CN100347274C - Modified thermal processing of heavy hydrocarbon feedstocks - Google Patents

Modified thermal processing of heavy hydrocarbon feedstocks Download PDF

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Publication number
CN100347274C
CN100347274C CNB2004100073371A CN200410007337A CN100347274C CN 100347274 C CN100347274 C CN 100347274C CN B2004100073371 A CNB2004100073371 A CN B2004100073371A CN 200410007337 A CN200410007337 A CN 200410007337A CN 100347274 C CN100347274 C CN 100347274C
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raw material
product
calcium
reheater
reactor
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CN1537923A (en
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巴里·弗瑞尔
道格·克拉克
杰里·F.·克里茨
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Yiwanhuo HTL oil Co.
Yiwanhuo HTL Petroleum Co.,Ltd.
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Ensyn Petroleum International Ltd
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Abstract

The present invention is directed to the upgrading of heavy petroleum oils o f high viscosity and low API gravity that are typically not suitable for pipelining without the use of diluents. It utilizes a short residence-time pyrolytic reactor operating under conditions that result in a rapid pyrolytic distillation with coke formation. Both physical and chemical changes taking place lead to an overall molecular weight reduction in the liquid product and rejection of certain components with the byproduct coke. The liquid product is upgraded primarily because of its substantially reduced viscosity, increased API gravity, and the content of middle and light distillate fractions. While maximizing the overa ll liquid yield, the improvements in viscosity and API gravity can render the liquid product suitable for pigelining without the use of diluents. This invention particularly relates to reducing sulfur emissions during the combustion of byproduct coke (or coke and gas), to reducing the total acid number (TAN) of the liquid product, and to reducing the hydrogen sulfid e content of one, or more than one component of the product stream. The method comprises introducing a particulate heat carrier into an up-flow reactor, introducing the feedstock at a location above the entry of the particulate heat carrier, allowing the heavy hydrocarbon feedstock to interact with the heat carrier for a short time, separating the vapors of the . product stream from the particulate heat carrier and liquid and byproduct solid matter, regenerating the particulate heat carrier in the presence of the calcium compound, and collecting a gaseous and liquid product from the product stream.

Description

The improvement hot-work of heavy hydrocarbon feeds
Technical field
The present invention relates to the Rapid Thermal processing (RTP of viscous oil TM).More particularly, the present invention relates to the method that a kind of reduction comes from one or more gaseous fraction hydrogen sulfide contents in the quick hot worked product stream of heavy hydrocarbon feeds.
Background technology
Heavy oil and asphalt source are replenishing the decline that tradition is light and medium crude oil (medium crude oil) is produced, and increase steadily from the production in these sources.Reduce their viscosity and proportion unless add thinner, otherwise for the specification standards of pipeline, pipeline can not be handled these crude oil.Alternatively, can realize desirable character by the initial stage upgrading.But the crude oil of dilution or the synthetic crude of upgrading obviously are different from traditional crude oil.As a result, asphalt mixture or synthetic crude are not easy to process in traditional fluid catalytic cracking refinery.Therefore, in both cases, in the refinery of configuration process, must further process, perhaps dilution or upgrading raw material.
Many heavy hydrocarbon feeds also have and comprise a large amount of BS﹠amp; The feature of W (basic sediment and water).This raw material is owing to its corrodibility and have sand and water, thereby is not suitable for pipeline transportation or refining.Typically, have less than 0.5wt.%BS﹠amp; The raw material of W feature can pass through pipeline transportation, and those comprise greater amount BS﹠amp; The raw material of W needs processing or processing to a certain degree, thereby reduces BS﹠amp before transportation; W content.These processing comprise storing allows water and particle deposition and hot-work except that anhydrating and other component.But these are handled can increase running cost.Therefore, in technology, need a kind of high efficiency method come the transportation of raw material and further before the processing upgrading have obvious BS﹠amp; The raw material of W content.
Heavy oil and pitch can use a large amount of methods to come upgrading, comprise hot-work (for example, US4,490,234; US 4,294, and 686; US 4,161,442), hydrocracking (US 4,252,634), viscosity breaking (US 4,427,539; US 4,569, and 753; US 5,413, and 702), perhaps catalytic cracking (US 5,723, and 040; US 5,662, and 868; US 5,296, and 131; US 4,985, and 136; US4,772,378; US 4,668, and 378; US 4,578, and 183) program.Several these programs, for example viscosity breaking or catalytic cracking is at the upper reaches of reactor and the particulate contact material of dirty use inertia or catalytic.Catalytic Contact material major part is based on zeolite (referring to for example (US5,723,040; US 5,662, and 868; US 5,296, and 131; US 4,985, and 136; US 4,772, and 378; US 4,668, and 378; US 4,578, and 183; US 4,435, and 272; US 4,263,128), and viscosity breaking typically use the inertia contact material (for example US 4,427,539; US 4,569,753), carbonaceous solids (for example US 5,413,702), perhaps inertia kaolin solid (for example US 4,569,753).
It is known in technology that fluid catalytic cracking (FCC) or other device are used for direct formed asphalt raw material.But the chemical compound lot that exists in the starting material disturbs these processing by being deposited on the contact material.These contamination of raw material things comprise metal, for example vanadium and nickel, coke precursor, for example (Kang Laxun (Conradson)) carbon residue, and bituminous matter.Remove unless in regeneratory furnace, burn, otherwise the deposition of these materials can cause poisoning and need replacing contact material prematurely.This is especially correct for the contact material that uses for the FCC process, because the control of the efficient cracking of process and suitable temp requires contact material to comprise seldom or do not comprise the flammable deposition material or the metal that can disturb catalytic process.
In order to reduce the pollution of catalytic material in the catalytic cracking unit, advised by viscosity breaking (US 5,413,702; US 4,569, and 753; US 4,427,539), heat (US 4,252,634; US 4,161,442) or other process come pretreating raw material, typically use FCC class reactor and be lower than operation under the required temperature of cracking stock (for example US 4,980,045; US4,818,373 and US 4,263,128).These systems and FCC apparatus serial operation, and FCC played a part pretreater.Design these preprocessing process and be used for removing polluting material, and under any cracked condition of mitigation, operate from raw material.These processing have guaranteed that the upgrading of raw material and control cracking take place in the FCC reactor under optimal conditions.
Several these processes (for example US 4,818, and 373; US 4,427, and 539; US 4,311, and 580; US 4,232, and 514; US 4,263, and 128) be used for processing " Residual oil " (i.e. the raw material that produces from the whole crude fractionation) and bottom fraction especially, thus optimization is from the recovery of initial feed supply.The process of disclosed recovery Residual oil or bottom fraction is a physics, and relates to preferential evaporation or fractionation raw material, and raw material has seldom or do not have chemical transformation.These processes also with remove melts combine and the raw material that is suitable for FCC processing be provided.The preferential evaporation of Residual oil occurs under the non-cracking conditions, does not reduce the viscosity of feed composition, and has guaranteed that cracking takes place in the FCC reactor under the condition of control.These approach all do not disclose the upgrading of raw material in this pre-treatment (promptly removing metal and charcoal) process.Be used for hot worked other process of raw material and relate to hydrogenation (hydrogen treatment), this has caused some chemical transformation of raw material.
US 4,294, and 686 disclose and are used for the vapor distillation process in the presence of hydrogen that pre-treatment FCC processes raw material.The document also indicates the viscosity that this process can also be used to reduce raw material, thereby makes raw material can be suitable for transporting in pipeline.But it openly is not used for producing the use of the short residence time reactor that can transport raw material.
During heavy-hydrocarbon oil processing, sulphur is produced and is become the component of stack gas, needs to use suitable washer to remove.US 4,325, and 817, US 4,263,128 described and used different catalysts to come SO in the absorption and regeneration stove oxidizing atmosphere xThen, catalyzer is transferred in the reducing atmosphere of reactor, sulphur is converted to hydrogen sulfide there, uses washer to remove from stack gas then.Similar process is at US 4,980, and open in 045, reactive oxidants aluminium in this patent (preferably gama-alumina) is used as fine-particle solid, perhaps as the fine-particle solid component in the heavy oil preprocessing process.Reactive oxidants aluminium is used to be absorbed in oxygen and has gaseous sulfur compound in the lower flue gas.US 4,604, and 268 have instructed and use cerium oxide to remove hydrogen sulfide in the gas.
The optional process of removing desulfuration from liquid stream comprises zinc oxide silica and the fluorochemicals that uses US 5,077,261 instructions, and perhaps US 5,102, metal silicate, zinc oxide, silicon-dioxide and the molybdenumdisulphide (US 5,310,717) of instruction in 854.US 4,661, and 240 disclose the method for using calcium to reduce sulphur release between coking period.
The present invention relates to the upgrading heavy hydrocarbon feeds, such as, but be not limited to the method for heavy oil or asphalt stock, this method is used the short residence time pyrolysis reactor of operating under the condition of reacting the upgrading raw material by cracking and coking.The raw material that uses in this process can comprise the BS﹠amp of obvious level; W and still can have been processed, thereby increase the efficient that raw material is handled effectively.Process according to the present invention provides the part upgrading raw material of the API gravity of viscosity that preparation shows reduction and increase.Process described herein is optionally removed metal, salt, water and is known as bitum carbonaceous material.This process makes the maximization of liquefaction productive rate by minimizing charcoal and oxidation generation.In addition, the liquefied product that is produced by the inventive method shows the total acid value (TAN) of reduction with respect to untreated hydrocarbon feed.The present invention also provides a kind of method that is used for being reduced in the sulfurous gas content that produces during processing raw material.
By reducing the TAN of product, heavy oil feedstock with high TAN requires higher market value, because they can use known reforming system, for example processing is easily advanced-gone on foot to FCC or other catalytic cracking program, otherwise because its corrosion property requires the market value of reduction.High TAN oil comprises high-caliber naphthenic acid usually, needs dilution before processing or refining.
The present invention further provides the method for hydrogen sulfide content that a kind of reduction comes from one or more gaseous fractions of crude oil Rapid Thermal processed products stream.
A target of the present invention is the shortcoming that overcomes prior art.
Above-mentioned target realizes that by the combination of features that principal right of the present invention requires dependent claims discloses further advantageous embodiment of the present invention.
Summary of the invention
The present invention relates to the Rapid Thermal processing (RTP of viscous oil raw material TM).More particularly, the present invention relates to the method that a kind of reduction comes from one or more gaseous fraction hydrogen sulfide contents of the quick hot worked product stream of heavy hydrocarbon feeds.
The invention provides the method that a kind of reduction comes from one or more gaseous fraction hydrogen sulfide contents of the quick hot worked product stream of heavy hydrocarbon feeds, this method comprises:
(i) the Rapid Thermal processing of heavy hydrocarbon feeds in the presence of calcium cpd;
The (ii) Rapid Thermal processing of heavy hydrocarbon feeds in the presence of calcium cpd, and the regeneration in reheater in the presence of calcium cpd of particulate thermal barrier;
The (iii) Rapid Thermal of heavy hydrocarbon feeds processing, and the regeneration in reheater in the presence of calcium cpd of particulate thermal barrier.
In preferred embodiments, the Rapid Thermal procedure of processing comprises makes heavy hydrocarbon feeds be less than about 5 seconds with the interaction of particulate thermal barrier in reactor, thereby produces product stream, and wherein the ratio of particulate thermal barrier and heavy hydrocarbon feeds was from about 10: 1 to about 200: 1.
In another embodiment, method of the present invention further comprises the step of removing the mixture that comprises product stream and particulate thermal barrier from reactor.
In other embodiments, method of the present invention further comprises the step of from mixture separated product stream and particulate thermal barrier.
In another embodiment, method of the present invention further is included in the step of regeneration of particle thermal barrier in the reheater.In preferred embodiments, the temperature of reheater is from about 600 to about 900 ℃, preferably from about 600 to about 815 ℃, more preferably from about 700 to about 800 ℃.
In further embodiment, the inventive method comprises that further collection distillates product and bottoms from product stream.
The invention still further relates to aforesaid method, wherein bottoms is accepted further Rapid Thermal procedure of processing, comprise and make product liquid in reactor, be less than about 5 seconds with the interaction of particulate thermal barrier, thereby produce product stream, wherein the ratio of particulate thermal barrier and heavy hydrocarbon feeds was from about 10: 1 to about 200: 1.
In above-mentioned method, add calcium cpd to about 5 times amount with about 0.2 of the stoichiometry that enters sulphur in the system response device.Preferably, the amount of the calcium cpd of adding is about 1.7 to 2 times of sulphur content stoichiometry in by product charcoal and the gas.
On raw material enters in the flow reactor before, perhaps prior to flow reactor on entering enter separation column before in heavy hydrocarbon feeds, add calcium cpd.In addition, calcium cpd can add in the sand reheater, and perhaps calcium cpd adds in sand reheater and the heavy hydrocarbon feeds.
In embodiments of the invention, before the Rapid Thermal procedure of processing, raw material is introduced in the separation column of separate raw materials volatile constituent from the raw material liq component.Collect gaseous fraction, and liquid ingredient is accepted aforesaid Rapid Thermal processing.In another embodiment, raw material combines with calcium cpd before in introducing separation column.
The present invention also provides a kind of method of upgrading heavy hydrocarbon feeds, and this method comprises:
(i) the Rapid Thermal processing of heavy hydrocarbon feeds in the presence of calcium cpd;
The (ii) Rapid Thermal processing of heavy hydrocarbon feeds in the presence of calcium cpd, and the regeneration in reheater in the presence of calcium cpd of particulate thermal barrier;
The (iii) Rapid Thermal of heavy hydrocarbon feeds processing, and the regeneration in reheater in the presence of calcium cpd of particulate thermal barrier.
The present invention also provides aforesaid method, wherein calcium cpd is selected from lime acetate, calcium formiate, calcium propionate, contains the bio oil composition of calcium salt (for example at US 5,264, described in 623, the content of this patent disclosure is incorporated herein for referencial use), from contain calcium salt bio oil composition isolating calcium salt, Ca (OH) 2[CaOH 2O], CaCO 3, lime [CaO], and their mixture.Calcium cpd can be selected from MgO, Mg (OH) 2And MgCO 3Magnesium compound be used in combination.Calcium cpd can combine with the water of raw material and 0～5% (wt/wt).In embodiments of the present invention, water is the form of steam.
The present invention proposes the demand of this area, relate to the part chemical modification or the gentle cracking of raw material, and reduced the H of gaseous product stream simultaneously heavy oil or the quick upgrading process of asphalt stock 2S content.A large amount of heavy hydrocarbon feeds comprise and contain obvious amount BS﹠amp; The raw material of W can be processed by method as herein described, and the SO that produces in the stack gas x(perhaps any gaseous sulfur species) burst size, and the hydrogen sulfide content of one or more gaseous fractions in the product stream.With respect to initial (undressed) raw material, the product of being produced by the inventive method also shows the total acid value (TAN) of reduction.As a result, the product that the present invention produces has the corrodibility of reduction, and can transport and be used for further processing and upgrading.Therefore, the present invention is suitable for processing the crude oil of high TAN, for example from Marlim, the Kuito of Angola, Heidrun, Troll, Balder, Alba and the Gryhpon in the North Sea of Brazil.
Method described herein can also reduce the pollutant level in the raw material, thereby the pollution that has alleviated the catalytic Contact material, the material with the component that exists in heavy oil or asphalt stock that for example those use in cracking or hydrocracking.The calcium cpd that uses in the inventive method cannot directly use with cracking catalyst (catalyzer that for example uses in FCC), because it can change the surface acidity of catalyzer unfriendly, for example in these systems, use amorphous alumina, aluminium oxide-silicon oxide or crystalline form (zeolite) aluminium oxide-silicon oxide catalyzer.But calcium is easy to remove from product stream during Rapid Thermal processing, thereby the calcium contents of product is low.
Process described herein can be used to process many different raw materials, thereby produces required product.For instance, the raw material with high TAN and low sulfur content feature can be processed by add calcium cpd before processing in raw material.In this case, reduced the TAN of product, and the hydrogen sulfide content of one or more gaseous fractions of product stream.Alternatively, show high sulfur content but the raw material of low TAN does not need to add calcium cpd (because TAN has reduced) in raw material, but for the sulphur that reduces during the heat-carrier regeneration discharges, and the hydrogen sulfide content of one or more gaseous fractions of product stream, calcium cpd can be added in the sand reheater, in the raw material, perhaps among both.Similarly, the raw material with high TAN and high sulfur content feature can be processed by calcium cpd being joined in raw material and the sand reheater, thereby has reduced the TAN in the product, reduced the SO in the stack gas that produces from the sand reheater xDischarge, and reduced the hydrogen sulfide content of one or more gaseous fractions of product stream.
