 30wt% of radiant-type furnace leaving described steam cracker furnace.

4. the method for paragraph 3, is wherein heated to the temperature of 538-649 DEG C with viscosity breaking liquid phase at least partially by the liquid phase from step (c); Afterwards the liquid phase quenching of viscosity breaking is also sent to another gas/liquid separation subsequently, wherein viscosity breaking liquid phase is separated into the liquid phase of viscosity breaking and the gas phase of viscosity breaking; Thereafter the gas phase of viscosity breaking is incorporated into the thermal transition district of step (d).

5. the either method of paragraph 1-4, is wherein heated to the temperature of 593-649 DEG C by the liquid bottom phase in the claim 1 from the gas/liquid separation in step (b) in claim 1 or from the liquid phase of step (c) in claim 2.

6. the either method of paragraph 1-5, wherein thermal transition district comprises coke granule, wherein said district has coke granule/fresh feed ratio (wt/wt) (preferably at least 3:1 of at least 1:1, preferred at least 5:1, or from 1:1 to 50:1, preferably from 3:1 to 30:1), based on recycle coke solid and the weight of fresh feed entering described district.

7. the either method of paragraph 1-5, wherein said thermal transition district is delay coking device, fluid coker, Flexicoker ^tM, visbreaker or shortening visbreaker.

8. the either method of paragraph 1-5, wherein said thermal transition district is delay coking device.

9. the either method of paragraph 1-8,25 DEG C or more lower operations below the service temperature of wherein said thermal transition district stove section of steam cracker after thermal transition district.

10. the either method of paragraph 1-9, wherein vacuum resid feed comprises the hydrogen higher than 10.0wt%.

The either method of more than 11. claims, the charging wherein entering thermal transition district comprises the hydrogen higher than 11.0wt%.

Any means of 12. paragraph 1-11, the temperature wherein leaving the gas in thermal transition district is 399-482 DEG C.

The either method of 13. paragraph 1-12, wherein before entering gas/liquid separation, is sent to the convection zone of steam cracker by the thermal transition residual oil of claim 1.

The either method of 14. paragraph 2-13, wherein before entering into gas/liquid separation, is sent to the convection zone of steam cracker by the thermal transition liquid phase of claim 2.

The either method of 15. paragraph 1-14, wherein hydrogen or steam are joined the raw material of heating by arbitrfary point in the process.

The either method of 16. paragraph 1-15, wherein said steam cracker convection zone is heated to the charging in thermal transition district, and the effluent in thermal transition district is directly sent to gas/liquid separation, and is sent to the radiation section of steam cracker subsequently, and do not transport through any intermediate heat exchanger.

The either method of 17. paragraph 1-16, wherein at least the alkene of 40wt% from the salvage material (weight of total hydrocarbon material based on leaving radiant-type furnace) leaving radiant-type furnace.

The either method of 18. paragraph 1-17, wherein the first thermal transition district is fluid coker.

The either method of 19. paragraph 1-18, wherein the first thermal transition district is shortening visbreaker.

The either method of 20. paragraph 1-19, wherein the first thermal transition district is the hydrogenation visbreaker operated under 400 to the temperature being less than 649 DEG C.

21. systems comprising the hydrocarbon feed of vacuum residuum for cracking, comprising:

A) be less than the first thermal transition district operated at the temperature of 649 DEG C, it is selected from: delay coking device, fluid coker, Flexicoker ^tM, visbreaker or shortening visbreaker, described first thermal transition district is connected with b) steam cracker furnace fluid, and described b) steam cracker furnace has the gas/liquid separation be connected with described stove fluid.

The system of 22. paragraphs 21, comprises the second gas/liquid separation be connected with described thermal transition district fluid further.

