CN101297021A - Methods of cracking a crude product to produce additional crude products - Google Patents

Methods of cracking a crude product to produce additional crude products Download PDF

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Publication number
CN101297021A
CN101297021A CNA2006800395616A CN200680039561A CN101297021A CN 101297021 A CN101297021 A CN 101297021A CN A2006800395616 A CNA2006800395616 A CN A2006800395616A CN 200680039561 A CN200680039561 A CN 200680039561A CN 101297021 A CN101297021 A CN 101297021A
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hydrocarbon
catalytic cracking
fluid
logistics
stream
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W·毛
V·奈尔
A·W·M·勒斯
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21BEARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21BEARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B36/00Heating, cooling or insulating arrangements for boreholes or wells, e.g. for use in permafrost zones

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • Mining & Mineral Resources (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Fluid Mechanics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Resistance Heating (AREA)

Abstract

The invention provides a method for producing petroleum crude product, which includes, producing a formation fluid using the underground home position treatment process; separating the formation fluid, producing liquid logistics and first air logistics; rectifying the liquid logistics, producing one or a plurality of petroleum crude product; and catalytic cracking petroleum crude product whose boiling point is more than 343 EDG C, and producing one or a plurality of additional petroleum crude product. The first air logistics can include olefin hydrocarbon. The boiling point of at least one petroleum crude product is more than 343 EDG C and at least one additional petroleum crude product is the second air logistics.The first air logistics can include olefin hydrocarbon. The boiling point of at least one petroleum crude product is more than 343 EDG C and at least one additional petroleum crude product is the second air logistics.