Therefore gaseous fraction with reduction hydrogen sulfide content can be used for the post-treatment firing system without any need for appreciable cleaning or adjusting, for example is used for steam boiler or hot firing system.Alternatively, having the gaseous fraction that reduces hydrogen sulfide content can recirculation be used for fast pyrolysis reactor, perhaps is collected and lays in the application that is used for future.Having the gaseous fraction that reduces hydrogen sulfide content can not obtain to clean and the outlying zone of adjustments of gas is useful especially.
Description of drawings
These and other feature of the present invention will become more obvious from explanation with reference to the accompanying drawings, wherein:
Fig. 1 relates to the embodiment synoptic diagram of the embodiment of the present invention of raw material pyrolysis process system.Line A-D and I-L represent optional thief hole.
Fig. 2 relates to raw material is introduced the embodiment synoptic diagram of embodiment of the present invention of the charging system of raw material pyrolysis process system.
Fig. 3 relates to raw material is introduced the embodiment synoptic diagram of embodiment of the present invention of the charging system of two stage process subordinate phase, uses raw material pyrolysis process described herein system.
Fig. 4 relates to be used to obtain the embodiment synoptic diagram of embodiment of the present invention of the recovery system of raw material, and raw material or collect from primary condenser perhaps is recycled to the subordinate phase of two stage process of using raw material pyrolysis process described herein system.
Fig. 5 relates to the embodiment synoptic diagram of the embodiment of the present invention of multistage raw material pyrolysis process system.Line A-E and I-N represent optional thief hole.
Shown in Figure 6 is that (i) comes from the SO in the stack gas of the sand reheater that uses among the embodiment of the present invention embodiment 2Concentration value (ppm), (ii) the temperature value of sand reheater (℃), the both measures as the function of time.SO 2The temperature value of concentration value and sand reheater is to have or do not exist Ca (OH) 2Situation under during the formed asphalt raw material, measure.Referring to the definition literal that arrives the timed interval of J mark with A.
Fig. 7 is Fig. 6 from 13:05 hour to 14:15 hour enlarged view.
Fig. 8 represents to come from SO in the stack gas of the sand reheater that uses among the embodiment of the present invention embodiment 2Concentration (ppm) is to the variation diagram of time.SO 2Concentration value is at Ca (OH) 2Existence under during the processing of San Ardo heavy oil feedstock (from Bakersfiele, California obtain), measure.
Embodiment
The present invention relates to the Rapid Thermal processing (RTP of viscous oil raw material TM).More particularly, the present invention relates to the method that a kind of reduction comes from one or more gaseous fraction hydrogen sulfide contents of the quick hot worked product stream of heavy hydrocarbon feeds.
Following explanation only is a preferred embodiment of by way of example, and is used to implement the combination of essential feature of the present invention without limits.
The invention provides the method that a kind of reduction comes from one or more gaseous fraction hydrogen sulfide contents of the quick hot worked product stream of heavy hydrocarbon feeds, this method comprises:
(i) the Rapid Thermal processing of heavy hydrocarbon feeds in the presence of calcium cpd;
The (ii) Rapid Thermal processing of heavy hydrocarbon feeds in the presence of calcium cpd, and the regeneration in reheater in the presence of calcium cpd of particulate thermal barrier;
The (iii) Rapid Thermal of heavy hydrocarbon feeds processing, and the regeneration in reheater in the presence of calcium cpd of particulate thermal barrier.
The present invention also provides and reduced SO in the stack gas during the upgrading heavy hydrocarbon feeds xThe method that discharges is included in that calcium cpd exists down or calcium cpd is directly added and comes Rapid Thermal processing heavy hydrocarbon feeds in sand reheater or the revivifier.
The present invention further provides reduction heavy hydrocarbon feeds, product, perhaps the method for both total acid values (TAN) is included in calcium cpd and has Rapid Thermal processing heavy hydrocarbon feeds down.
The present invention also provides during the upgrading heavy hydrocarbon feeds and has reduced SO in the stack gas xDischarge and reduce heavy hydrocarbon feeds, product or heavy hydrocarbon feeds and come from the method for the total acid value (TAN) of its product.This method is included in calcium cpd and has Rapid Thermal processing heavy hydrocarbon feeds down, and optional calcium cpd is directly added in the sand reheater.
The present invention also provides a kind of method, is used for (i) reduction stack gas SO during the upgrading heavy hydrocarbon feeds xDischarge, (ii) reduce heavy hydrocarbon feeds, product, perhaps heavy hydrocarbon feeds and come from the total acid value (TAN) of its product, and the hydrogen sulfide content that (iii) reduces one or more gaseous fractions of product stream.This method is included in calcium cpd and has Rapid Thermal processing heavy hydrocarbon feeds down, and wherein calcium cpd can also directly add in the sand reheater alternatively.
" raw material " or " heavy hydrocarbon feeds " often means the oil source oil of the high-density that is called (but being not limited to) heavy crude, heavy oil, (oil-sand) pitch or refining Residual oil (oil or pitch) and viscosity.But term " raw material " can also comprise the bottom fraction of petroleum crude oil, for example normal pressure tower bottoms or vacuum tower bottoms.It can also comprise and comes from coal and resinous shale oil.In addition, raw material can comprise a large amount of BS﹠amp; W (basic sediment and water) for instance, but is not limited to be higher than the BS﹠amp of 0.5wt.%; W content.Heavy oil and pitch are preferred raw materials.
In order to use, raw material can have following feature:
I) high TAN, low sulfur content,
Ii) low TAN, high sulfur content,
Iii) high TAN, high sulfur content,
Iv) low TAN, low sulfur content.
Having top i) raw material of feature can come pre-treatment by add calcium cpd in processing forward direction raw material.This pretreated effect is the TAN that has reduced in raw material and the product, and has reduced the hydrogen sulfide content of one or more gaseous fractions of product stream.Above having ii) the raw material of feature do not need in raw material, to add calcium cpd, but calcium cpd can be added among sand reheater, raw material or both, discharge thereby during heat-carrier regeneration, reduce sulphur, and reduce the hydrogen sulfide content of one or more gaseous fractions of product stream.Above having iii) the raw material of feature can process by in raw material and sand reheater, adding calcium cpd, thereby reduce TAN in the product, reduce the SO in the stack gas that from the sand reheater, produces x(or any gaseous sulfur species) discharge, and reduce the hydrogen sulfide content of one or more gaseous fractions of product stream.The reason of adding the additional quantity calcium cpd in the sand reheater is that it can make than reducing raw material and the more calcium of product and reduces high sulfur content in the stack gas.When iv) raw material of feature, need not in raw material and sand reheater, to add calcium cpd.Therefore, the present invention is suitable for processing the crude oil that has extensive character in a large number, for example those have the crude oil of high TAN feature, Marlim, the Kuito of Angola, Heidrun, Troll, Balder, Alba and the Gryhpon in the North Sea, Saskatchewan heavy crude, perhaps Athabasca pitch including, but not limited to Brazil.
These heavy oil and asphalt stock typically viscosity and be difficult to the transportation.Pitch typically comprises most of compound polycyclic hydrocarbon bituminous matter, and they can increase the viscosity of this raw material, and certain form pre-treatment of this raw material is essential for transportation.This pre-treatment is used solvent cut before typically being included in transportation.
As described herein, for enriching brea, the raw material that came from the Tar sands compound before upgrading is not by preprocessing (embodiment 1 referring to this examples of materials is analyzed thinks that this embodiment is restrictive).But the preprocessing of oil sands bitumen relates to method well known in the art, comprises heat or cold water treatment, perhaps produces the solvent extraction of pitch gas-oil solution.These processing treatment are typically isolated pitch from sand.For instance, this water preprocessing is handled to relate to and is formed the pitch-hot water/NaOH slurry that comprises Tar sands, therefrom makes the sand sedimentation, and also removes shakeout and add more hot water in the pitch that suspends in order to dilute main ingredient.Cold water processing relates to pulverizes oil-sand and it is suspended in the oil fuel in water, use solvent cut pitch then and separate bitumen from sand-water residue.Cold water processing is described in US 4,818 more completely, in 373 open (being incorporated herein for referencial use).These bitumen product are the candidate feed that are used for further processing described herein.
Pitch can use process of the present invention or other process such as FCC, viscosity breaking, hydrocracking to wait upgrading.The pre-treatment of Tar sands raw material can also comprise heat or cold water treatment, for example in order to use process described herein, perhaps other upgrading process comprises that upgrading raw materials such as degreasing (using Rapid Thermal processing as herein described), FCC, hydrocracking, coking, viscosity breaking partly remove the shakeout component before.Therefore, should be appreciated that term " raw material " also comprises pretreated raw material, describes the raw material of preparation including, but not limited to those as this paper.
Light raw material can also be processed according to the inventive method as herein described.For instance, as described in more detail below, the product liquid that obtains from pyrolysis processing first as herein described can be further processed (for example compound recirculation and multistage processing by the inventive method; Referring to Fig. 5 and embodiment 3 and 4), thus obtain to have the product liquid that reduces viscosity, reduces metal (especially nickel, vanadium) and water-content and bigger API gravity field feature.In addition, from the product liquid of other process acquisition well known in the art, such as, but be not limited to US 5,662,868; US4,980,045; US 4,818, and 373; US 4,569, and 753; US 4,435, and 272; US 4,427, and 538; US 4,427, and 539; US 4,328, and 091; US 4,311, and 580; US 4,243, and 514; US4,294,686, can be as the raw material of process described herein.Therefore, the present invention has also considered to comprise the product liquid of gas oil, vacuum gas oil, topped oil or preprocessing from the use of the light raw material of heavy oil or pitch acquisition.These light raw materials can use method of the present invention to handle, thereby these raw materials of upgrading are used for using, such as, but be not limited to the further processing of FCC, hydrocracking etc.
The product liquid that obtains from process as herein described can be suitable for transportation in pipeline and allow its further processing elsewhere.Typically, further process the remote position that occurs in raw material production.But directly input is further in the device of upgrading raw material to use product liquid that the inventive method produces, and such as, but be not limited to coking, viscosity breaking or hydrocracking etc., this is considered to also within the scope of the invention.At this on the one hand, pyrolysis reactor of the present invention partly upgrading raw material, played the pretreater effect that further processes raw material simultaneously, such as, but be not limited to open in following patent: US 5,662,868; US 4,980, and 045; US 4,818, and 373; US 4,569, and 753; US 4,435, and 272; US 4,427, and 538; US4,427,539; US 4,328, and 091; US 4,311, and 580; US 4,243, and 514; US 4,294,686 (all patents are incorporated herein for referencial use).
Raw material of the present invention uses fast pyrolysis reactor as at US 5,792,340 (W/O91/11499; EP 513,051) in disclosed reactor process.Can also use other known riser reactor, such as, but be not limited to US 4,427,539 with short residence time; US 4,569, and 753; US 4,818, and 373; US 4,243,514 (these patents are incorporated herein for referencial use).Reactor is preferably moving under about 600 ℃ temperature from about 450 ℃, more preferably from about 480 ℃ to about 550 ℃.The duration of contact of thermal barrier and raw material is preferably from about 0.01 to about 20 seconds, more preferably from about 0.1 to about 5 seconds, most preferably from about 0.5 to about 2 seconds.
Preferably, the thermal barrier that uses in the pyrolysis reactor be catalytically inactive or show low catalytic activity.This thermal barrier can be a fine-particle solid, preferably sand, for example silica sand.Silica sand means any sand that is higher than about 80% silicon-dioxide that comprises, and preferably is higher than about 95% silicon-dioxide, and more preferably is higher than about 99% silicon-dioxide.Should be understood to top composition and be can be as an example of the silica sand of thermal barrier described herein, but the variation of these component ratios can exist and still is suitable for use as thermal barrier in other silica sand.Can also use other known inert particulate thermal barrier or contact material, for example at US 4,818, aluminum oxide, magnesium and the calcium oxide of disclosed kaolinton, rutile, low surface area in 373 or US4,243,514.
As summarizing in more detail below, one aspect of the present invention relates to using fast pyrogenation to process raw material and adds calcium cpd in the forward direction stock oil, such as, but be not limited to lime acetate, calcium formiate, calcium propionate, contain the bio oil composition of calcium salt (for example at US 5,264, described in 623, the content of this patent disclosure is incorporated herein for referencial use), from contain calcium salt bio oil composition isolating calcium salt, Ca (OH) 2[CaOH 2O], CaCO 3, lime [CaO], perhaps their mixture.Calcium cpd can be selected from MgO, Mg (OH) 2And MgCO 3Magnesium compound be used in combination.Comprise CaCO 3The calcite type Wingdale, perhaps comprise CaMg (CO 3) 2The dolomite type Wingdale also can be used as calcium cpd.
Calcium cpd by preferably with 0～5% water, more preferably be added in the raw material with 1～3% water.Be used to pyrolysis heavy oil in process of the present invention, for example in the situation of vacuum tar residue, calcium cpd is preferably used vapo(u)r blasting to introduce in the pyrolysis reactor.The calcium cpd that uses among the present invention can also more preferably use with the form of fine powder with the powder type that grinds.
The moisture that exists in the reactor is evaporated during the raw material pyrolysis, and forms the product stream of part.This water can use retrieving arrangement such as liquid/vapor separator or freezing plant to reclaim, dirty and the mist eliminator (for example mist eliminator 60 of Fig. 1) that these devices can be positioned at condensation tower (for example condenser 40 and 50 of Fig. 1) for instance before, perhaps use to strengthen retrieving arrangement (45, can be positioned at after the mist eliminator in the time of Fig. 1).
In raw material, add neutralized acid in oily of calcium cpd, by the total acid value test (TAN tests: ASTM D664 neutralization value, referring to embodiment 7A; Another TAN test comprises ASTM D974) determine, and reduced the release (referring to embodiment 8A) of gaseous sulfur.If can in raw material, obtain, for example when using steam during the course, then can use CaO replaced C a (OH) 2Reduce acid.At the processing initial stage, the reduction of oily TAN value may cause improving the life-span of equipment used in performance and the pyrolysis system.In addition, in reheater (30, Fig. 1 also is called revivifier, perhaps the coke combustion chamber), add calcium cpd and make the flue gas desulfurization (FGD) (referring to embodiment 8A and B) that from the sand reheater, produces, reduce gasiform sulphur, SO x, perhaps other gaseous sulfur species.
Therefore, the present invention relates to the process of Rapid Thermal processing heavy hydrocarbon feeds in the presence of the interpolation calcium cpd.Calcium cpd can add at any point of Rapid Thermal system of processing.Preferred inlet is revivifier (sand reheater) or enters reactor or fractional column raw material before, thereby reduces the hydrogen sulfide content of one or more gaseous fractions of sulphur release, TAN, product stream, perhaps all these three kinds.
SO xMean gasiform oxysulfide species, for example SO 2And SO 3But other can also can be removed from stack gas as herein described or raw material with the interactional gaseous sulfur species of calcium cpd.
The raw material that Rapid Thermal processing comprises calcium cpd has formed the Ca-S compound in revivifier, for example calcium sulfate, calcium sulfite or sulfurated lime.Separate in the particulate thermal barrier that these compounds can use from Rapid Thermal system of processing as herein described, and can remove if desired.Alternatively, in raw material, add particulate lime and played thermal barrier, and be recycled and pass through system.If calcium cpd is recycled with the particulate thermal barrier, a part of then calcium cpd need periodically be removed, and adds new calcium cpd again in raw material.
The present invention has also described for the desulfurization that strengthens stack gas and has added lime acetate, calcium formiate, calcium propionate in the sand reheater, contain the bio oil composition of calcium salt (for example at US 5,264, described in 623, the content of this patent disclosure is incorporated herein for referencial use), from contain calcium salt bio oil composition isolating calcium salt, Ca (OH) 2[CaOH 2O], CaCO 3, lime [CaO], and their mixture.Use method as herein described, by in the sand reheater, adding the desulfurization that lime has been realized stack gas, the amount of adding is corresponding to about 0.2 to about 5 times of stoichiometry, preferably stoichiometry required about 1.0 to about 3 times, more preferably corresponding to about 1.7 to about 2 times of the needed stoichiometry of sulphur in the coke that enters sand reheater (coke burner).Add calcium cpds with about 1.7 to about 2 times of stoichiometric amounts, can remove in the stack gas up to about 90% or more SO x
The amount of adding the calcium cpd in raw material or the sand reheater to can be by analyzing sulphur (SO x) level that discharges and add compound and come the method for balance sulphur level to determine.