The system of 23. paragraphs 21 or 22, wherein the first thermal transition district is fluid coker, and described fluid coker comprises:

I) fluidized-bed gasifier,

Ii) transfer line reactor, it comprises the hydrocarbon opening for feed be connected compared with lower part fluid with described separator, and pyrolysis product outlet line,

Iii) solid pipeline, the comparatively lower part of described fluidized-bed gasifier is connected with described transfer line reactor by it, and

Iv) at least one cyclonic separator, it has the entrance being connected to described pyrolysis product outlet line, the crackate outlet at described cyclonic separator top, and the solid outlet bottom described cyclonic separator.

The system of 24. paragraphs 23, is included in the air/steam entrance bottom described fluidized-bed gasifier further.

The system of 25. paragraphs 23 or 24, wherein said fluid coker comprises fluidized-bed heater canister further, it has and connects the recirculated solids pipeline of described heater canister compared with lower part and described gasifier, with at least one gas pipeline, described gas pipeline divides and comparatively the connecting between lower part of described heater canister in the higher part of described gasifier.

Arbitrary system of 26. paragraph 23-25, wherein said cyclonic separator solid outlet be connected to described fluidized-bed gasifier or described heater canister any one or the two.

Arbitrary system of 27. paragraph 23-26, comprises and connects described heating container and described gasifier two solid pipelines compared with lower part.

Arbitrary system of 28. paragraph 23-27, wherein said transfer line reactor is vertical-lift pipe reactor, and wherein said solid pipeline and described hydrocarbon feed entrance are connected to the comparatively lower part of described reactor.

Arbitrary system of 29. paragraph 23-28, wherein said transfer line reactor is downflow reactors, and the higher part that wherein said solid pipeline and described hydrocarbon feed entrance are connected to described reactor is divided.

In another embodiment, the present invention relates to:

1A. is used for the method that cracking comprises the hydrocarbon feed of vacuum residuum, comprising:

A the hydrocarbon feed comprising vacuum residuum is sent to the first thermal transition district by (), wherein by described heating raw materials to the temperature being less than 649 DEG C, wherein at least the vacuum residuum of 30wt% to be converted into below 566 DEG C the material of boiling;

B the residual oil of described thermal transition is incorporated into gas/liquid separation to form gas phase and liquid phase by (), described separator is connected with steam cracker furnace fluid;

C described gas phase is sent to described steam cracker furnace (radiant-type furnace in preferred steam cracker furnace) by (); With

The method of 2A. paragraph 1A, wherein from the liquid bottom phase of the gas/liquid separation of step (b): be brought to the temperature of 538-649 DEG C with viscosity breaking liquid bottom phase at least partially; Afterwards the liquid bottom phase quenching of viscosity breaking is sent to the second gas/liquid separation subsequently, wherein viscosity breaking liquid bottom is separated into second liquid phase and the second gas phase mutually; Thereafter then the second gas phase is incorporated into the steam cracker furnace of step (c).

The method of 3A. paragraph 1A, is wherein heated to the temperature of 593-649 DEG C mutually from the liquid bottom of the gas/liquid separation of step (b).

The method of 4A. paragraph 1A, wherein thermal transition district comprises coke granule, and wherein said district has the coke granule/fresh feed ratio (wt/wt) of at least 1:1, based on recycle coke solid and the weight of fresh feed entering described district.

The method of 5A. paragraph 1A, wherein said thermal transition district is delay coking device, fluid coker, Flexicoker ^tM, visbreaker or shortening visbreaker.

The method of 6A. paragraph 5A, wherein said thermal transition district is delay coking device.

The method of 7A. paragraph 1A, 25 DEG C or more lower operations below the service temperature of wherein said thermal transition district stove section of steam cracker after thermal transition district.

The method of 8A. paragraph 1A, wherein vacuum resid feed comprises the hydrogen higher than 10.0wt%.

The method of 9A. paragraph 1A, the charging wherein entering thermal transition district comprises the hydrogen higher than 11.0wt%.

The method of 10A. paragraph 1A, the temperature wherein leaving the gas in thermal transition district is 399-482 DEG C.