Description

The cracking crude oil products is produced the method for additional crude oil products
Technical field
Relate generally to of the present invention by various subsurface formations for example hydrocarbon containing formation produce the method and system of hydrocarbon, hydrogen and/or other products.
Background technology
The hydrocarbon that from subsurface formations, obtains usually as the energy, as raw material with as the consumer's goods.The worry that obtainable hydrocarbon source is exhausted and the worry that the total mass of the hydrocarbon produced descends caused having developed the method for gathering more effectively, processing and/or using obtainable hydrocarbon source.Can use in-situ method from subsurface formations, to shift out hydrocarbon materials.May need to change the chemistry and/or the physicals of the hydrocarbon materials in the subsurface formations, from subsurface formations, shift out more easily to allow hydrocarbon materials.Chemistry and physical change can comprise the reaction in of the viscosity variation that produces extensible fluid, forms hydrocarbon materials in variation, changes in solubility, variable density, phase transformation and/or the stratum.Fluid can be but be not limited to gas, liquid, emulsion, slurry and/or have logistics with the solid particulate of the similar flow performance of liquid-flow.
The resident fluid that uses the situ heat treatment method to obtain from subsurface formations can be sold and/or be processed to produce commerical prod.The resident fluid of producing by the situ heat treatment method can have and different performance and/or the compositions of resident fluid that obtains by conventional production method.The resident fluid that uses the situ heat treatment method to obtain from subsurface formations may not satisfy the industrial standards of transportation and/or commercial applications.Therefore, need to handle improving one's methods and system of the resident fluid that from various hydrocarbon containing formations, obtains.
Summary of the invention
The treatment process of the resident fluid that embodiment relate generally to described herein is produced from subsurface formations.
In some embodiments, the invention provides: by underground original position pyrolysis heat treating process grown place layer fluid; Separate this resident fluid, produce the liquid stream and first gas stream, wherein first gas stream comprises alkene; The rectifying liquid stream is produced one or more crude oil products, and wherein the boiling Range Distribution Analysis of at least a crude oil products is 38-343 ℃; With the catalytic cracking boiling Range Distribution Analysis be 38-343 ℃ crude oil products, produce one or more additional crude oil products, the boiling point that wherein at least a additional crude oil products is second gas stream and this gas stream is 38 ℃ at the most, wherein measures boiling Range Distribution Analysis by ASTM method D5307.
In some embodiments, the invention provides the method for producing one or more crude oil products, this method comprises: by underground situ heat treatment method grown place layer fluid; Separate this resident fluid, produce liquid stream; In first catalytic cracking system, this liquid stream of catalytic cracking by contacting this liquid stream and catalytic cracking catalyst is produced crude oil products logistics and useless catalytic cracking catalyst; This useless catalytic cracking catalyst of regenerating is produced the regenerated cracking catalyst; In second catalytic cracking system, the catalytically cracked gasoline hydrocarbon stream by contact gasoline hydrocarbon logistics and regenerated catalytic cracking catalyst is produced and is contained carbon number and be the thick olefin stream of at least 2 hydrocarbon and the exhausted cracking catalyst of regenerating; With from thick olefin stream, separate alkene, wherein the carbon number of alkene is 2-5; With provide exhausted regeneration cracking catalyst to first catalytic cracking system from second catalytic cracking system.
In further embodiment, capable of being combined from specific embodiments feature and from the feature of other embodiment.For example from the feature of an embodiment can with the characteristics combination from any other embodiment.
In further embodiment, use any method, system or well heater described herein, carry out the processing of subsurface formations.
In further embodiment, can add additional feature in specific embodiments described herein.
Description of drawings
Benefiting under following detailed description and the situation with reference to the accompanying drawings, advantage of the present invention will become apparent for a person skilled in the art, wherein:
Fig. 1 has provided the synoptic diagram of the embodiment of a part of situ heat treatment system that handles hydrocarbon containing formation.
Fig. 2 has described and has handled the synoptic diagram that the mixture of being produced by the situ heat treatment method is used the embodiment of system.
Fig. 3 has described and has handled the synoptic diagram that the liquid stream of being produced by the situ heat treatment method is used the embodiment of system.
Although the present invention is easy to carry out various improvement and alternative form, its specific embodiments provides by the by way of example in the accompanying drawing, and can describe in detail herein.Accompanying drawing may not be pro rata.Yet, should be appreciated that accompanying drawing and detailed description thereof are not intended to limit the invention to particular forms disclosed, on the contrary, the present invention intends covering spirit of the present invention and interior all improvement, equivalence and the replacement scheme of scope that drops on the claims definition.
Embodiment
Following explanation relate generally to is handled the System and method for of the hydrocarbon in the stratum.This stratum be can handle and hydrocarbon product, hydrogen and other products obtained.