Use the fast pyrolysis processes raw material to cause the generation of the product vapor solid by-product relevant with thermal barrier.Separated thermal barrier from product stream after, enriched product steam obtains product liquid and gaseous by-product.For instance, but should not think restriction, as described herein from the product liquid that heavy oil upgrading produces, it is characterized in that having following character:
-full boiling point is lower than about 660 ℃, is preferably lower than about 600 ℃, and more preferably is lower than about 540 ℃;
-API gravity is at least about 12, and preferably is higher than about 17 (API gravity=[141.5/ proportion]-131.5 wherein; API gravity is high more, and material is light more);
The metal content of-very big reduction comprises V and Ni;
The levels of viscosity of-very big reduction (reduced more than 25 times than raw material, for example determined) at 40 ℃, and
-the liquid product yield of 60vol% at least, preferably productive rate is higher than about 70vol%, and more preferably productive rate is higher than about 80%.
According to method as herein described, from the product liquid that the formed asphalt raw material obtains, should not think restriction, its feature has:
-API gravity from about 10 to about 21;
-15 ℃ density @ from about 0.93 to about 1.0;
The metal content of-very big reduction comprises V and Ni;
-than the viscosity (for example determining) of the very big reduction of raw material reduction, reach above 20 times at 40 ℃
-the liquid product yield of 60vol% at least, preferably productive rate is higher than about 75vol%.
The high yield of the product liquid that produces according to the present invention and the viscosity of reduction permission product liquid seldom or not add under the thinner in interpolation further to be processed to refinery by pipeline transportation.In addition, product liquid shows pollutent (bituminous matter, metal and the water) level of reduction.Therefore, product liquid can also as raw material or directly, perhaps after the transportation, for example being used to use, FCC, hydrocracking wait further and process.
In addition, product liquid of the present invention can use the generally well-known simulation distil in this area (SimDist) analysis to characterize, such as, but be not limited to ASTM D 5307-97 or HT 750 (NCUT).The product liquid that SimDist analysis revealed processing heavy oil or pitch obtain has one of following surface properties, perhaps following combination of features (referring to embodiment 1,2 and 5):
Have and be lower than 50% component and produce (vacuum resid cut) in temperature more than 538 ℃;
Comprising from about 60% to about 95% product is producing below 538 ℃.Preferably from about 62% to about 85% product is producing (promptly before the vacuum resid cut) during the SimDist below 538 ℃;
Having from about 1.0% to about 10% product liquid is producing below 193 ℃.Preferably from about 1.2% to about 6.5% producing (promptly before raw gasline and kerosene(oil)fraction) below 193 ℃;
Having from about 2% to about 6% product liquid produces 193～232 ℃.Preferably from about 2.5% to about 5% 193～232 ℃, produce (kerosene(oil)fraction);
Having from about 10% to about 25% product liquid produces 232～327 ℃.Preferably from about 13% to about 24% 232～327 ℃, produce (diesel oil distillate);
Having from about 6% to about 15% product liquid produces 327～360 ℃.Preferably from about 6.5% to about 11% 327～360 ℃, produce (light vacuum gas oil (VGO) cut);
Having from about 34.5% to about 60% product liquid produces 360～538 ℃.Preferably from about 35% to about 55% 360～538 ℃, produce (heavy VGO cut);
The vacuum gas oil as distillation fraction (VGO) that obtains from Rapid Thermal Working liquids product as herein described can come catalytic cracking as raw material, thereby the heavy compound of VGO is changed into a large amount of compounds than light weight, for example gas (C 4Lighter), gasoline, light cracked oil and heavy gas oil.The quality of VGO cut and characteristic can use standard method well known in the art to analyze, for example little activity test (MAT), the K-factor and aniline point analysis.The minimum temperature of equal-volume aniline and test sample complete miscibility has been determined in the aniline point analysis.The aniline point of petroleum product and hydrocarbon solvent is determined typically to use ASTM method D611 to implement.Product with high aniline point feature has low aromatics, cyclic hydrocarbon, and high paraffinic hydrocarbon (more high-molecular weight component).Therefore the VGO of prior art is characterized by has low aniline point, has bad cracking characteristic, so be worthless as the raw material of catalytic cracking.Aniline point all is favourable than any increase of prior art raw material, and the VGO that needs to have high aniline point feature in this area.Typically, the cracking feature of aniline point and raw material and the calculating aniline point that obtains from MAT are well relevant.But observation aniline point and the expected value of the VGO that produces according to described program are not inconsistent.The estimation aniline point of several raw materials is higher than the value (referring to embodiment 6, table 16 and 17) of measurement.This shows that it is unique that the VGO that uses the inventive method to produce compares with the VGO of prior art.In addition, VGO of the present invention is characterized by has unique hydrocarbon distribution, comprises about 38% single aromatic hydrocarbon and thiophene aromatic hydrocarbon.The molecule of these types has a plurality of side chains that can obtain from cracking, and provides than typically having low-level single aromatic hydrocarbon and the higher level of conversion of thiophene aromatic hydrocarbon in the prior art.Do not wish to be subject to theory, the increasing amount of single aromatic hydrocarbon and thiophene aromatic hydrocarbon may cause the catalytic cracking character of observation in the MAT test and the difference between definite aniline point.
Thereby be used for the first method that the upgrading raw material obtains to have required character product liquid and relate to single-stage technology.With reference to Fig. 1, in brief, the fast pyrogenation system comprises the feed system (10 that generally is expressed as raw material injecting reactor (20), also see ginseng Fig. 2 and 3), from product vapor (for example 100 and 180, heat of dissociation carrier and thermal barrier is recycled to the inorganic thermal barrier reheat system of particulate (30) of thermal barrier separation system, reheat and the regenerative heat carrier of reheat/regeneration system rapidly (30) Fig. 1), and elementary (40) and secondary (50) condenser of collecting product.Alternatively, fractional column such as, but be not limited to C-400 fractional column (discussing in more detail hereinafter), can be used for replacing separation condenser to collect product from steam.The calcium sill, such as but not limited to lime acetate, calcium formiate, calcium propionate, contain the bio oil composition of calcium salt (for example at US 5, described in 264,623, the content of this patent disclosure is incorporated herein for referencial use), from contain calcium salt bio oil composition isolating calcium salt, Ca (OH) 2[CaOH 2O], CaCO 3, lime [CaO] and their mixture can add in the reheater (30), thereby reduce SO in the stack gas xDischarge, perhaps can add and reduce TAN in the raw material, and reduce the hydrogen sulfide content of one or more gaseous fractions in the product stream.
The raw material of preheating just enters reactor below mixing zone (170), and by the make progress air flow contact of the intravital thermal lag carrier of traffic flow, and the thermal lag carrier is typically by the recycle gas of recirculation gas circuit (210) supply.Raw material can obtain after by fractional column, and wherein gaseous fraction is removed, and nonvolatile element is transferred to and is used for further processing in the reactor.Short mix and the heat transfer by conduction from the thermal barrier to the raw material are carried out in the short residence time transform portion of reactor.Raw material can be by entering in the reactor one of at least along the several position of reactor length.Different inlet points shown in Fig. 1 and 2 are limiting examples of these in-positions.By several inlet points are provided along reactor length, can change the length of residence time in the reactor.For example, for long residence time, raw material enters reactor by position down at reactor, and for the residence time than weak point, the position of raw material on reactor leans on enters reactor.Under all these situations, the raw material of introducing mixes in the mixing zone (170) of reactor with the mobile thermal barrier that makes progress.The product vapor that produces during the pyrolysis use suitable condensing works (40,50, Fig. 1) cool off or fractional column is collected, obtain product liquid.
In order to reduce the SO in the stack gas 2Discharge, entering reactor (20) any some place before, for example in feeding line (270,280, Fig. 1 and 5), perhaps before or after 160 (Fig. 2), in feeding line, add the calcium sill, such as but not limited to lime acetate, calcium formiate, calcium propionate, contain the bio oil composition of calcium salt (for example at US 5,264, described in 623, the content of this patent disclosure is incorporated herein for referencial use), from contain calcium salt bio oil composition isolating calcium salt, Ca (OH) 2[CaOH 2O], CaCO 3, lime [CaO], and their mixture.Add calcium sill such as CaO in sand reheater (30), can carry out in the pipeline (290,300) from cyclonic separator 100 or 180, cyclonic separator is recirculated into sand and coke in the sand reheater.Calcium cpd can also directly add in the sand reheater.
Be to be understood that other fast pyrogenation system that uses optional heat carrier, thermal barrier separator, different quantities or big or small condenser, comprise the difference of reactor design, can be used to prepare upgraded product of the present invention.For instance, do not think to be limited, in US 4,427,539; US4,569,753; US 4,818, and 373; US 4,243, and disclosed reactor can be modified under condition as herein described and operate in 514 (these patents are incorporated herein for referencial use), have the chemical modification product that increases API and reduce viscosity thereby produce.Reactor preferably from about 450 ℃ to about 600 ℃, more preferably turns round under about 550 ℃ temperature from about 480 ℃.
Then after pyrolysis feed in the presence of the inert heat carrier, the coke that comprises pollutent in the raw material is deposited on the inert heat carrier.These pollutents comprise metal (for example nickel and vanadium), nitrogen and sulphur.Therefore, inert heat carrier needs regeneration before introducing in the reaction stream again.Inert heat carrier is regeneration in sand reheater or revivifier (30, Fig. 1 and 5).Thermal barrier can arrive about 900 ℃ at the fluidized-bed inherent about 600 of sand reheater (30), preferably from 600 to 815 ℃, more preferably regenerates by burning under from 700 to 800 ℃ the temperature.In addition, when needs, can remove settling from thermal barrier by acid treatment, for example US 4,818, disclosed content in 373 (these patents are incorporated herein for referencial use).Then, the regenerated thermal barrier of heating is introduced in the reactor (20) and again as the thermal barrier of fast pyrogenation.
(10, Fig. 2) raw material with preheating offers reactor (20) to feed system.The embodiment of the feed system that limits by any way is not as shown in Figure 2, but other embodiment of feed system all within the scope of the invention, such as, but be not limited to feeding preheating apparatus as Fig. 5 (hereinafter describe), and can choose wantonly with feed system (10, Fig. 5) be used in combination.(be typically expressed as 10, Fig. 2) be designed to provides the preheating material of regulating flow to reactor assembly (20) to feed system.Feed system shown in Fig. 2 comprises that use indirect heating band (130) is heated to 80 ℃ raw material preheating surge tank (110), and links to each other with recirculation/transferpump (120).Raw material also mixes in 80 ℃ of following thermostatically heating in this jar.The raw material of heat is pumped to primary feed jar (140) from surge tank, the primary feed jar also uses indirect heating band (130) heating if desired.But, be to be understood that for the raw material of heating is provided to reactor, also can change feed system.Primary feed jar (140) can also be equipped recirculation/transferpump (150).Heated spot transfer limes (heat traced transfer lines) (160) is maintained at about 100～300 ℃, and by injection nozzle (70, Fig. 2) enter before the reactor preheated.The atomizing of locating near the injection nozzle (70) that is positioned at reactor (20) mixing zone (170) can realize by any proper device.Nozzle arrangement should provide in the homodisperse material inflow reactor.For instance, not restriction by any way can be used the single-phase flow atomizing, perhaps the mechanical pressure of two-phase flow atomizing nozzle.Under the situation of two-phase flow atomizing nozzle, the byproduct gas of steam or recirculation can be used as carrier.For the accurate feedback control (for example pressure unit, temperature sensor, DC controller, No. 3 valve gas meters etc.) of system, instrumentation can be scattered in total system.
Feedstock conversion (typically is lower than 750 ℃ in the temperature of gentleness, preferably from about 450 ℃ to about 600 ℃, more preferably from about 480 ℃ to about 550 ℃) under in the mixing zone (170, Fig. 1 and 2 for example) beginning in, and continuously by transform portion and junction (for example pipe arrangement, pipe support) in the reactor assembly (20), until primary separation system (for example 100), wherein thermal barrier is removed from product vapor stream.Solid thermal carriers and solid coke by product are removed from product vapor stream in the primary separation device.Preferably, product vapor stream is separated with thermal barrier after flowing out from reactor as quickly as possible, makes that the residence time of product vapor stream in thermal barrier is short as far as possible.
The primary separation device can be the isolating device of any suitable solid, such as, but be not limited to cyclonic separator well known in the art, U-beam separator, or Rams Horn separator.Cyclonic separator is illustrated among Fig. 1,3 and 4.Solid separator, for example elementary cyclonic separator (100) preferably is equipped with the liner of high abrasion.Any solid of not collecting in elementary gathering system is transported downwards, and can reclaim in secondary separation device (180).Secondary separation device can be identical with the primary separation device, and perhaps it can comprise optional solid separating device, changes separator, for example Rams Horn separator, perhaps impingement separators such as, but be not limited to cyclonic separator well known in the art, 1/4.Secondary cyclone (180) illustrates in Fig. 1 and 4, but other separator also can be used as secondary separation device.
The solid of removing in elementary and secondary gathering system is transferred to the container that is used for heat-carrier regeneration, such as, but be not limited to direct contact reheater system (30).In direct contact reheater system (30), coke and byproduct gas are oxidized, thereby the technology heat energy that can be directly passed to solid thermal carriers (for example 310, Fig. 1,5) and regenerative heat carrier is provided.Keep the temperature of direct contact reheater, and with feedstock conversion (reactor) system independence.But, as mentioned above, can use other method to come the regenerative heat carrier, such as, but be not limited to acid treatment.
From the hot product flows of secondary separation device elementary collection post (primary condenser, 40, be cooled in Fig. 1).Vapour stream is quickly cooled to from invert point is lower than about 400 ℃.Preferably, vapour stream is cooled to about 300 ℃.Product is extracted out from elementary post and is pumped in (220) product conservation tank recirculation in reactor perhaps as mentioned below.Can use secondary condenser (50) to collect any material (225) of fleeing from primary condenser (40).The product of extracting out from secondary condenser (50) also is pumped to (230) product conservation tank.Residual not condensable gases is by compression in blower (190), and a part returns heat-carrier regeneration system (30) by pipeline (200), and residual gas is by pipeline (210) Returning reactor (20) and be used as thermal barrier and conveying medium.
Hot product flows can also be cooled in fractional column, and fractional column is designed to provide the liquid of different piece and the steam above the post, and this is being known in the art.The non-limiting example of fractional column is the C-400 fractional column, and this fractional column provides the liquids recovery of three different pieces.But, can also use to comprise still less or more part of liquids recovery.The bottom of fractional column can produce normally by pipeline 270 recirculation and return liquid flow in the reactor or end product all.The steam from this bottom that is also referred to as volatile constituent is sent to the middle part that produces steam, and this steam is cooled and delivers to the product conservation tank.Steam or volatile constituent from the middle part are sent to the top.The top produces starting material, and starting material are cooled and deliver to the product conservation tank, perhaps is used at the middle part or the top cooling.The excess liq that exists in the post is cooled and delivers to the product conservation tank, and is used to the needs of recycle gas from the steam of column top.If desired, fractional column can further be connected to dirty steam condenser.
In optional approach, come from quick hot worked product stream described herein (320, Fig. 1,3～5) and can directly be added in the secondary system of processing, by coming upgrading such as, but be not limited to FCC, viscosity breaking, hydrocracking or other catalytic cracking process.Then, the product that comes from the level two application can be collected, and for example in one or more condensation towers, as mentioned above, perhaps typically uses with these secondary systems of processing.As another possibility, coming from quick hot worked product stream described herein can at first be condensed, then or transportation, for example by pipeline transportation to level two, perhaps directly be attached to level two.
As another possibility, elementary heavy hydrocarbon reforming system, for example FCC, viscosity breaking, hydrocracking or other catalytic cracking process can come partly upgrading raw material as front-end processing system.The product stream that Rapid Thermal system of processing of the present invention can be used for then or further upgrading comes from front end system, perhaps be used for upgrading vacuum resid cut well known in the art, bottom fraction, perhaps other residual refinery fractions, they come from front end system (FCC, viscosity breaking, hydrocracking or other catalytic cracking process), perhaps are used for both.
Preferably, the reactor that process of the present invention is used can produce the product liquid of high yield, for example is higher than 60vol% at least, and preferably productive rate is higher than 70vol%, and more preferably productive rate is higher than 80vol%, and produces minimum by product, for example coke and gas.Be unwilling to limit the scope of the invention by any way, the example of the felicity condition of raw material pyrolysis processing, and the production of product liquid is at US 5,792 is described in 340, and this patent is incorporated herein for referencial use.This process uses sand (silica sand) as thermal barrier, and temperature of reactor is from about 450 ℃ to about 600 ℃, and thermal barrier compares from about 10: 1 to about 200: 1 with the charging of raw material, and residence time was from about 0.35 to about 0.7 second.Preferably, temperature of reactor is from about 480 ℃ to about 550 ℃.Preferred charging ratio was from about 15: 1 to about 50: 1, and preferred charging ratio was from about 20: 1 to about 30: 1.In addition, should be appreciated that residence time longer in reactor, for example reach about 5 seconds, if desired can by by the position of reactor bottom with raw material introduce in the reactor, increase reactor self length, reduce viscosity (supposition has enough speed to make product vapor and thermal barrier outflow reactor) by the thermal barrier of reactor, perhaps their combination obtains.Preferred residence time was from about 0.5 to about 2 seconds.