The method of 11A. paragraph 1A, wherein before entering gas/liquid separation, is sent to the convection zone of steam cracker by the thermal transition residual oil of claim 1.

The method of 12A. paragraph 1A, wherein hydrogen or steam are joined the raw material of heating by arbitrfary point in the process.

The method of 13A. paragraph 1A, wherein said steam cracker convection zone is heated to the charging in thermal transition district, and the effluent in thermal transition district is directly sent to gas/liquid separation, and is sent to the radiation section of steam cracker subsequently, and do not transport through any intermediate heat exchanger.

The method of 14A. paragraph 1A, wherein at least the alkene of 40wt% from the salvage material (weight of total hydrocarbon material based on leaving radiant-type furnace) leaving radiant-type furnace.

The method of 15A. paragraph 1A, wherein the first thermal transition district is fluid coker.

The method of 16A. paragraph 1A, wherein the first thermal transition district is shortening visbreaker.

The method of 17A. paragraph 1A, wherein the first thermal transition district is the hydrogenation visbreaker operated under 400 to the temperature being less than 649 DEG C.

18A. is used for the method that cracking comprises the hydrocarbon feed of vacuum residuum, comprising:

A the vacuum residuum of at least 10wt%, containing the hydrocarbon feed of at least vacuum residuum of 1wt%, based on the weight of hydrocarbon feed, and is converted into the material seethed with excitement 566 DEG C below by () heat packs;

D () will be sent to the first thermal transition district from the liquid phase containing residual oil described in described separator at least partially; With the thermal transition described liquid phase containing residual oil at least partially;

E the liquid phase of described thermal transition is sent to gas/liquid separation by (), described separator is connected with steam cracker furnace fluid, to form the second gas phase and second liquid phase;

F described second gas phase is sent to described steam cracker furnace with thermal transition described second gas phase at least partially by (); With

The method of 19A. paragraph 18A, is wherein heated to the temperature of 538-649 DEG C with viscosity breaking liquid phase at least partially by the liquid phase from step (c); Afterwards the liquid phase quenching of viscosity breaking is also sent to another gas/liquid separation subsequently, wherein viscosity breaking liquid phase is separated into the liquid phase of viscosity breaking and the gas phase of viscosity breaking; Thereafter the gas phase of viscosity breaking is incorporated into the thermal transition district of step (d).

The method of 20A. paragraph 18A, is heated to the temperature of 593-649 DEG C by the liquid bottom phase in the claim 1 from the gas/liquid separation in step (b) in claim 1 or from the liquid phase of step (c) in claim 2.

The method of 21A. paragraph 18A, wherein thermal transition district comprises coke granule and described district has the coke granule/fresh feed ratio (wt/wt) of at least 1:1, based on recycle coke solid and the weight of fresh feed entering described district.

The method of 22A. paragraph 18A, wherein said thermal transition district is delay coking device, fluid coker, Flexicoker ^tM, visbreaker or shortening visbreaker.

The method of 23A. paragraph 18A, wherein said thermal transition district is delay coking device.

The method of 24A. paragraph 18A, 25 DEG C or more lower operations below the service temperature of wherein said thermal transition district stove section of steam cracker after thermal transition district.

The method of 25A. paragraph 18A, wherein vacuum resid feed comprises the hydrogen higher than 10.0wt%.

The method of 26A. paragraph 18A, the charging wherein entering thermal transition district comprises the hydrogen higher than 11.0wt%.

The method of 27A. paragraph 18A, the temperature wherein leaving the gas in thermal transition district is 399-482 DEG C.

The method of 28A. paragraph 18A, wherein before entering gas/liquid separation, is sent to the convection zone of steam cracker by the thermal transition residual oil of claim 1.

The method of 29A. paragraph 18A, wherein before entering into gas/liquid separation, is sent to the convection zone of steam cracker by the thermal transition liquid phase of claim 2.