Following explanation relate generally to is handled and is used the System and method for of situ heat treatment method by the resident fluid of hydrocarbon containing formation production.Can handle hydrocarbon containing formation obtain hydrocarbon product, hydrogen, methane and other products,
" hydrocarbon " is normally defined the molecule that is mainly formed by carbon and hydrogen atom.Hydrocarbon also can comprise other element, such as but not limited to halogen, metallic element, nitrogen, oxygen and/or sulphur.Hydrocarbon can be but be not limited to petrologen, pitch, pyrobitumen, oil, natural mineral wax and vasphaltic pyrobitumen.Hydrocarbon can be positioned at intracrustal matrices or adjacent with it.Parent rock can include but not limited to sedimentogeneous rock, sand, silicate, carbonate, diatomite and other porous medium." hydrocarbon fluid " is the fluid that comprises hydrocarbon.Hydrocarbon fluid can comprise, carries secretly or be entrained in the non-hydrocarbon fluids, and described non-hydrocarbon fluids is hydrogen, nitrogen, carbon monoxide, carbonic acid gas, hydrogen sulfide, water and ammonia for example.
" stratum " comprises one or more layers hydrocarbon bearing formation, one or more layers nonhydrocarbon layer, overlying strata and/or underlying formation." overlying strata " and/or " underlying formation " comprises a class or how inhomogeneous impermeable material.For example overlying strata and/or underlying formation can comprise rock, shale, mud stone or wet/tight carbonate.In position in some embodiments of heat treating process, overlying strata and/or underlying formation can comprise one deck hydrocarbon bearing formation or multilayer hydrocarbon bearing formation, and described hydrocarbon bearing formation is impermeable relatively and do not have experience to cause temperature in the situ heat treatment course of processing of the remarkable characteristic variations of hydrocarbon bearing formation in overlying strata and/or the underlying formation.For example underlying formation can comprise shale or mud stone, but does not allow to heat under the pyrolysis temperature of overlying strata during the situ heat treatment method.In some cases, overlying strata and/or underlying formation can have some perviousness.
" resident fluid " is meant the fluid that is present in the stratum, and can comprise pyrolyzation fluid, synthetic gas, moving fluid, visbreaking fluid and water (steam).Resident fluid can comprise hydrocarbon fluid and non-hydrocarbon fluids." moving fluid " is meant as the fluid in result's energy mobile hydrocarbon containing formation on thermal treatment stratum." visbreaking fluid " is meant the fluid that the viscosity as a result as the thermal treatment stratum has reduced.
" fluid of being produced " is meant the resident fluid that shifts out from the stratum.
" converted in-situ method " be meant by thermal source heating hydrocarbon containing formation with raise at least partially layer temperature to more than the pyrolysis temperature so that in the stratum, produce the method for pyrolyzation fluid.
" carbon number " is meant intramolecular carbonatoms.Hydrocarbon fluid can comprise the various hydrocarbon with different carbon numbers.Hydrocarbon fluid can be described by carbon number distribution.Can distribute and/or activity coefficients and relative volatilities carbon number and/or carbon number distribution by real boiling point.
" thermal source " is to provide heat to arrive any system at least a portion stratum by conduction and/or radiative transfer substantially.For example thermal source can comprise electric heater, for example insulated conductor, elongate member and/or the conductor arranged in conduit.Thermal source also can comprise by in the outside, stratum or internal-combustion fuel generate the system of heat.This system can be the burner of surface combustion burner, downhole gas burner, aphlogistic distributed combustion device and NATURAL DISTRIBUTION.In some embodiments, the heat that can in one or more thermals source, provide or generate by other power supply.But other energy direct heating stratum perhaps can apply energy to transmitting on the medium, and described transmission medium directly or indirectly heats the stratum.The one or more thermals source that apply heat to the stratum should be understood and the different energy can be used.Therefore, for example for given stratum, some thermal source can be supplied heat by resistance heater, some thermal source can provide heat by burning, and some thermal source can provide heat by one or more other energy (for example chemical reaction, sun power, wind energy, biological substance or other reproducible energy).Chemical reaction can comprise thermopositive reaction (for example oxidizing reaction).Thermal source also can comprise provide heat arrive with the heating location adjacent area and/or in its peripheral region the well heater of heater well for example.
" well heater " is any system or the thermal source that generates heat in well or in the nigh well bore region.Well heater can be but be not limited to electric heater, burner, with the burner of material in the stratum or the material reaction that from the stratum, produces and/or their combination.
" situ heat treatment method " is meant that adopting thermal source heating hydrocarbon containing formation to be higher than with the layer temperature that raise at least partially causes moving fluid, hydrocarbonaceous material visbreaking and/or pyrolytic method of temperature, so that produce moving fluid, visbreaking fluid and/or pyrolyzation fluid in the stratum.
Term " wellhole " is meant the hole in the stratum that forms by probing in the stratum or insertion conduit.Wellhole can have circular basically cross section, perhaps is other cross-sectional shape.Term as used herein " well " and " opening " can exchange with term " wellhole " and use when the opening that is meant in the stratum.