Be unwilling to be bound by theory, think that the raw material chemical modification that takes place as mentioned above partly is because the thermal barrier that uses in the inventive method compares with the height charging of raw material in reactor assembly.The ratio of carrier and raw material is typically from about 5: 1 to about 12.5: 1 in the prior art.But the ratio of carrier as herein described and raw material was from about 15: 1 to about 200: 1, and it has caused the quick ablation (ablative) from the thermal barrier to the raw material to be conducted heat.The thermal barrier of high volume and density has been guaranteed to have kept even higher treatment temp at reaction zone in mixing and the zone of transformation.Under this mode, the required temperature range of cracking process described herein is better control.This also allows to use low relatively temperature to minimize cracking, has guaranteed still can realize the appropriate cracking of raw material simultaneously.In addition,,, comprise metal (for example nickel and vanadium), coke owing to the big surface-area of thermal barrier is easy to adsorb pollutent and the inadvisable component that exists in raw material and the byproduct of reaction along with the increase of thermal barrier volume in the reactor, and nitrogen to a certain degree and sulphur.This has guaranteed that pollutent efficiently and is optimally removed during the raw material pyrolysis processing from raw material.Because use the thermal barrier of high surface area, thermal barrier self can be exceedingly not contaminated, and the metal of any absorption etc. is sloughed during heat-carrier regeneration easily.For the productive rate of processing of optimization raw material and product liquid, can carefully regulate the residence time of this system.
When comparing, has the residual oil fraction of remarkable conversion from the product liquid of hydrocarbon ils processing described herein with raw material.As a result, the present invention is characterized by from the product liquid that heavy oil upgrading produces, such as, but be not limited to, have API gravity, and more preferably be at least about 17 ° at least about 13 °.But as mentioned above, the product liquid that uses the inventive method to obtain from heavy oil upgrading is characterized by to have from about 10 end cuts to about 15% volume, from about 10 lighting ends to about 15% volume, remaining as middle distillate.
The viscosity of the product liquid that produces from heavy oil is reduced to 4.5 to about 10cSt@80 ℃ product level basically from 250cSt@80 ℃ initial feed level, perhaps from about 6343cSt@40 ℃ of about 15 to about cSt@40 ℃ of being reduced to product liquid of raw material.After single-stage technology, can obtain to be higher than the liquid yield of 80vol% and about 17 API gravity, viscosity at least than raw material reduced about 25 times (40℃).
Result that simulation distil (SimDist: for example ASTM D 5307-97, HT 750, (NCUT)) is analyzed has further disclosed different basically character between raw material and product liquid that this paper is produced.Simulation distil based on the heavy oil feedstock example, can determine at about about 1wt.% (kerosene(oil)fraction) that distills below 232 ℃, from about 232 ℃ to about 327 ℃ of about 8.7% (diesel oil distillates), and produce about 51.5% (the vacuum resid cut is analyzed fully referring to embodiment 1) more than 538 ℃.The SimDist of the product liquid of Chan Shenging analyzes to it is characterized by usually and has as mentioned above, but be not limited to and have following cut: approximately 4wt.% is at about produce below 232 ℃ (kerosene(oil)fraction), approximately 14.2wt.% from about 232 ℃ to about 327 ℃ of generation (diesel oil distillate), and 37.9wt.% is in generation (vacuum resid cut) more than 538 ℃.Should be appreciated that forming these values according to used raw material can change.These results show in the product liquid that is produced by the pressure fuel raw material and have significant chemical transformation, generally trend towards in lesser temps ebullient lower molecular weight component.
Therefore, the present invention relates to from the product liquid of step processing heavy oil acquisition, being characterized as of this product has one of following surface properties at least:
Have and be lower than 50% component and produce (vacuum resid cut) in the temperature more than 538 ℃;
Comprising from about 60% to about 95% product is producing below 538 ℃.Preferably from about 60% to about 80% product is producing (promptly before the vacuum resid cut) during the SimDist below 538 ℃;
Having from about 1.0% to about 6% product liquid is producing below 193 ℃.Preferably from about 1.2% to about 5% producing (promptly before raw gasline and kerosene) below 193 ℃;
Having from about 2% to about 6% product liquid produces 193～232 ℃.Preferably from about 2.8% to about 5% 193～232 ℃, produce (kerosene(oil)fraction);
Having from about 12% to about 25% product liquid produces 232～327 ℃.Preferably from about 13% to about 18% 232～327 ℃, produce (diesel oil distillate);
Having from about 5% to about 10% product liquid produces 327～360 ℃.Preferably from about 6.0% to about 8.0% 327～360 ℃, produce (light VGO cut);
Having from about 40% to about 60% product liquid produces 360～538 ℃.Preferably from about 30% to about 45% 360～538 ℃, produce (heavy VGO cut);
Similarly, after using method as herein described, the product liquid that obtains from single-stage processes asphalt stock is characterized by to have, but does not think restriction, and API gravity increased at least about 10 (API of raw material typically is about 8).In addition, reduce volume and can realize higher API gravity.The product that obtains from pitch also has following feature: have from about 0.93 to about 1.0 density and be lower than the viscosity (i.e. the product viscosity from about 15g/ml to about 60g/ml under 40 ℃, material viscosity is about 1500g/mi) of the very big reduction of 20 times of raw materials at least.The productive rate of the product liquid that obtains from pitch is at least 60% volume, and preferably productive rate is higher than about 75% volume.SimDist analyzes and also to have shown between asphalt stock and product liquid that this paper is produced having significantly different character.The SimDist analytical results shows for asphalt stock, the raw material of about 1% (wt.%) is at about distill below 232 ℃ (kerosene(oil)fraction), about 8.6% from about 232 ℃ to about 327 ℃ (diesel oil distillates), and about 51.2% is producing (the vacuum resid cut is analyzed fully referring to embodiment 2) more than 538 ℃.The SimDist of the product liquid of producing from pitch as mentioned above analyzes to it is characterized by usually to have, but be not limited to and have following surface properties: about 5.7% (wt.%) is at about produce below 232 ℃ (kerosene(oil)fraction), approximately 14.8wt.% from about 232 ℃ to about 327 ℃ of generation (diesel oil distillate), and 29.9wt.% is in generation (vacuum resid cut) more than 538 ℃.In addition, can be different according to these results of used raw material, but when comparing with asphalt stock, they show, and significant variation has taken place in many components in the product liquid, and generally trends towards processing the early stage lower molecular weight component that generates the product liquid that produces from Rapid Thermal during SimDist analyzes.
Therefore, the invention still further relates to the product liquid that obtains from a step formed asphalt, being characterized as of this product has one of following surface properties at least:
Have and be lower than 50% component and produce (vacuum resid cut) in the temperature more than 538 ℃;
Comprising from about 60% to about 95% product is producing below 538 ℃.Preferably from about 60% to about 80% product is producing (promptly before the vacuum resid cut) during the SimDist below 538 ℃;
Having from about 1.0% to about 6% product liquid is producing below 193 ℃.Preferably from about 1.2% to about 5% producing (promptly before raw gasline and kerosene) below 193 ℃;
Having from about 2% to about 6% product liquid produces 193～232 ℃.Preferably from about 2.0% to about 5% 193～232 ℃, produce (kerosene(oil)fraction);
Having from about 12% to about 25% product liquid produces 232～327 ℃.Preferably from about 13% to about 18% 232～327 ℃, produce (diesel oil distillate);
Having from about 5% to about 10% product liquid produces 327～360 ℃.Preferably from about 6.0% to about 8.0% 327～360 ℃, produce (light vacuum gas oil (VGO) cut);
Having from about 40% to about 60% product liquid produces 360～538 ℃.Preferably from about 30% to about 50% 360～538 ℃, produce (heavy VGO cut);
The product liquid of production as described herein also shows satisfactory stability.After during 30 days, finding is only having insignificant change (referring to embodiment 1 and 2) from the product liquid of heavy oil or asphalt stock production aspect SimDist analysis, viscosity and the API.
In addition, as disclosed herein, the further processing of the product liquid that obtains from processing heavy oil or asphalt stock can be followed method of the present invention and carry out.This further processing can be used the condition that is very similar to initial stage fast pyrolysis processes raw material, and perhaps improvement condition strengthens remove (the gentle cracked single-stage technology) of light product, follows the more cut of important place cracking recirculation (for example two-stage process).
Under simulated condition further under first kind of situation of processing, thereby, be recycled backheat from the product liquid of first pyrolysis processing and separate reactor for the further character of upgrading end product produces lighter product.In this arrangement, after the lighter fraction of product had been removed from product stream, first time the pyrolytic product liquid was used as the pyrolytic raw material second time.In addition, can also implement compound recirculation, the last running of wherein handling for the first time in the product stream is added back to (for example Fig. 3 summarizes in more detail below) in (recirculation) reactor with adding fresh feed.
The second method that the upgrading raw material obtains having required character product liquid relates to two step pyrolytic processes (referring to Fig. 2 and 3).This two-stage process is used not too heavy Rapid Thermal processing and then heavier quick hot worked combination.The first step of technology comprises raw material is exposed under the condition of gentle crackene component, thereby avoids overcracking and excessive gas and coke to produce.The example of these conditions includes, but are not limited to, and under about 150 ℃ raw material is injected the hot gas flow that comprises thermal barrier in the ingress of reactor.Raw material is being lower than 500 ℃, for example under 300 ℃, handles in reactor, and residence time is no more than about 1 second.Comprise than the product of light material (low-boiler) by separation in the condenser system (40) of the first step (100 and 180, Fig. 3) and remove.For the product liquid that reduces viscosity is provided, is collected in condenser (40) bottom isolating heavier material (240), and in reactor, accepts heavier cracking in subordinate phase.Two-stage process is than providing the single-stage technology that is equal to the viscous liquid product that higher productive rate is provided.The condition of using in the second stage includes, but are not limited to about 530 ℃ and arrives about 590 ℃ processing temperature.As shown in Figure 1, use elementary and secondary cyclone (being respectively 100,180) and elementary and secondary condenser (being respectively 40 and 50) are processed and collected from partial product.
Follow this two-stage process, the example of first step product is not thought restriction, has the productive rate of about 30vol%, about 19 API, and the feature that reduces the viscosity of several times than initial feed.The high boiling compound cut product that the processing recycle fraction is produced in the processing second stage typically is characterized as has the productive rate that is higher than about 75vol%, about 12 API, and than the viscosity of feedstock recycle cut reduction.For the product liquid of producing from heavy oil feedstock, the SimDist analytical characteristic is that about 7.4% (wt.%) distills (kerosene(oil)fraction about below 232 ℃, for raw material is 1.1%), about 18.9% from about 232 ℃ to about 327 ℃ of (diesel oil distillates, for raw material is 8.7%), and about 21.7% is producing (the vacuum resid cut is 51.5% for raw material, analyzes fully referring to embodiment 1) more than 538 ℃.For the product liquid of producing from asphalt stock, the SimDist analytical characteristic is that about 10.6% (wt.%) distills (kerosene(oil)fraction about below 232 ℃, for raw material is 1.0%), about 19.7% from about 232 ℃ to about 327 ℃ of (diesel oil distillates, for raw material is 8.6%), and about 19.5% is producing (the vacuum resid cut is 51.2% for raw material, analyzes fully referring to embodiment 1) more than 538 ℃.
The optional condition of two-stage process comprises following operation of fs: raw material is preheating in 150 ℃ and the injecting reactor, residence time was from about 0.01 to about 20 seconds, preferably from about 0.01 to about 5 seconds, arrive the residence time of about 620 ℃ of following processing in reactor less than 1 second (referring to Fig. 2) perhaps from about 0.01 second to about 2 seconds, and at about 530 ℃.Use elementary and secondary cyclone (being respectively 100 and 180, Fig. 2 and 4), and bottom product is transferred in the condenser (250) of heat.Start condenser system (Fig. 4), use reheater condenser (250) optionally to reclaim heavy bitumen matter component in the preceding arrangement of primary condenser (40).Heavy bitumen matter is collected and turns back in the reactor (20), is used for further processing (being subordinate phase).Subordinate phase is used than the higher temperature that uses in the fs or is more reside permanently and stays under the time, perhaps reaches more to reside permanently the reactor condition that stays the time (for example injecting than the low spot place) to operate down at reactor at higher temperature, thus the optimization product liquid.In addition, under this method, a part of product stream is recycled loss.
Compound and the still another kind of of two-stage process system improves, be called " multistage " technology, comprise by pipeline 280 initial feed (starting material) is introduced in the primary condenser (see figure 5), and use primary raw materials to cool off primary condenser or the interior product vapor of fractional column fast.The product of extracting out from primary condenser is recycled in the reactor 270 by pipeline 270 then, thereby combines " fs " and " subordinate phase " processing (being recirculation processing).In optional embodiment, can use primary condenser or fractional column to come from the liquid ingredient of original raw material, to separate the gaseous component of original raw material, and the liquid ingredient of original raw material, and come from the product liquid that processes raw material in condenser or the fractional column and be transferred in the flow reactor, accept Rapid Thermal processing there.In the embodiment of this multistage processing, primary raw materials before introducing primary condenser or fractional column can with the calcium cpd combination.Calcium cpd can also add (30) in the sand reheater, for example from the cyclonic separator that sand and coke is recirculated in the sand reheater, in 290 or 300 the pipeline.CaOH 2O or Ca (OH) 2Can directly be added in the sand reheater.
Multistage processing has realized the high-degree of conversion of residual oil fraction than single-stage or two-stage process biglyyer, and bigger the liquid mass (for example its viscosity) that has promoted product.Thereby the raw material of recirculation is exposed to gentle crackene component and avoids under the condition of overcracking and excess air and coke generation.The example of these conditions includes, but are not limited to, and under about 150 ℃ raw material is injected the hot gas flow that comprises thermal barrier in the ingress of reactor.Raw material is processed few about 2 seconds residence time of eyeball in reactor under the temperature between about 450 ℃ to about 600 ℃.Preferably, residence time was from about 0.8 to about 1.3 seconds, and temperature of reactor is from about 480 ℃ to about 550 ℃.Comprise than the product of light material (low-boiler) by separation in condenser system (40) (100 and 180, Fig. 5) and remove.Isolatingly in condenser (40) bottom be collected, and introduce again in the reactor (20) by pipeline 270 than heavy material (240).The product gas that flows out primary condenser (40) enters secondary condenser (50), collects the product liquid (using this method to analyze referring to embodiment 5) that reduces viscosity and high yield (300) there.In multistage processing, in order to produce the product that can collect from secondary condenser, feedstock recycle is by reactor, thus upgrading and optimization the character of product liquid.
If desired, for one, two, compound or multistage processing can also use optional feed system.For instance, elementary heavy hydrocarbon reforming system, for example FCC, viscosity breaking, hydrocracking or other catalytic cracking process can come part upgrading raw material as the front end system of processing.Rapid Thermal system of processing of the present invention can be used for further upgrading then and come from the product stream of front end system, perhaps be used for other vacuum resid cut, bottom fraction that comes from front end system (FCC, viscosity breaking, hydrocracking or other catalytic cracking process) well known in the art of upgrading, perhaps residual refinery fractions perhaps is used for both.
Therefore, the present invention also provides the method for processing heavy hydrocarbon feeds, and as shown in Figure 5, wherein raw material (initial feed or starting material) obtains from feed system (10), and in pipeline (280, can be heated as previously mentioned), be transported to primary condenser (40) or fractional column.The elementary product that obtains from primary condenser/fractional column can also be recycled to reactor (20) in elementary product recirculation line (270).If desired, elementary product recirculation line can be heated, and can comprise as shown in Figure 5 preheating apparatus and come once more recirculation former expected and be used to introduce the required temperature of reactor (20).Above-mentioned calcium cpd can be added in the raw material of introducing before condensation tower or the fractional column, perhaps adds before entering reactor.In preferred embodiments, before raw material is introduced into the base portion of fractional column, in raw material, add calcium cpd.
Then illustrated process recycling as mentioned above and in Fig. 5, have and be higher than 60% and the product of characteristic at the above productive rate of 75% (wt%) and below having preferably, restriction by any way can not produced from pitch or heavy oil feedstock: from about API of 14 to 19; From about 20 viscosity to about 100 (cSt@40 ℃), and low metal content (referring to embodiment 5).