The method of 30A. paragraph 18A, wherein hydrogen or steam are joined the raw material of heating by arbitrfary point in the process.

The method of 31A. paragraph 18A, wherein said steam cracker convection zone is heated to the charging in thermal transition district, and the effluent in thermal transition district is directly sent to gas/liquid separation, and is sent to the radiation section of steam cracker subsequently, and do not transport through any intermediate heat exchanger.

The method of 32A. paragraph 18A, wherein at least the alkene of 40wt% from the salvage material (weight of total hydrocarbon material based on leaving radiant-type furnace) leaving radiant-type furnace.

The method of 33A. paragraph 18A, wherein the first thermal transition district is fluid coker.

The method of 34A. paragraph 18A, wherein the first thermal transition district is shortening visbreaker.

The method of 35A. paragraph 18A, wherein the first thermal transition district is the hydrogenation visbreaker operated under 400 to the temperature being less than 649 DEG C.

36A. is used for the system that cracking comprises the hydrocarbon feed of vacuum residuum, comprising:

The system of 37A. paragraph 36A, comprises the second gas/liquid separation be connected with described thermal transition district fluid further.

The system of 38A. paragraph 36A, wherein the first thermal transition district is fluid coker, and described fluid coker comprises:

I) fluidized-bed gasifier,

Ii) transfer line reactor, comprises the hydrocarbon opening for feed be connected compared with lower part fluid with described separator, and pyrolysis product outlet line,

The system of 39A. paragraph 38A, is included in the air/steam entrance bottom described fluidized-bed gasifier further.

The system of 40A. paragraph 38A, wherein said fluid coker comprises fluidized-bed heater canister further, it has and connects the recirculated solids pipeline of described heater canister compared with lower part and described gasifier, with at least one gas pipeline, described gas pipeline divides and comparatively the connecting between lower part of described heater canister in the higher part of described gasifier.

The system of 41A. paragraph 38A, wherein said cyclonic separator solid outlet be connected to described fluidized-bed gasifier or described heater canister any one or the two.

The system of 42A. paragraph 38A, comprises and connects described heating container and described gasifier two solid pipelines compared with lower part.

The system of 43A. paragraph 38A, wherein said transfer line reactor is vertical-lift pipe reactor, and wherein said solid pipeline and described hydrocarbon feed entrance are connected to the comparatively lower part of described reactor.

The system of 44A. paragraph 38A, wherein said transfer line reactor is downflow reactors, and the higher part that wherein said solid pipeline and described hydrocarbon feed entrance are connected to described reactor is divided.

Embodiment

By a series of coking condition of summing up in ephemeris 1 with three kinds of vacuum residuum of various quality and hydrogen richness.In order to maximize 1050 ℉ produced with the light gas reduced ^-cut product liquid, Selection radio puts into practice the coking condition of milder on severity usually.Analyze from the product of pyrogenic reaction to determine the productive rate of petroleum naphtha, overhead product and gas oil, and determine basic liquid product quality (proportion, hydrogen richness etc.).

Subsequently, the productive rate of the chemical product using the realistic model of Steam cracking processes can be produced by complete boiling range coking product with estimation.The steam cracked products productive rate selected is given prominence in table 2.That easily can find out that this coking adds that Steam cracking processes makes it possible to high yield produces chemical products by vacuum residuum, comprises ethylene/propene and butylene.When initial vacuum residuum has when the higher level of hydrogen of 11-12wt% or more scope, be conducive to high olefin productive rate.The tar of heavy lesser value and the productive rate of Gas oil products reduce along with feed hydrogen content and increase.