Analyze according to SimDist, the product liquid that obtains from multistage processing heavy oil is characterized by and comprises one of following at least character:
Have and be lower than 50% component and produce (vacuum resid cut) in the temperature more than 538 ℃;
Comprising from about 60% to about 95% product is producing below 538 ℃.Preferably from about 70% to about 90%, and more preferably from about 75% to about 87% product is producing (promptly before the vacuum resid cut) during the SimDist below 538 ℃;
Having from about 1.0% to about 6% product liquid is producing below 193 ℃.Preferably from about 1.2% to about 5%, and more preferably from about 1.3% to about 1.8% producing (promptly before raw gasline and kerosene) below 193 ℃;
Having from about 2% to about 6% product liquid produces 193～232 ℃.Preferably from about 2.8% to about 5% 193～232 ℃, produce (kerosene(oil)fraction);
Having from about 15% to about 25% product liquid produces 232～327 ℃.Preferably from about 18.9% to about 23.1% 232～327 ℃, produce (diesel oil distillate);
Having from about 8% to about 15% product liquid produces 327～360 ℃.Preferably from about 8.8% to about 10.8% 327～360 ℃, produce (light vacuum gas oil (VGO) cut);
Having from about 40% to about 60% product liquid produces 360～538 ℃.Preferably from about 42% to about 55% 360～538 ℃, produce (heavy VGO cut);
The product liquid that obtains from the multistage processing of pitch has the feature of one of following surface properties at least:
Have and be lower than 50% component and produce (vacuum resid cut) in the temperature more than 538 ℃;
Comprising from about 60% to about 95% product is producing below 538 ℃.Preferably from about 60% to about 85% producing (promptly before the vacuum resid cut) during the SimDist below 538 ℃;
Having from about 1.0% to about 8% product liquid is producing below 193 ℃.Preferably from about 1.5% to about 7% producing (promptly before raw gasline and kerosene) below 193 ℃;
Having from about 2% to about 6% product liquid produces 193～232 ℃.Preferably from about 2.5% to about 5% 193～232 ℃, produce (kerosene(oil)fraction);
Having from about 12% to about 25% product liquid produces 232～327 ℃.Preferably from about 15% to about 20% 232～327 ℃, produce (diesel oil distillate);
Having from about 5% to about 12% product liquid produces 327～360 ℃.Preferably from about 6.0% to about 10.0% 327～360 ℃, produce (light vacuum gas oil (VGO) cut);
Having from about 40% to about 60% product liquid produces 360～538 ℃.Preferably from about 35% to about 50% 360～538 ℃, produce (heavy VGO cut);
These results show that jointly most of low volatility component has changed into more high-volatile component in the product liquid (light raw gasline, kerosene and diesel oil) in one of two kinds of raw materials.These results show the product liquid quality of the suitable pipeline transportation of upgrading one-tenth basically.
The present invention also provides during Rapid Thermal processing heavy hydrocarbon feeds and has reduced the method that sulphur discharges in the stack gas.The SO that reduces 2Release can be by adding lime, such as, but be not limited to Ca (OH) in the forward direction raw material that processes raw material 2, CaO or CaOH obtain.Can also in sand reheater (30), add calcium cpd, for example CaOH 20 or Ca (OH) 2Strengthen the desulfurization of stack gas.For instance, restriction by any way with the amount corresponding to 1.7 times of the required stoichiometric ratios of sulphur in the coke that enters the sand reheater, is added lime in the sand reheater, has caused about 95% flue gas desulfurization (FGD) (referring to Fig. 6 and embodiment 8A and B).Adding the amount of the calcium cpd in raw material or the sand reheater to can determine according to the level of analyzing sulphur in the stack gas.
As table 18, shown in the embodiment 7A, in raw material or sand reheater, add calcium cpd and can not change pyrolysis heavy hydrocarbon feeds under the situation that is not having calcium cpd, the character of the product liquid of producing such as, but be not limited to pitch.In addition, the Rapid Thermal first being processed or during in raw material, add the TAN that calcium cpd reduced product (referring to table 18, embodiment 7A, relatively " during 1, charging ", calcium with " during 3; Prod " add before the TAN of raw material, quick hot worked product in the presence of calcium cpd).As table 19, shown in the embodiment 7B, to (Bakersfiled adds the Ca (OH) of 3.0wt.% in heavy oil feedstock California) from the SanArdo oil field 2, the TAN value of raw material has reduced by 3 times with respect to untreated raw material, and has caused having the product liquid that is lower than the about 5 times TAN value of raw material TAN value that is untreated.The reduction of this raw material TAN value can prolong the life-span of fast pyrolysis reactor, and life-span of other assembly in the system of processing.
The Rapid Thermal first being processed or during in raw material, add the hydrogen sulfide content that above-mentioned calcium cpd has also reduced one or more gaseous fractions in the product stream.As table 20, shown in the embodiment 9, with Ca (OH) 2The form calcium that in heavy hydrocarbon feeds, adds 1.2wt.% caused H in the quantitative reduction product gas 2S content.In order to remove fully that product flows the hydrogen sulfide in each component and the concrete amount of adding calcium cpd in given raw material can be determined according to analyzing the hydrogen sulfide levels that exists in the product stream that fast pyrogenation obtains under the situation that is not having calcium cpd.
Therefore, the invention provides the method for hydrogen sulfide content that a kind of reduction comes from one or more gaseous fractions of heavy hydrocarbon feeds Rapid Thermal processed products stream, this method comprises:
(i) the Rapid Thermal processing of heavy hydrocarbon feeds in the presence of calcium cpd:
The (ii) Rapid Thermal processing of heavy hydrocarbon feeds in the presence of calcium cpd, and the regeneration in reheater in the presence of calcium cpd of particulate thermal barrier;
The (iii) Rapid Thermal of heavy hydrocarbon feeds processing, and the regeneration in reheater in the presence of calcium cpd of particulate thermal barrier.
By reducing product, heavy oil feedstock with high TAN, for example come from San Ardo oil field (Bakersfiled, California, the TAN of heavy oil feedstock embodiment 7B), otherwise owing to its corrodibility reduces its market value, this heavy oil product is more suitable for further processing such as, but be not limited to FCC, viscosity breaking, hydrocracking or other catalytic cracking process in using reforming system well known in the art now.Therefore, by processing in the presence of calcium have high TAN feature the heavy hydrocarbon feeds upgrading product and provide product for a large amount of further working methods.
Fig. 6 and 7 expressions are when add Ca (OH) in sand reheater or raw material and pipeline 2The time, during the processing of asphalt oil raw material, SO in the stack gas 2Value is to the variation of time.In the sand reheater, add Ca (OH) 2Starting point be labeled as an A, C, E (Fig. 6), and in raw material, add Ca (OH) 2Starting point be labeled as a G, H and I (Fig. 6).At an A place, calcium (8.4wt% of raw material weight) is added in the sand reheater, and stops at the B place.Ca (OH) 2Again add at the C place, and stop once more, sentence lower concentration (6.6wt.%) at E and add once more and stop at the F point again at the D place.At the G point, Ca (OH) 2(1wt% of raw material weight) is added in the raw material, then adds the Ca (OH) of 2wt.% at the H point 2, add 4wt.% at the I point.SO as can be seen 2Horizontal respone in different Ca (OH) 2End to add.The result shows add Ca (OH) in sand reheater or raw material 2For the SO that reduces in the stack gas 2Level is effective.In raw material, add calcium for realizing identical SO in the stack gas 2Reduce the Ca (OH) that needs still less 2
After stopping in sand reheater or raw material, adding calcium, to compare during with the experiment beginning, the delay that reaches baseline sulphur level in the stack gas has reduced (relatively before the A point and between B and C, perhaps at about G point SO of place xLevel).The reduction that discharges may be because Ca (OH) 2Pass through system with the recirculation of particulate thermal barrier.When being recycled, calcium also plays a part thermal barrier.If Ca (OH) 2With the recirculation of particulate thermal barrier, if in raw material, add new Ca (OH) so 2, a part of Ca (OH) 2Can periodically be removed.If desired, Ca (OH) 2Can from the particulate thermal barrier, separate as required.
Fig. 7 is illustrated in the experiment that Fig. 6 describes at Ca (OH) 2The time course of first hour after being added in the sand reheater, and corresponding SO xReduce.Ca (OH) in the 13:09 adding 2Amount is about 70% of sulphur charging stoichiometry, and is about 1.7 to 2 times that enter sulfur chemistry metered amount in the reheater.There is not Ca (OH) 2Situation under, SO in the stack gas in system 2Starting point concentration be about 1400ppm.In case begin with Ca (OH) at 13:09 2Inject the sand reheater, SO 2Level reduces fast.SO 2Be reduced to fast about 85%, then more gradually be reduced to about 95% SO 2Reduce end value.
Fig. 8 represents when add Ca (OH) in raw material 2The time, come from San Ardo oil field (Bakersfiled, the SO during heavy oil feedstock California) in the stack gas in processing 2The variation of value.There is not Ca (OH) 2Situation under, SO in the stack gas in system 2Starting point concentration be about 500ppm.In case in raw material, add Ca (OH) 2, SO 2Level is reduced to fast and is approximately 50% of initial value.Along with the interpolation of calcium, SO 2Reduce continuously.
Therefore, the invention provides a kind of method, be used for (i) reduction stack gas SO during the upgrading heavy hydrocarbon feeds xDischarge, (ii) reduce in the product liquid total acid value (TAN), (iii) reduce the hydrogen sulfide content in the product stream, and their combination, this method is included in calcium cpd and has Rapid Thermal processing heavy hydrocarbon feeds down.
In addition, the invention provides the method for Rapid Thermal processing heavy hydrocarbon feeds in the presence of calcium cpd, comprising:
I) provide the particulate thermal barrier to enter in the flow reactor;
Ii) heavy hydrocarbon feeds is introduced in the last flow reactor, to such an extent as to the particulate thermal barrier compares from about 10: 1 to about 200: 1 with the charging of heavy hydrocarbon feeds;
Heavy hydrocarbon feeds and described thermal barrier are interacted less than about 5 seconds residence time, thereby produce product stream;
Iv) separated product flows from the particulate thermal barrier; And
V) from product stream, collect gaseous state (for the first time) and liquid (for the second time) product.
Wherein, in step I), ii), iii), iv), v), perhaps add calcium cpd in their combination, its amount is about 0.2% to 5 times of raw material sulfur chemistry metered amount.
Above description do not plan to limit by any way the present invention of claim, each characteristics combination of being discussed in addition is not absolute demand for the present invention.
The present invention will be described in the following embodiments further.But, be to be understood that these embodiment just are used to the purpose of setting forth, and should be used for limiting the scope of the invention by any way.
Embodiment 1: heavy oil (single-stage)
Use as US 5,792 pyrolysis process of the pyrolysis reactor of describing in 340 enforcement Saskatchewan heavy oil and Athabasca pitch (seeing Table 1) under temperature on a large scale.
Table 1: the feature of heavy oil and asphalt stock
Compound Heavy oil 1) Pitch 2)
80 ℃ of (cSt) armaticity of 60 ℃ of (cSt) viscosity@of 40 ℃ of (cSt) viscosity@of API ° of viscosity@of carbon (wt%) hydrogen (wt%) nitrogen (wt%) sulphur (wt%) ash content (wt%) vanadium (ppm) nickel (ppm) water content (wt%) gravity (13CNMR) 84.27 10.51 ＜0.5 3.6 0.02 127 43 0.8 11.0 6500 900 240 0.31 83.31 10.31 ＜0.5 4.8 0.02 204 82 0.19 8.6 40000 5200 900 0.35
1) Saskatchewan heavy oil
2) Athabasca pitch (pure)
In brief, processing conditions comprise from about 500 ℃ to about 620 ℃ temperature of reactor.The particulate thermal barrier compares approximately from 20: 1 to about 30: 1 with the charging of raw material, and residence time was from about 0.35 to about 0.7 second.These conditions are summarized (table 2) below in more detail.
The single-stage processing of table 2:Saskatchewan heavy oil
Temperature of reactor ℃ Nian Du @40 ℃ (cSt) Productive rate wt% Mi Du @15 ℃ g/ml API° Productive rate Vol%
620 592 590 590 4.6 1) 15.2 1) 20.2 31.6 71.5 74.5 70.8 75.8 0.977 0.970 0.975 0.977 13.3 14.4 13.6 13.3 72.7 76.2 72.1 77.1
560 560 550 550 4) 10.0 1) 10.0 1) 20.8 15.7 79.9 2) 83.0 3) 78.5 59.8 2) 0.963 0.963 0.973 0.956 15.4 16.2 3) 14.0 16.5 82.3 2) 86.3 3) 80.3 61.5 2)
550 4) 530 530 15.7 32.2 32.2 62.0 3) 80.9 2) 83.8 3) 0.956 0.962 0.962 18.32，3 15.7 16.6 3) 65.1 3) 82.8 2) 87.1 3)
1) Nian Du @80 ℃
2) productive rate does not comprise overhead condensation
3) productive rate of Gu Jiing and API with overhead condensation
4) not all liquid is caught in test.
Analysis is at the content of metal, water and the sulphur of 620 ℃, 592 ℃ and the 560 ℃ product liquids of operating down.These results represent in table 3.The level of nickel, vanadium and water is reduced by 72,69 and 87% respectively, and the content of sulphur and nitrogen keeps identical or reduces seldom.There is not metal to be concentrated in the product liquid.
Table 3: the metal analysis of product liquid 1)(ppm)
Component Saskatchewar heavy oil Operate @620 ℃ Operate @592 ℃ Operate @560 ℃
Ferro-aluminum nickel zinc calcium ＜1 ＜1 44 2 4 ＜1 2 10 ＜1 2 11 4 12 2 3 ＜1 ＜1 9 1 1
Magnesium boron sodium silicon vanadium 3 21 6 1 127 1 42 5 10 39 2 27 5 140 43 ＜1 ＜1 4 4 39
Potassium water (wt%) sulphur (wt%) 7 0.78 3.6 7 0.19 3.5 ＜1 0.06 3.9 4 0.10 3.5
1) in raw material and the product liquid copper, tin, chromium, lead, cadmium, titanium, molybdenum, barium and manganese all less than 1ppm.The gas yield of two kinds of operations is illustrated in the table 4.
Table 4: the gasometry of pyrolysis operations
Gas (wt%) Operate @620 ℃ Operate @560 ℃
Total gas yield ethylene-ethane propene and methane 11.8 27.0 8.2 30.0 24.0 7.2 16.6 16.4 15.4 21.0
The yield point of raw material (pour point) is enhanced and is reduced to about 54F ° from 32F °.Conradson carbon is reduced to about 6.6wt% by 12wt%.Based on the analysis of these operations, can obtain higher API value and productive rate productive rate to about 560 ℃ temperature of reactor for about 530.Under these temperature, can obtain 14 to 18.3 API gravity, product productive rate from about 80 to about 87vol%, and from about 15 to @40 ℃ of about 35cSt () or @40 ℃ of about 10cSt () viscosity (in 550 ℃ productive rates are not included in this scope, not being optimised) because liquid yield is captured in this operating period.These product liquids have reflected significant upgrading degree, and show the quality that is suitable for pipeline transportation.
Provide table 5 from the raw material of several individual operation acquisition and simulation distil (SimDist) analysis of product liquid.SimDist analyzes and carries out according to generalized agreement among the ASTM D 5307-97, and this agreement has reported to have the residue that is higher than 538 ℃ of boiling points.Other method that can also use SimDist to analyze, for example HT 750 (NCUT; Comprised that the boiling point up to 750 ℃ distributes).These results show that the component more than 50% is producing more than 538 ℃ in the raw material.They are high molecular weight components of low volatility.On the contrary, in product liquid, most of components, about 62.1% product is more volatile and is producing below 538 ℃.
Table 5: the SimDist of single-stage processing back raw material and product liquid analyzes (538 ℃ of temperature of reactor)
Cut Temperature (℃) Raw material R245
Light raw gasoline is light/the heavy VGO vacuum resid of the light VGO of the medium raw gasoline raw gasoline of medium raw gasoline/kerosene kerosene diesel oil ＜71 71-100 100-166 166-193 193-232 232-327 327-360 360-538 ＞538 0.0 0.0 0.0 0.1 1.0 8.7 5.2 33.5 51.5 0.5 0.3 1.4 1.0 2.8 14.2 6.5 35.2 37.9
Further being characterized as of raw material has about 0.1% component and produces (raw gasline/kerosene(oil)fraction) down at 193 ℃, and product liquid is approximately 6%.Diesel oil distillate also shows the significant difference between raw material and product liquid, and (232-327 ℃) produces 8.7% and 14.2% respectively under this temperature range.These results show that jointly the most of component that has low volatility in the raw material has been converted into high-volatile component in the product liquid (raw gasline, kerosene and diesel oil).
The stability of product liquid is determined (table 6) in can also be during 30 days.Do not observe the noticeable change of product liquid viscosity, API and density in during 30 days.
Table 6: the stability of single-stage processing back product liquid
Cut Time=0 7 days 14 days 30 days
Mi Du @15.6 ℃ (g/cm 3) @40 ℃ of Nian Du of API (deg.API) (cSt) 0.9592 15.9 79.7 0.9590 15.9 81.2 0.9597 15.8 81.2 0.9597 15.8 83.2
Embodiment 2 pitches (single-stage)
Use is at US 5,792, and the pyrolysis reactor of describing in 340 is implemented several operations of Athabasca bituminous.Processing conditions comprises from 520 ℃ to 590 ℃ temperature of reactor.The particulate thermal barrier compares from about 20: 1 to about 30: 1 with the charging of raw material, and residence time was from about 0.35 to about 1.2 seconds.These conditions and gained product liquid are summarized in following (table 7) more in more detail.
Table 7: single-stage is processed undiluted Athabasca pitch
Cracking temperature ℃ 40 ℃ of viscosity @ (cSt) Productive rate wt% 15 ℃ of density @ Metal V (ppm) * Metal Ni (ppm) ** API
519 525 528 545 590 205 201 278 151 25.6 81.0 74.4 82.7 77.4 74.6 nd 0.979 nd 0.987 0.983 nd 88 nd 74 nd nd 24 nd 27 nd 13.0 12.9 12.6 11.8 12.4
*Raw material V 209ppm
*Raw material Ni 86ppm
These results show and can the method according to this invention process unfluxed asphalt, thereby production viscosity is from much larger than @40 ℃ of 40000cSt () be reduced to @40 ℃ of about 25.6～200cSt () product liquid (depend on operational condition; Referring to table 8 and 9), productive rate more than 75% to about 85%, and the API of product is improved to about 12～13 from 8.6.In addition, according to embodiment 1, product liquid has shown in essence upgrading raw material.The SimDist of product liquid analyzes and other character is listed in the table 8, and stability study is listed in the table 9.
Table 8: the character and the SimDist of single-stage processing back raw material and product liquid analyze
(temperature of reactor: 545 ℃)
Cut Temperature (℃) Raw material R239 14 days 30 days
@40 ℃ of Mi Du @15.5 ℃ of API Nian Du -- -- -- 0.9871 11.7 162.3 0.9876 11.6 169.4
Light raw gasoline is light/the heavy VGO vacuum resid of the light VGO of the medium raw gasoline raw gasoline of medium raw gasoline/kerosene kerosene diesel oil ＜71 71-100 100-166 166-193 193-232 232-327 327-360 360-538 ＞538 0.0 0.0 0.0 0.1 0.9 8.6 5.2 34.0 51.2 0.2 0.2 1.5 1.0 3.1 15.8 7.9 43.9 26.4 0.1 0.2 1.4 1.0 3.0 14.8 7.6 42.0 29.9
Table 9: the stability (temperature of reactor: 525 ℃) of single-stage processing back product liquid
Cut Temperature (℃) The R239 raw material 0 day 7 days 14 days 30 days
Mi Du @15.6 ℃ *@40 ℃ of API Nian Du ** -- -- -- 1.0095 8.5 30380 0.979 12.9 201.1 0.980 12.7 213.9 0.981 12.6 214.0 0.981 12.6 218.5
Light raw gasoline is light/the heavy VGO vacuum resid of the light VGO of the medium raw gasoline raw gasoline of medium raw gasoline/kerosene kerosene diesel oil ＜71 71-100 100-166 166-193 193-232 232-327 327-360 360-538 ＞538 0.0 0.0 0.0 0.1 1.0 8.7 5.2 33.5 51.5 0.1 0.1 1.5 1.0 2.6 14.1 7.3 41.3 32.0 0.1 0.1 1.5 1.0 2.6 14.1 7.3 41.3 32.0 0.1 0.1 1.5 1.0 2.6 14.3 7.4 41.7 31.2 0.1 0.1 1.4 1.1 2.7 14.3 7.4 42.1 30.8
*g/cm 3
**cSt
Slight variation of each value is all within the error of used test method in the stability study (table 9 and other stability study disclosed herein), and is acceptable in the technology.These results show that product liquid is stable.
These results show that being higher than 50% component in the raw material produces (vacuum resid cut) in the temperature more than 538 ℃.This cut be characterized as high molecular weight component with low volatility.On the contrary, after several operations, being characterized as of product liquid comprises about 68～74% product and is more volatile and producing below 538 ℃.About 0.1% the component of further being characterized as of raw material is producing (raw gasline/kerosene(oil)fraction) below 193 ℃, and is approximately 2.7～2.9% in the product liquid.Diesel oil distillate also shows the significant difference between raw material and product liquid, and (232-327 ℃) produces 8.7% (raw material) and 14.2% (product liquid) respectively under this temperature range.These results show that jointly the most of component that has low volatility in the raw material has been converted into high-volatile component in the product liquid (raw gasline, kerosene and diesel oil).These results have shown that product liquid has obtained upgrading basically, and show the character that is suitable for transporting.
Embodiment 3: the compound/recirculation of raw material
Be configured in US 5,792, the pyrolysis reactor of describing in 340 makes and reclaims condenser product liquid is imported pipeline, arrives reactor (referring to Fig. 3 and 4).
Processing conditions comprise from about 530 ℃ to about 590 ℃ temperature of reactor.For initial and recirculation operation, use the charging ratio of about 30: 1 particulate thermal barrier and raw material, and from about 0.35 to about 0.7 second residence time.These conditions are summarized (table 10) below in more detail.The then pyrolysis of raw material uses the reheater condenser that is positioned at before the primary condenser to remove and collect lighter cut (referring to Fig. 4), and the heavy component recirculation of product liquid is returned reactor and is used for further processing (also seeing Fig. 3).Under this arrangement, the recirculation flow (260) that comprises last running mixes with new raw material (270), produces compound raw material (240), uses then and processes in the identical condition of pyrolysis reactor initial operation.
Table 10: use Saskatchewan heavy crude oil and undiluted
The Athabasea bituminous is compound/recirculation operation
Raw material Cracking temperature ℃ Productive rate Vol% API° The rate of recovery 4) Vol％ Reclaim 4) API°
Heavy oil 590 560 550 550 530 77.1 1) 86.3 2) 50.1 1) 65.1 2.3) 87.1 2) 13.3 16.2 14.0 18.3 16.6 68.6 78.1 71.6 56.4 78.9 17.1 21.1 17.8 22.9 21.0
Pitch 590 75.2 2) 12.4 67.0 16.0
1) productive rate and API gravity comprise overhead condensation (reality)
2) productive rate and API gravity comprise overhead condensation (estimation)
3) not every liquid is recovered in this operation
4) these values are represented the total yield of recirculation operation after product, and have removed the last running of about 10% recirculation loss.Therefore, this is the conservative estimation of productive rate, because some last running will produce the light constituent that can enter product stream, not every last running finally all becomes coke.
After first time cycle of treatment, API gravity is increased to about 13 to about 18.5 from 11.0 of heavy oil feedstock, and further is being increased to about 17 to about 23 after the circulation for the second time.For the pitch that has about 8.6API in the raw material, observing similar API increases, and is increased to approximately 12.4 after operation for the first time, is increased to 16 after the recirculation operation.When API increased, productive rate correspondingly was increased to about 87% from about 77% in operation back for the first time, be increased to 79% from about 67% after the recirculation operation.Therefore, relevant with the production of light product, liquid yield has increased.But the light product of upgrading need be used for transportation, and this product has been reached in the recirculation of product liquid.
Embodiment 4: the bi-level treatment of heavy oil
Heavy oil or asphalt stock also use the two-stage pyrolytic process to process, and comprise for fear of the generation of overcracking and excess air and coke and raw material is exposed to the first step under the gentle crackene component condition.Lighter material is removed after first step processing, and residual is received in more heavily cracking under the comparatively high temps than heavy material.The condition of processing comprises from about 510 to about 530 ℃ temperature of reactor (515 ℃ data provide below) in the first step, and in the second stage, uses from about 590 to about 800 ℃ temperature (590 ℃ data provide table 11).The particulate thermal barrier in two stages is about 30: 1 with the charging of raw material than all, and residence time was from about 0.35 to about 0.7 second.These conditions are summarized (table 11) below in more detail.
The double-stage operation of table 11:Saskatchewan heavy oil
Cracking temperature ℃ 80 ℃ of viscosity @ (cSt) Productive rate wt% 15 ℃ of g/ml of density @ API° Productive rate Vol% 1)
515 590 515&590 5.3 52.6 nd 29.8 78.9 nd 0.943 0.990 nd 18.6 11.4 13.9 31.4 78.1 86.6
" nd " do not mean and determines
1) do not catch light condensable materials.Therefore these values are the estimations of guarding.
These results show the gentle cracking of avoiding overcracking and excess air and coke to produce, and then more heavily cracking has produced the product liquid that has increase API and still show good product yield characteristics than heavy material.
Other of use two stage process operated, and relates under about 150 ℃ the raw material injection being maintained the hot gas flow under about 515 ℃ and enter reactor under about 300 ℃ (processing temperatures).The product that comprises than light material (low-boiler) is separating in condenser system after the first step and is removing.In cyclonic separator bottom isolating than heavy material be collected and in reactor near heavier cracking, thereby the product liquid that reduces viscosity and high yield is provided.Used condition is that processing temperature is about 530-590 ℃ in the second stage, the processed and collection of second stage product.
After this two stage process, first step product (starting fraction) be characterized as productive rate, about 19 API, and fall the viscosity that is several times lower than than initial feed with about 30vol%.The high boiling fraction product that recycle fraction processing back produces in the second stage typically is characterized as has the productive rate that is higher than about 75vol%, about 12 API gravity, and than the viscosity of feedstock recycle cut reduction.
Embodiment 5: heavy oil and bituminous " multistage " are handled, and use the raw material of cancellation in primary condenser.
Heavy oil and asphalt stock can also use generalized in table 5 " multistage " pyrolytic process to process.In this system, be configured in US 5,792, the pyrolysis reactor of describing in 340 makes primary condenser that product liquid is imported feed line, arrives reactor, and raw material is introduced in the primary condenser system, there the product vapor that produces during the cancellation pyrolysis.
Processing conditions comprise from about 530 ℃ to about 590 ℃ temperature of reactor.For initial and recirculation operation, use the charging ratio of about 20: 1 to 30: 1 particulate thermal barrier and raw material, and from about 0.35 to about 0.7 second residence time.These conditions are summarized (table 12) below in more detail.The then pyrolysis of raw material, lighter distillate flow be to secondary condenser, and the product liquid heavy component recirculation that obtains from primary condenser is returned reactor and is used for further processing (see figure 5).
Table 12: from multistage feature of processing the product liquid of Saskatehewan heavy oil and pitch acquisition
Cracking temperature ℃ 40 ℃ of viscosity @ (cSt) Productive rate wt% 15.6 ℃ of g/ml of density @ API° Productive rate Vol% 1)
Heavy oil 543 557 561 80 24 53 62.6 58.9 70.9 0.9592 0.9446 0.9568 15.9 18.2 16.8 64.9 62.1 74.0
Pitch 538 40 61.4 0.9718 14.0 71.1
Show the character that is suitable for transporting from the product liquid of the multistage processing of raw material, have from @40 ℃ of heavy oil 6343cSt () and @40 ℃ of pitch 30380cSt () a lot of viscosity reduced.Similarly, API is increased to from 15.9 to 18.2 from about 11 (heavy oil), and is increased to 14.7 from 8.6 (pitches).In addition, the productive rate of heavy oil is from 59 to 68% for heavy oil under these reaction conditionss, is 82% for pitch.
Table 13: use multistage processing from the character of the product liquid of heavy oil preparation and
SimDist (feedstock property sees Table 1 and 5)
Cut Temperature (℃) R241 * R242 **30 days R244 ***
0 day 30 days
@40 ℃ of Mi Du @15.6 ℃ of API Nian Du -- -- -- 0.9592 15.9 79.7 0.9597 15.8 83.2 0.9465 17.8 25.0 0.9591 15.9 49.1
Light raw gasoline is light/the heavy VGO vacuum resid of the light VGO of the medium raw gasoline raw gasoline of medium raw gasoline/kerosene kerosene diesel oil ＜71 71-100 100-166 166-193 193-232 232-327 327-360 360-538 ＞538 0.0 0.0 0.1 0.6 2.8 21.8 10.8 51.1 12.7 0.2 0.1 0.4 0.6 2.5 21.0 10.2 45.0 20.0 0.3 0.2 2.5 1.8 5.0 23.1 9.9 44.9 12.3 0.3 0.3 1.8 1.5 3.5 18.9 8.8 43.2 21.7
*534 ℃ of temperature of reactor
*557 ℃ of temperature of reactor
* *561 ℃ of temperature of reactor
Under these operational conditions, API is increased to about 15.9 to 17.8 from 11.Along with the levels of viscosity of very big reduction, 62.6 (wt% have been realized; R241), 58.9 (wt%; R242) and 70.9 (wt%; R244) product productive rate.Obtained upgrading in essence and shown the character that is suitable for pipeline transportation with respect to these product liquids of raw material.
SimDist result shows in the raw material that the component more than 50% is producing (vacuum resid cut) more than 538 ℃, and being characterized as of product liquid comprises about 78 to 87% more volatile and at the product that produces below 538 ℃.Further being characterized as of raw material has about 0.1% component and producing (raw gasline/kerosene(oil)fraction) below 193 ℃, and product liquid is approximately 1.3 to 4.8%.Kerosene and diesel oil distillate also show the significant difference between raw material and product liquid, 1% feedstock fraction produces down at 193～232 ℃, be 2.8 to 5% promptly for product liquid, and (232-327 ℃, diesel oil) produced 8.7% (raw material) and 18.9 to 23.1% (product liquids) under this temperature range.These results show that jointly the most of component that has low volatility in the raw material has been converted into high-volatile component in the product liquid (light raw gasline, kerosene and diesel oil).These results show product liquid in essence by upgrading, and show the character that is suitable for transporting.
Table 14: " two-stage " processing is descended from the character of the product liquid of bitumen production and SimDist (reaction
Actuator temperature: 538 ℃; For feedstock property referring to table 1,8 and 9)
Cut Temperature (℃) R243
@40 ℃ of Mi Du @15.6 ℃ of API Nian Du -- -- -- 0.9737 13.7 45.4
Light raw gasoline is light/the heavy VGO vacuum resid of the light VGO of the medium raw gasoline raw gasoline of medium raw gasoline/kerosene kerosene diesel oil ＜71 71-100 100-166 166-193 193-232 232-327 327-360 360-538 ＞538 0.3 0.4 3.6 1.9 4.4 19.7 9.1 41.1 19.5
Under these operational conditions, API is increased to about 14 from 8.6.Along with the levels of viscosity (30380cSt (is @40 ℃ from raw material) of very big reduction about 45cSt in the product liquid) obtained the product productive rate of 68.4wt%.
Component in the SimDist analysis revealed raw material more than 50% produces (vacuum resid cut) under the temperature more than 538 ℃, and 80.5% product liquid is producing below 538 ℃.Further being characterized as of raw material has about 0.1% component and produces (raw gasline/kerosene(oil)fraction) down at 193 ℃, and product liquid is approximately 6.2%.Diesel oil distillate also shows the significant difference between raw material and product liquid, and (232-327 ℃) produced 8.7% (raw material) and 19.7% (product liquid) under this temperature range.These results show that jointly the most of component that has low volatility in the raw material has been converted into high-volatile component in the product liquid (raw gasline, kerosene and diesel oil).These results show product liquid in essence by upgrading, and show the character that is suitable for transporting.
Embodiment 6: other features of vacuum gas oil (VGO)
Obtain vacuum gas oil (VGO) from a large amount of non-refinable crude raw materials, raw material comprises:
Athabasca pitch (ATB; ATB-VGO (243) and ATB-VGO (255));
From the hydrotreated VGO of Athabasca pitch (hydrogenation-ATB);
Athabasca VGO Residual oil mixture (ATB-VGO Residual oil);
Hydrotreated ATB-VGO Residual oil (hydrogenation ATB-VGO Residual oil; From obtaining) with the ATB-255 identical operations; And
Kerrobert heavy oil (KHC).
The standard program distillation that use separates in ASTM D2892 and ASTM D5236 is produced VGO from the product liquid that the hot-work above-mentioned raw materials obtains.
For hydrogen treatment Athabasca pitch VGO, reactor condition is as follows:
Temperature of reactor: 720 ;
Reactor pressure: 1,500psig;
Space velocity: 0.5;
Hydrogenation speed: 3625SCFB;
Alaskan North Slope crude oil (ANS) is used for reference.
These VGO character are provided at table 15.