Table 1: the coking of the gentleness sternness degree of various quality vacuum residuum

Initial vacuum resid feed	A	B	C
				API ^*	5.4	9.8	16.5
%H	10.18	11.21	12.16
				Condition
Cell pressure psig (kPa)	3(20.7)	20(137.9)	20(137.9)
				The flat equal temperature ℉ (DEG C) of coking bed	820(438)	800(427)	824(440)
Productive rate wt%
				H ₂S	0.58	0.68	0.20
Methane	2.10	2.08	1.77
				Other C4 ^-	4.10	4.90	5.20

Petroleum naphtha (C5-, 400 ℉ (204 DEG C))	11.61	15.75	18.83
				Overhead product (400 ℉-650 ℉ (204-343 DEG C))	19.67	21.53	23.69
Bottom material (650 ℉ ⁺(343℃))	38.38	24.38	17.41
				Coke	23.57	24.38	17.41
Hydrogen richness
				Petroleum naphtha (400 ℉ ^-(204℃ ^-))	13.7	14.1	14.2
Overhead product (400 ℉-650 ℉ (204-343 DEG C))	12.5	12.64	13.2
				Bottom material (650 ℉ ⁺(343℃))	11	11.8	12.3

^*aPI=American Petroleum Institute (API) is with the proportion of degree

Table 2: the steam cracking productive rate of the wide fraction coking liquid using steam cracker process simulation model to estimate

Initial vacuum resid feed	A	B	C
				API	5.4	9.8	16.5
SC productive rate wt%
				The productive rate of ethene+propylene+C4	28.4	33.9	38.6
Tar (C17+)	26.7	18.0	13.9

Unless otherwise indicated, the implication of the term used herein implication that their this areas should be adopted common; Especially can with reference to HandbookofPetroleumRefiningProcesses, the third edition, RobertA.Meyers, editor, McGraw-Hill (2004).In addition, all preference files, patent, patent application, test procedure (such as ASTM method) and other document quoted herein are by reference to being incorporated to herein completely, to this degree, these disclosures and the present invention are consistent and in all jurisdictions, this being incorporated to allows.In addition, when numerical lower limits and numerical upper limits are listed herein, any lower limit is expected to the scope of any upper limit.

Above the present invention describes with reference to numerous embodiment and specific embodiment.Those skilled in the art will propose a lot of variant according to description detailed above.All these obvious variants are in the scope of whole expections of appending claims.

Claims

C described gas phase is sent to described steam cracker furnace by ();

(d) from the alkene of salvage material at least 30wt% of radiant-type furnace leaving steam cracker furnace, based on the weight of total hydrocarbon material leaving radiant-type furnace;

(e) will from the liquid bottom of the gas/liquid separation of step (b) at the temperature of 538-649 DEG C viscosity breaking with the bottom phase of production viscosity breaking;

F () is by the bottom phase quenching of viscosity breaking;

G () is separated out from the bottom of the viscosity breaking of quenching (i) second liquid phase and (ii) second gas phase in the second gas/liquid separation; With

H second gas phase is incorporated into the steam cracker furnace of step (c) by ().

2. the process of claim 1 wherein that thermal transition district comprises coke granule, described district has the coke granule/fresh feed weight ratio of at least 1:1, based on recycle coke solid and the weight of fresh feed entering described district.

3. the process of claim 1 wherein that described thermal transition district is delay coking device, fluid coker, Flexicoker ^tM, visbreaker or shortening visbreaker.

4. the process of claim 1 wherein 25 DEG C or more the lower operations below the service temperature of the stove section of steam cracker furnace of described first thermal transition district.

5. the process of claim 1 wherein that the charging entering thermal transition district comprises the hydrogen higher than 11.0wt%.

6. the process of claim 1 wherein before entering gas/liquid separation, described thermal transition residual oil is sent to the convection zone of steam cracker.

7. hydrogen or steam are joined the raw material of heating by the arbitrfary point that the process of claim 1 wherein in the process.

8. the method for claim 1, wherein said steam cracker furnace convection zone is heated to the charging in thermal transition district, and the effluent in thermal transition district is directly sent to gas/liquid separation, and is sent to the radiation section of steam cracker furnace subsequently, and do not transport through any intermediate heat exchanger.