Table 15: from the VGO character of a large amount of heavy oil feedstocks acquisitions
ATB-VGO (243) ATB-VGO (255) The ATB-VGO Residual oil KHC- VGO ANS- VGO Hydrogenation-AT B-VGO
API gravity 13.8 15.2 11.8 ** 15.5 21.7 22.4
Sulphur wt% 3.93 3.76 4.11 ** 3.06 1.1 0.27
Aniline point,  110 125 148-150 119 168 133.4
*See Table 17 for the aniline point that calculates
*Estimate
Use little activity test (MAT) to determine the cracking characteristic (also referring to table 16) of every kind of VGO below under the condition:
Temperature of reaction 1000 ;
30 seconds operating times;
Catalyzer and oily ratio 4.5;
Catalyzer is a balance FCC catalyzer.
The result of MAT test is provided in the table 16, and the result shows that the cracking conversion rate of ATB-VGO (243) is approximately 63%, and KHC-VGO is about 6%, and ANS-VGO is about 73%, and hydrogenation-ATB-VGO is about 74%.In addition, from identical operations (being ATB-VGO (255)), the cracking conversion rate of hydrogenation-ATB-VGO Residual oil is than high about 3% the volume of VGO.The simulation of ATB-VGO and hydrogenation-ATB-VGO combines the temperature that the catalyzer refrigerating unit maintains the revivifier in the performance constraint.
Table 16: little activity test (MAT) result
ATB-VGO-243 ATB-VGO-255 The ATB-VGO Residual oil Hydrogenation-AT B-VGO ANS- VGO KHC- VGO
Catalyst cupport (gram) 4.5054 4.5137 4.5061 4.5064 4.5056 4.5238
Raw material load (gram) 1.0694 1.055 1.0553 1.0188 1 1.0753
Catalyst/oil (gram) 4.2 4.3 4.3 4.4 4.5 4.2
Preheating temperature () 1015 1015 1015 1015 1015 1015
Bed tempertaure () 1000 1000 1000 1000 1000 1000
Oil injection length (second) 30 30 30 30 30 30
Transformation efficiency (wt%) 62.75％ 65.69％ 65.92％ 73.02％ 74.08％ 65.24％
Standard (wt%) H 2S 2.22％ 2.28％ 1.90％ 0.79％ 0.13％ 2.43％
H 2 0.19％ 0.16％ 0.18％ 0.17％ 0.24％ 0.16％
CH 4 1.44％ 1.24％ 1.33％ 1.12％ 1.07％ 1.34％
C 2H 2 0.00％ 0.00％ 0.00％ 0.00％ 0.00％ 0.00％
C 2H 4 1.01％ 0.94％ 1.05％ 0.97％ 0.93％ 0.91％
C 2H 6 1.03％ 0.86％ 0.94％ 0.76％ 0.66％ 0.94％
C 3H 4 0.00％ 0.00％ 0.00％ 0.00％ 0.00％ 0.00％
C 3H 6 4.11％ 3.99％ 4.39％ 5.15％ 4.55％ 3.73％
C 3H 6 1.01％ 1.01％ 1.06％ 1.16％ 1.01％ 1.00％
C 4H 6 0.00％ 0.00％ 0.00％ 0.00％ 0.00％ 0.00％
1-C 4H 8 0.90％ 1.71％ 1.02％ 1.19％ 1.09％ 0.81％
1-C 4H 8 0.96％ 0.69％ 0.92％ 1.05％ 0.83％ 0.79％
c-2-C 4H 8 0.69％ 0.69％ 0.81％ 0.97％ 0.80％ 0.65％
t-2-C 4H 8 0.98％ 0.43％ 1.13％ 1.36％ 1.14％ 0.91％
1-C 4H 10 2.58％ 2.65％ 3.20％ 4.31％ 4.59％ 2.44％
N-C 4H 10 0.38％ 0.48％ 0.50％ 0.65％ 0.63％ 0.48％
C5-430 39.53％ 43.54％ 42.35％ 49.10％ 52.67％ 41.97％
430 -650 23.29％ 22.50％ 22.30％ 18.75％ 18.92％ 22.60％
650 -800 10.71％ 8.86％ 9.03％ 6.06％ 5.27％ 8.85％
800 3.24％ 2.94％ 2.75％ 2.17％ 1.74％ 3.31％
Coke 5.73％ 5.04％ 5.13％ 4.28％ 3.73％ 6.69％
The material balance 97.93％ 98.04％ 98.03％ 96.59％ 97.10％ 98.16％
Aniline point uses ASTM method D611 to determine.As a result, and transformation efficiency and in table 17A and B, provide with the productive rate that vol% calculates.When with when the result's (data not shown) based on wt% compares, obtain similar result.The cracking conversion rate of ATB-VGO (243) and KHC-VGO is than ANS-VGO low 21% and 16% volume.Hydrotreated ATB is than low 5% volume of ANS-VGO.
Measurement aniline point on the table 17A:vol% basis
ANS- VGO vol％FF ATB- VGO (243) vol％FF Hydrogenation ATB-VGO vol%FF KHC- VGO vol％ FF ATB- VGO (255) vol％FF
Raw feed speed: MBPD 68.6 68.6 68.6 68.6 68.6
Valve temperature out  971 971 971 971 971
Raw feed temperature  503 503 503 503 503
Regenerator temperature  1334 1609 1375 1562 1511
Transformation efficiency 73.85 53.01 68.48 57.58 56.53
C 2Lighter Wt%FF 4.13 8.19 4.53 7.70 7.37
H 2S 0.54 1.37 0.12 1.18 1.35
H 2 0.18 0.21 0.22 0.25 0.20
Methane 1.35 2.87 1.65 2.65 2.45
Ethene 1.00 1.37 1.31 1.51 1.31
Ethane 1.07 2.36 1.23 2.11 2.06
Total C 3 9.41 7.15 10.01 8.18 7.05
Propylene 7.37 5.79 7.81 6.54 6.06
Propane 2.04 1.35 2.20 1.64 1.44
Total C 4 13.79 9.35 13.05 11.57 10.34
Trimethylmethane 4.25 2.40 4.85 3.21 2.65
Normal butane 1.08 0.35 1.07 0.53 0.39
Total butylene 8.46 6.60 7.13 7.83 7.30
Gasoline (C 5-430) 58.46 35.35 51.56 39.43 38.58
LCGO(430-650) 20.78 34.74 27.08 32.06 32.05
HCGO+DO(650) 5.37 12.25 4.44 10.36 11.42
Coke, Wt% 5.50 5.83 5.53 5.82 5.70
API gravity 21.7 13.9 22.4 15.5 15.2
Aniline point:  (measurement) 168 110 133.4 119.0 125
When considering result's (table 16) of MAT test, listed ATB-VGO among the table 17A, the transformation efficiency difference of KHC-VGO and hydrogenation ATB-VGO and ANS-VGO (contrast) is greater than expection.This is for ATB-VGO (243), and (255), KHC-VGO, hydrogenation ATB-VGO, ATB-VGO Residual oil, and hydrogenation ATB-VGO Residual oil all is correct.In order to determine whether the aniline point of measuring is not the reliable indication of ATB-, KHC-and hydrogenation-VGO,, use standard method well known in the art to calculate aniline point based on distillation and API gravimetric data.The calculating aniline point of different VGO and cracking conversion rate provide in table 17B and C.
Calculating aniline point on the table 17B:vol% basis
ANS-VGO vol％FF ATB-VGO (243) vol％FF Hydrogenation ATB-VGO vol%FF K-HC-VGO vol％FF
Raw feed: MBPD 68.6 68.6 68.6 68.6
Valve temperature out  971 971 971 971
Raw feed temperature  503 503 503 503
Regenerator temperature  1334 1464 1272 1383
Transformation efficiency 73.85 57.45 74.25 62.98
C 2Lighter Wt%FF 4.13 6.79 3.53 6.05
H 2S 0.54 1.40 0.13 1.25
H 2 0.18 0.17 0.18 0.16
Methane 1.35 2.14 1.21 1.86
Ethene 1.00 1.19 1.07 1.20
Ethane 1.07 1.89 0.94 1.57
Total C 3 9.41 7.33 10.10 8.27
Propylene 7.37 5.93 8.10 6.59
Propane 2.04 1.40 2.00 1.68
Total C 4 13.79 10.76 15.26 12.18
Trimethylmethane 4.25 2.75 5.01 3.37
Normal butane 1.08 0.41 1.18 0.54
Total butylene 8.46 7.60 9.07 8.27
Gasoline (C 5-430) 58.46 39.71 57.07 45.57
LCGO(430-650) 20.78 30.85 22.20 27.70
HCGO+DO(650) 5.37 11.70 3.55 9.32
Coke, Wt% 5.50 5.56 5.33 5.46
API gravity 21.7 13.8 22.4 15.5
Aniline point:  (measurement) 168 135.0 158.0 144.0
Calculating aniline point on the table 17C:vol% basis, continuous table
ATB-VGO (255) vol％FF Hydrogenation ATB-VGO (255) vol%FF ATB-VGO Residual oil vol%FF Hydrogenation ATB-VGO Residual oil vol%FF
Raw feed: MBPD 68.6 68.6 68.6 68.6
Valve temperature out  971 971 971 971
Raw feed temperature  503 503 503 503
Regenerator temperature  1374 1238 1345 * 1345 *
Transformation efficiency 60.86 75.29 83.82 72.34
C 2Lighter 6.13 3.36 4.80 4.13
H 2S 1.42 0.12 1.55 0.04
H 2 0.14 0.17 0.18 0.60
Methane 1.85 1.13 1.43 1.56
Ethene 1.10 1.04 0.48 0.79
Ethane 1.63 0.89 1.17 1.14
Total C 3 7.54 10.44 7.66 8.49
Propylene 6.07 8.62 5.97 6.76
Propane 1.47 1.82 1.69 1.73
Total C 4 11.58 16.56 12.99 12.60
Trimethylmethane 2.96 4.96 3.34 3.75
Normal butane 0.44 1.19 0.49 0.99
Total butylene 8.18 10.40 9.16 7.85
Gasoline (C 5-430) 43.38 56.87 45.61 56.66
LCGO(430-650) 28.61 21.09 26.28 21.59
HCGO+DO(650) 10.52 3.62 9.89 6.06
Coke, Wt% 5.43 5.30 7.54 6.42
API gravity 15.2 23.9 11.8 20.0
Aniline point:  (measurement) 145 168 148.0 170.0
All increased and more with consistent based on all aniline points of aniline point that calculate from MAT test established data.For example, aniline point is as follows:
ATB-VGO (243) is 135 
ATB-VGO (255) is 145 
KHC-VGO is 135 
The ATB-VGO-Residual oil is 148 
Hydrogenation ATB-VGO is 158 , and
Hydrogenation ATB-VGO-Residual oil is 170 .
For ANS-VGO (contrast), aniline point and product productive rate do not change.The product productive rate that increases along with the calculating aniline point that increases is consistent with MAT result's cracking difference in the table 16.
These results show that RTP product VGO has the side chain that obtains from cracking in a large number, and provide than coming from the higher transformation efficiency of aniline point measurement.
Embodiment 7: calcium adds coming from the influence of the quick hot worked product liquid character of heavy hydrocarbon feeds
A: calcium adds the influence to the product liquid character that comes from pitch processing, comprises TAN (total acid value)
During the Rapid Thermal processing of normal running, implement baseline test (cycle 1, table 18).Second test relates to (cycle 2, table 18) interpolation Ca (OH) in the sand reheater 2(8.4wt%), and the 3rd test at Ca (OH) 2With carry out under the mixing of asphalt stock (cycle 3, table 18).In the sand reheater, add Ca (OH) 2In-line carries out, and returns sand and coke to the sand reheater from separator 180 simultaneously.Use feed line (270) with Ca (OH) 2Add in the raw material.The rapid processing of raw material is implemented under from 510 to 540 ℃ temperature.The temperature range of sand reheater is from 730～815 ℃.API gravity and force of gravity use ASTM method D4052 to determine; Viscosity uses ASTM D445 to determine; Ash content uses D482-95 to determine, MCRT (the residual test of little carbon) uses ASTM D4530-95 to analyze; TAN (total acid value) uses D664 to analyze; Sulphur uses D4294 to measure; Metal (Ni, V, Ca and Mg) uses D5708 to determine.Represent at table 18 from the raw material of every kind of processing and the composition of product liquid.
Table 18: raw material (Feed), have or do not exist Ca (OH) 2Following Rapid Thermal is decomposed the liquid that obtains
The composition of body product (Prod) (cycle 1～3 is defined as follows)
Operation 278 Cycle 1 Feed Cycles 3 Feed Cycle 1 Prod Cycles 2 Prod Cycles 3 Prod
API gravity (degree API) @20 ℃ of @550 ℃ of (wt%) MCRT of (cSt) Hui Fen of proportion Nian Du (wt%) neutralization value TAN (total acid value: sulphur (wt%) metal Ni mg KOH/g), ppm metal V, ppm metal Ca, ppm metal M g, ppm 7.9 0.9992 n/a 0.07 13.2 3.37 4.1 66 176 4.8 0.2 5.4 1.0184 n/a 5.17 15.1 1.06 1.9 67 182 18650 138 14.0 0.9727 626 0.14 6.7 2.49 4.2 21 63 52 4 12.8 0.9803 633 1.24 7.0 2.01 3.1 20 74 3877 31 13.6 0.9755 663 0.20 6.2 0.55 4.0 20 59 476 4
Cycle 1: normal heat processing (not adding calcium cpd)
Cycle 2: in the sand reheater, add Ca (OH) 2
Cycle 3: in raw material, add Ca (OH) 2
These results represent to add the API gravity or the proportion that can not change product liquid in any tangible mode in sand reheater or raw material.When raw material at Ca (OH) 2Existence under add man-hour, the TAN value of product liquid has reduced.But as Ca (OH) 2Be added in the reheater reduction maximum of TAN value when being added into raw material than it.Specifically, when during raw material processing with Ca (OH) 2When being added in the sand reheater, the TAN value in the product is reduced to 2.01 from 2.49, but Ca (OH) 2The TAN value of product has been reduced to 0.55 significantly when being added to raw material.
At Ca (OH) 2Exist the product liquid of producing down to show Ca (OH) 2Concentration increases.This is to work as Ca (OH) 2Observed when producing product liquid under being added in raw material or the sand reheater, show portion C a (OH) 2With the particulate thermal barrier by recirculation from the sand reheater.Separation Research (data do not provide) show water (1～3wt%) in the presence of in pitch, add CaO (3wt%), perhaps in pitch, add Ca (OH) 2(1～16%) has caused the bituminous acid content to be lower than 0.05 (mg KOH/g) from the TAN of 3.22 (mg KOH/g) to being reduced to.
B: calcium adds coming from the influence of the product liquid TAN with high TAN value and the processing of low sulfur content heavy oil feedstock
This test relates to Ca (OH) 2Form to heavy oil feedstock, (Bakersfield, adding total amount in Califomia) is the Ca of 1.2wt% in San Ardo oil field.Use feed line (270) with Ca (OH) 2Add in the raw material.The Rapid Thermal processing of raw material is implemented under from 70 to 100 ℃ temperature.The temperature of sand reheater is from 730～815 ℃.Raw material is introduced in the reactor under the speed of 50lbs./hr.Use ASTM method D664 to analyze TAN (total acid value).Raw material, usefulness total amount 3.0wt%Ca (OH) are untreated 2The raw material of handling is represented in table 19 with the TAN value that comes from Rapid Thermal processing calcium processing raw material.
Table 19: heavy oil feedstock, Ca (OH) 2Existing down, Rapid Thermal decomposition raw material obtains
The TAN value of product liquid
Operation 286 Ca，wt％ TAN，mg KOH/g
Untreated raw material 0.00605 5.03
With 3.0wt%Ca (OH) 2The raw material of handling (raw material that calcium is handled) 1.21 1.65
Come from calcium and handle the product of raw material a 0.00316 0.87
Come from calcium and handle the product of raw material b 0.00565 1.01
Come from calcium and handle the product of raw material c 0.0039 0.99
A: from the product of first condenser sampling
B: from the product of second condenser sampling
C: the product of from mist eliminator, sampling
The product that is produced by this experiment shows and is lower than the about 5 times TAN value of the raw material that is untreated.The product TAN value that comes from first condenser, second condenser or mist eliminator does not have significant difference.The TAN value (1.65) of raw material was hanged down 3 times than the TAN value of the raw material that is untreated (5.03) when experiment finished.Because low corrodibility, the reduction of this raw material TAN value can prolong the life-span of other used in fast pyrolysis reactor and system of processing assembly.The Ca content wt% of every kind of product liquid is lower than adding Ca (OH) 2The calcium contents that exists in the preceding raw material, this shows that the calcium cpd that is added in the raw material enters condenser or mist eliminator with product.
Embodiment 8: calcium adds the S0 to discharging in the stack gas during the fast pyrogenation heavy hydrocarbon feeds 2The influence of concentration
A: calcium adds the SO to discharging in the stack gas during the fast pyrogenation asphalt stock 2The influence of concentration
When estimating the formed asphalt raw material, in the charging of sand reheater (30, the fluidized-bed reheater) or Rapid Thermal system of processing, add calcium, such as, but be not limited to calcium hydroxide (Ca (OH) 2) interests, carry out the release test program.In the pipeline that sand and coke is turned back in the sand reheater, carry out the interpolation in the sand reheater from separator 180.Use the interpolation of feed line (270) in raw material.
Test and come quantitatively and in raw material or sand reheater, add Ca (OH) 2Potential relevant sulfurous gas (SO 2, perhaps any gaseous sulfur species) reduction.Also particulate matter and combustion gases are carried out release test.This time course analysis is provided in Fig. 6 and 7.Fig. 6 represents to implement the time course of calcium interpolation several times in sand reheater and feed line, and Fig. 8 represents to add to the sand reheater time course of calcium.
With reference to Fig. 7 and 8, represented during SO in the stack gas basically by the Rapid Thermal formed asphalt raw material described in the embodiment 1 2(SO x) discharge the sampling along with the time, from 510 to 540 ℃ of temperature of reaction.The temperature of sand reheater is from 730～815 ℃.Residence time is 1～2 second under each temperature.The average reactor temperature recorder is shown in the top fritter of Fig. 7.
Use SICK AG GME64 infrared gas analyzer to analyze sulphur.At the SO that does not add under any 2Baseline is recorded in about 1000 to about 1400 fluctuations.
The reheater charging is mainly the Ca (OH) that relative raw material uses 8.4wt% 2Because the sulphur content of raw material is about 5wt%, the stoichiometric ratio of raw materials of Ca/S is about 0.7 relatively.But the original sulphur of 35～45wt% finishes in reheater because only have an appointment, so the stoichiometric ratio of reheater Ca/S is about 1.7～2.As the Ca (OH) that in raw material, adds 4wt% 2The time, the stoichiometric ratio of raw materials of Ca/S is about 0.3 relatively, and is about 1 in reheater.
Provided the time line (see figure 7) of experiment below:
13:00 (the A)-Ca (OH) of interpolation 8.4wt% in the sand reheater 2(raw material, about 1.7～2 times of stoichiometries are heavy) causes stack gas SO 2Be released in 5 minutes fast and be reduced to 400 from about 1400 tempestuously, and in next hour, be reduced to about 200 level (this part of Fig. 7 is represented) in Fig. 8;
14:18 (B)-stop to add Ca (OH) 2Cause SO 2Discharge about 1150 levels that stably are increased near baseline.This lower baseline may be because Ca (OH) 2With the recirculation in system of particulate thermal barrier;
16:15 (C)-after obtaining stable baseline, in the sand reheater, add Ca (OH) 2(8.4wt%), and observe SO 2Reduce the second time that discharges fast.
16:50 (D)-stop to add Ca (OH) 2, sulphur discharges corresponding increase.
17:13 (E)-adding more a spot of Ca (OH) in the sand reheater 2(6.6wt%), SO 2Discharge once more and reduce;
17:36 (F)-stop to add Ca (OH) 2The baseline of Jiang Diing (at 17:59 with respect at 12:00, perhaps at 15:00) may be because Ca (OH) once more 2Recirculation in system;
The Ca (OH) of 18:00 (G)-1wt% (raw material relatively) 2Be added in the raw material, and notice SO 2The slight reduction that discharges;
The Ca (OH) of 18:37 (H)-2wt% (raw material relatively) 2Be added in the raw material, and SO 2Discharging for the second time, reduction faster is tangible;
The Ca (OH) of 19:12 (I)-4wt% (raw material relatively) 2Be added in the raw material, and observe SO 2Discharge faster and reduce;
20:29 (J)-stop to add Ca (OH) 2
Based on these data, belong to Ca (OH) 2Be injected into sulphur the removing efficient and can reach 95% in the sand reheater fluidized-bed from stack gas.
In raw material, add Ca (OH) 2Also caused SO in the stack gas 2Reduction gradually.Be lower than the Ca (OH) of stoichiometry 2Cause the SO of edge (being lower than ratio) 2Reduce.Chemical approximately metered amount obviously is more effective.Expectation sulphur discharges and can reduce by 90% when mixing with raw material with stoichiometry.
B: calcium adds the SO that discharges in the stack gas during the high TAN of fast pyrogenation, the low sulfur-bearing heavy oil feedstock 2The influence of concentration
(Bakersfield, the interests of adding calcium in the time of California) in the charging of Rapid Thermal system of processing are carried out the release test program, such as, but be not limited to adding calcium hydroxide (Ca (OH) in processing heavy oil raw material San Ardo oil field in order to estimate 2).Use feed line (270) in raw material, to add.
Test and come quantitatively and in raw material or sand reheater, add Ca (OH) 2Potential relevant sulfurous gas (SO 2, perhaps any gaseous sulfur species) reduction.Also particulate matter and combustion gases are carried out release test.Fig. 9 represents to implement the time course of calcium interpolation several times in feed line.
With reference to Fig. 8, represented in Rapid Thermal processing heavy oil raw material San Ardo oil field (Bakersfield, California) during, SO in the stack gas 2Release is along with the sampling of time, from 70 to 100 ℃ of temperature of reaction.The temperature of sand reheater is from 730～815 ℃.Residence time is 1～2 second under each temperature.
Use SICK AG GME64 infrared gas analyzer to analyze sulphur.At the SO that does not add under any 2Baseline is recorded in about 1000 to about 1400 fluctuations.
Provided the time line (see figure 7) of experiment below:
15:20 (A)-in the presence of 5% water, in raw material, add the Ca (OH) of 1.5wt% (raw material) 2Cause stack gas SO 2Be released in about 30 minutes from about 500 and be reduced to 250, and in following 1.8 hours, be reduced to about 200 level;
17:37 (B)-in raw material adds the Ca (OH) of 1.5wt% (based on raw material) for the second time 2Cause stack gas SO 2Be released in and further be reduced to about 160 level after following 0.65 hour;
Embodiment 9: calcium adds the H that produces during the high TAN of fast pyrogenation, the low sulfur-bearing heavy oil feedstock 2The influence of S amount
The Rapid Thermal of stock oil adds trade union and produces hydrogen sulfide (H 2S) as by product, the composition of its meeting pollution products stream.H 2The concentration of S depends on the concentration and the type of sulphur compound in the raw material.This embodiment shows that the Rapid Thermal processing of stock oil in the presence of calcium cpd can reduce the hydrogen sulfide (H that pollution products gas body is formed 2S) amount.
(Califomia) there are not and exist Ca (OH) in San Ardo oil field, Bakersfield to comprise the heavy oil feedstock of 2.2wt% sulphur 2Situation under accept Rapid Thermal processing.Ca (OH) never 2The product gas that following pyrolysis feed is produced comprises the H of about 1vol% 2S (seeing sample 1, table 20).With Ca (OH) 2Form add 0.6wt% calcium and make H in the product 2The concentration of S is reduced to about 0.4vol%, has approximately reduced by 60% hydrogen sulfide content (referring to sample 2～3, table 20).Further in raw material, add Ca (OH) 2(total amount of 1.2wt%) is with H 2S content is reduced to GC detectability following (sample 4, table 20).Ca (OH) 2The validity that reduces hydrogen sulfide content is subjected to the influence (sample 5, table 20) of raw material/sand ratio.
Table 20: do not have and exist Ca (OH) 2Situation under Rapid Thermal decompose heavy hydrocarbon
H in the gaseous product that raw material produced 2The content of S
Product gas is collected sample 1 2 3 4 5
Calcium adds, Ca wt% in the raw material - 0.6 0.6 1.2 1.2
Feeding rate, 1b/hr 50 50 50 50 100+
H 2S (does not contain N 2，O 2)，vol％ 0.97 0.46 0.39 0.00 0.37
Ca handles the H that removes 2S percentage ratio - 53 60 100 62
All quoted passages are incorporated herein for referencial use.
The present invention is described with reference to embodiment preferred.But, those skilled in the art be it is apparent that can make a large amount of variations and modification, and do not deviate from scope of the present invention as herein described.

Claims (46)

1, a kind of reduction comes from the method for one or more component hydrogen sulfide contents of the product stream of heavy hydrocarbon feeds, and it comprises:
I) Rapid Thermal of heavy hydrocarbon feeds processing;
The processing of wherein said Rapid Thermal is included in and under 450 ℃-600 ℃ the temperature heavy hydrocarbon feeds and inert particulate thermal barrier is interacted in last flow reactor to be less than for 5 seconds, and the generation product flows, and
The ratio of wherein said particulate thermal barrier and heavy hydrocarbon feeds is 10: 1-200: 1 and
Ii) regeneration of particle thermal barrier in reheater forms regenerated particulate thermal barrier;
The iii) supreme flow reactor of particulate thermal barrier of reclaiming;
Wherein:
A) carry out in the presence of the calcium cpd of the Rapid Thermal of heavy hydrocarbon feeds processing in joining described reactor; Perhaps
B) carry out in the presence of the Rapid Thermal of the heavy hydrocarbon feeds processing calcium cpd in joining described reactor, the particulate thermal barrier in described reheater, joining the other amount in the described reheater calcium cpd in the presence of regenerate; Perhaps
C) the particulate thermal barrier is joining regeneration in the presence of the calcium cpd in the described reheater in described reheater, and
The amount that wherein adds calcium cpd is 0.2-5 a times of sulfur chemistry metered amount in the raw material.
2, the method for claim 1, it also comprises removes the step that comprises product stream and particulate thermal barrier mixture from described reactor.
3, the method for claim 2, it also comprises the step of from described mixture separated product stream and particulate thermal barrier.
4, the method for claim 3, it also comprises from described product stream collects the step that distillates product and bottoms.
5, the method for claim 4, wherein said bottoms are accepted further Rapid Thermal processing steps.
6, the method for claim 5, wherein said further Rapid Thermal procedure of processing are included in and make bottoms and the interaction of particulate thermal barrier be less than for 5 seconds in the reactor, produce product stream, and wherein the ratio of particulate thermal barrier and heavy hydrocarbon feeds is 10: 1-200: 1.
7, the process of claim 1 wherein that described raw material combines with calcium cpd before introducing reactor.
8, the process of claim 1 wherein and operate under the temperature of described reheater in 600-900 ℃ of scope.
9, the process of claim 1 wherein and operate under the temperature of described reheater in 600-815 ℃ of scope.
10, the process of claim 1 wherein and operate under the temperature of described reheater in 700-800 ℃ of scope.
11, the process of claim 1 wherein and operate under the temperature of described reheater in 480-550 ℃ of scope.
12, the process of claim 1 wherein that described calcium cpd adds in the reheater.
13, the method for claim 12, wherein said calcium cpd had both added in the reactor, also added in the reheater.
14, the process of claim 1 wherein add calcium cpd amount be sulfur chemistry metered amount in the raw material 1.7-2 doubly.
15, the process of claim 1 wherein that described calcium cpd is selected from following group: lime acetate, calcium formiate, calcium propionate, contain the bio oil composition of calcium salt, isolating calcium salt, Ca (OH) from contain calcium salt bio oil composition 2, CaO, CaCO 3And their mixture.
16, the process of claim 1 wherein that described calcium cpd combines with raw material and 0～5 weight % water.
17, the method for claim 16, wherein said water are the forms of steam.
18, the process of claim 1 wherein the release that reduces sulfenyl gas in the stack gas.
19, the process of claim 1 wherein and reduce total acid value in the product liquid.
20, the process of claim 1 wherein that raw material is introduced into fractional column before described Rapid Thermal procedure of processing, the volatile constituent of this fractional column separate raw materials from the liquid ingredient of raw material, and described liquid ingredient carries out Rapid Thermal processing.
21, the method for claim 20, wherein said raw material combined with calcium cpd before introducing fractional column.
22, the process of claim 1 wherein that described calcium cpd is selected from Ca (OH) 2, CaO and their mixture.
23, the process of claim 1 wherein that described calcium cpd is Ca (OH) 2
24, a kind of method of upgrading heavy hydrocarbon feeds, it comprises:
I) Rapid Thermal of heavy hydrocarbon feeds processing;
The processing of wherein said Rapid Thermal is included in and under 450 ℃-600 ℃ the temperature heavy hydrocarbon feeds and inert particulate thermal barrier is interacted in last flow reactor to be less than for 5 seconds, and the generation product flows, and
The ratio of wherein said particulate thermal barrier and heavy hydrocarbon feeds is 10: 1-200: 1 and
Ii) regeneration of particle thermal barrier in reheater forms regenerated particulate thermal barrier; With
The iii) supreme flow reactor of particulate thermal barrier of reclaiming;
Wherein:
A) carry out in the presence of the calcium cpd of the Rapid Thermal of heavy hydrocarbon feeds processing in joining described reactor; Perhaps
B) carry out in the presence of the Rapid Thermal of the heavy hydrocarbon feeds processing calcium cpd in joining described reactor, the particulate thermal barrier in described reheater, joining the other amount in the described reheater calcium cpd in the presence of regenerate; Perhaps
C) the particulate thermal barrier is joining regeneration in the presence of the calcium cpd in the described reheater in described reheater, and
The amount that wherein adds calcium cpd is 0.2-5 a times of sulfur chemistry metered amount in the raw material.
25, the method for claim 24, it also comprises removes the step that comprises product stream and particulate thermal barrier mixture from described reactor.
26, the method for claim 25, it also comprises the step of from described mixture separated product stream and particulate thermal barrier.
27, the method for claim 26, it also comprises from described product stream collects the step that distillates product and bottoms.
28, the method for claim 27, wherein said bottoms are accepted further Rapid Thermal processing steps.
29, the method for claim 28, wherein said Rapid Thermal procedure of processing are included in and make bottoms and the interaction of particulate thermal barrier be less than for 5 seconds in the reactor, produce product stream, and wherein the ratio of particulate thermal barrier and heavy hydrocarbon feeds is 10: 1-200: 1.
30, the method for claim 24, wherein said raw material combines with calcium cpd before introducing reactor.
31, the method for claim 24 is operated under the temperature of wherein said reheater in 600-900 ℃ of scope.
32, the method for claim 24 is operated under the temperature of wherein said reheater in 600-815 ℃ of scope.
33, the method for claim 24 is operated under the temperature of wherein said reheater in 700-800 ℃ of scope.
34, the method for claim 24 is operated under the temperature of wherein said reheater in 480-550 ℃ of scope.
35, the method for claim 24, wherein said calcium cpd adds in the reheater.
36, the method for claim 35, wherein said calcium cpd had both added in the reactor, also added in the reheater.
37, the method for claim 24, the amount that wherein adds calcium cpd are 1.7-2 times of sulfur chemistry metered amount in the raw material.
38, the method for claim 24, wherein said calcium cpd are selected from following group: lime acetate, calcium formiate, calcium propionate, contain the bio oil composition of calcium salt, isolating calcium salt, Ca (OH) from contain calcium salt bio oil composition 2, CaO, CaCO 3, and their mixture.
39, the method for claim 24, wherein said calcium cpd combines with raw material and 0～5 weight % water.
40, the method for claim 39, wherein said water are the forms of steam.
41, the method for claim 24 wherein reduces the release of sulfenyl gas in the stack gas.
42, the method for claim 24 wherein reduces the total acid value in the product liquid.
43, the method for claim 24, wherein before described Rapid Thermal procedure of processing, raw material is introduced into fractional column, the volatile constituent of this fractional column separate raw materials from the liquid ingredient of raw material, and described liquid ingredient carries out Rapid Thermal processing.
44, the method for claim 43, wherein said raw material combined with calcium cpd before introducing fractional column.
45, the method for claim 24, wherein said calcium cpd are selected from Ca (OH) 2, CaO and their mixture.
46, the method for claim 24, wherein said calcium cpd are Ca (OH) 2
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WO1997031083A1 (en) * 1996-02-22 1997-08-28 Exxon Chemical Patents Inc. Process for obtaining olefins from residual and other heavy feedstocks
CN1195019A (en) * 1997-03-31 1998-10-07 中国科学院长春应用化学研究所 Technique for separating alkylate product

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Publication number Priority date Publication date Assignee Title
WO1997031083A1 (en) * 1996-02-22 1997-08-28 Exxon Chemical Patents Inc. Process for obtaining olefins from residual and other heavy feedstocks
CN1195019A (en) * 1997-03-31 1998-10-07 中国科学院长春应用化学研究所 Technique for separating alkylate product

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