9. the process of claim 1 wherein that the first thermal transition district is fluid coker.

10. comprise the method for the hydrocarbon feed of vacuum residuum for cracking, comprising:

D () will be sent to the first thermal transition district with the thermal transition described liquid phase containing residual oil at least partially from the liquid phase containing residual oil described in described separator at least partially, wherein the first thermal transition district is Flexicoker ^tM, one or more in fluid coker or delay coking device;

(g) from the alkene of salvage material at least 30wt% of radiant-type furnace leaving described steam cracker furnace, based on the weight of total hydrocarbon material leaving radiant-type furnace.

The method of 11. claims 10, is wherein heated to the temperature of 538-649 DEG C with viscosity breaking liquid phase at least partially by the liquid phase from step (c); Afterwards the liquid phase quenching of viscosity breaking is also sent to another gas/liquid separation subsequently, the liquid phase of wherein viscosity breaking is separated into the liquid phase of viscosity breaking and the gas phase of viscosity breaking; Thereafter the gas phase of viscosity breaking is incorporated into the thermal transition district of step (d).

The method of 12. claims 10, wherein thermal transition district comprises coke granule and described district has the coke granule/fresh feed weight ratio of at least 1:1, based on recycle coke solid and the weight of fresh feed entering described district.

The method of 13. claims 10, wherein said thermal transition district is delay coking device, fluid coker, Flexicoker ^tM, visbreaker or shortening visbreaker.

The method of 14. claims 10, wherein said thermal transition district is delay coking device.

The method of 15. claims 10, the charging wherein entering thermal transition district comprises the hydrogen higher than 11.0wt%.

The method of 16. claims 10, wherein before entering gas/liquid separation, is sent to the convection zone of steam cracker by thermal transition residual oil.

The method of 17. claims 10, wherein hydrogen or steam are joined the raw material of heating by arbitrfary point in the process.

The method of 18. claims 10, wherein the first thermal transition district is fluid coker.

19. systems comprising the hydrocarbon feed of vacuum residuum for cracking, comprising:

A) be less than the first thermal transition district operated at the temperature of 649 DEG C, this first thermal transition district is selected from: delay coking device, fluid coker, Flexicoker ^tM, visbreaker or shortening visbreaker, described first thermal transition district is connected with b) steam cracker furnace fluid, and described b) steam cracker furnace has the gas/liquid separation be connected with described steam cracker furnace fluid; Wherein

I () configures described first thermal transition district will be converted into the converted product comprising (A) coke granule and (B) steam and product liquid by hydrocarbon feed at least partially;

(ii) described steam cracker furnace at least comprises convection zone and radiation section;

(iii) described convection zone is configured to receive and to heat this steam and product liquid to make steam and product liquid evaporation at least partially;

(iv) described gas/liquid separation is configured to be separated with product liquid with the steam through heating by steam; With

V () configures described radiation section to receive the steam be separated from described gas/liquid separation.

The system of 20. claims 19, comprises the second gas/liquid separation be connected with described thermal transition district fluid further.

The system of 21. claims 19, wherein the first thermal transition district is fluid coker, and described fluid coker comprises:

I) fluidized-bed gasifier,

The system of 22. claims 21, is included in the air/steam entrance bottom described fluidized-bed gasifier further.

The system of 23. claims 21, wherein said fluid coker comprises fluidized-bed heater canister further, it has and connects the recirculated solids pipeline of described heater canister compared with lower part and described gasifier, with at least one gas pipeline, described gas pipeline divides and comparatively the connecting between lower part of described heater canister in the higher part of described gasifier.

The system of 24. claims 21, wherein said transfer line reactor is vertical-lift pipe reactor, and wherein said solid pipeline and described hydrocarbon opening for feed are connected to the comparatively lower part of described reactor.