" pyrolysis " is owing to apply the chemical bond rupture that heat causes.For example pyrolysis can comprise by independent heating compound is changed into one or more other materials.Heat can be transferred on a part of stratum to cause pyrolysis.In some stratum, a part of stratum and/or other material in the stratum can promote pyrolysis by catalytic activity.
" pyrolyzation fluid " or " pyrolysis product " is meant the fluid that produces basically in the process of pyrolysed hydrocarbon.The fluid that produces by pyrolytic reaction can mix with other fluid in the stratum.This mixture will be regarded as pyrolyzation fluid or pyrolysis product." pyrolysis zone " as used herein is meant and reacted or reacted the stratum volume (for example permeable relatively stratum is as tar sand formation) that forms pyrolyzation fluid.
" cracking " be meant involve that organic compound decomposes and molecular recombination with the technology of generation than the greater amt molecule that exists at first.In cracking, be accompanied by hydrogen atom transfer generation series reaction between the molecule.For example petroleum naphtha can experience heat cracking reaction formation ethene and H 2
" visbreaking " be meant in heat treatment process in the fluid disentanglement of molecule and/or in heat treatment process macromole resolve into than small molecules, thereby cause fluid viscosity to descend.
" condensable hydrocarbon " is the hydrocarbon of condensation under 25 ℃ and 1 bar absolute pressure.Condensable hydrocarbon can comprise the mixture of carbon number greater than 4 hydrocarbon." uncondensable hydrocarbon " is uncondensable hydrocarbon under 25 ℃ and 1 bar absolute pressure.Uncondensable hydrocarbon can comprise carbon number less than 5 hydrocarbon.
" obstruction " is meant obstruction and/or suppresses one or more compositions by process vessel or pipe flow.
" alkene " is the molecule that comprises the unsaturated hydrocarbons with one or more non-aromatics carbon-carbon double bonds.
" gasoline hydrocarbon " is meant that boiling range is the hydrocarbon of 32 ℃ of (90)-204 ℃ (400).Gasoline hydrocarbon includes but not limited to straight-run spirit, petroleum naphtha, fluidisation or thermocatalysis cracked gasoline, VB gasoline and coker gasoline.Measure gasoline hydrocarbon content by ASTM method D2887.
" petroleum naphtha " is meant that under 0.101MPa boiling Range Distribution Analysis is 38-200 ℃ a hydrocarbon component.Measure petroleum naphtha content by the method D5307 of American Society for testing and materials (ASTM).
" kerosene " is meant that under 0.101MPa boiling Range Distribution Analysis is 204-260 ℃ a hydrocarbon.Measure kerosene content by ASTM method D2887.
" diesel oil " is meant that boiling Range Distribution Analysis is the hydrocarbon of 260-343 ℃ (500-650) under 0.101MPa.Measure diesel oil content by ASTM method D2887.
" VGO " or " vacuum gas oil " is meant that under 0.101MPa boiling Range Distribution Analysis is 343-538 ℃ a hydrocarbon.Measure VGO content by ASTM method D5307.
" upgrading " is meant the quality that improves hydrocarbon.The quality that for example improves heavy hydrocarbon can cause the increase of heavy hydrocarbon API Gravity.
" API Gravity " is meant the API Gravity under 15.5 ℃ (60).Measure API Gravity by ASTM method D6822.
" periodictable " is meant the periodictable by International Union of Pure and Applied Chemistry (IUPAC) in October, 2005 regulation.
" X hurdle metal " or " the multiple metal on X hurdle " are meant one or more metals on X hurdle in the periodictable, and/or one or more compounds of one or more metals on X hurdle in the periodictable, and wherein X is equivalent to the column number (for example 1-12) of periodictable.For example " the 6th hurdle metal " is meant the metal in the 6th hurdle of periodictable, and/or the compound of one or more metals in the 6th hurdle of periodictable.
" X hurdle element " or " the multiple element on X hurdle " are meant one or more elements on X hurdle in the periodictable, and/or one or more compounds of one or more elements on X hurdle in the periodictable, and wherein X is equivalent to the column number (for example 13-18) of periodictable.For example " the 15th hurdle element " is meant the compound of one or more elements on the 15th hurdle in the element on the 15th hurdle in the periodictable and/or the periodictable.
In the application's scope, in the periodictable in the weight of metal, the periodictable in the weight of metallic compound, the periodictable in the weight of element or the periodictable weight of the compound of element all calculate with the weight of metal or the weight of element.For example if every gram catalyzer uses 0.1g MoO 3, then the weight of molybdenum is the 0.067g/g catalyzer in the catalyzer that is calculated.
" upgrading " is meant the quality that improves hydrocarbon.The quality that for example improves heavy hydrocarbon can cause the increase of the API Gravity of heavy hydrocarbon.
" turning oil " is meant the mixture of light cycle and heavy recycle stock." light cycle " is meant that the boiling Range Distribution Analysis by fluid catalytic cracking system production is 430 (221 ℃) hydrocarbon to 650 (343 ℃).Measure light cycle content by ASTM method D5307." heavy recycle stock " is meant that the boiling Range Distribution Analysis by fluid catalytic cracking system production is 650 (343 ℃) hydrocarbon to 800 (427 ℃).Measure heavy recycle stock content by ASTM method D5307.
" octane value " is meant with canonical reference fuel and compares, the evaluation representation of the anti-seismic performance of motor spirit.Measure the octane value that calculates by ASTM D6730.
" tiny balloon " is meant when molten component is blown into ball for example by the volatilization organic constituent hollow saccharoid that forms at high temperature the thermal process.
" physical stability " is meant that resident fluid does not demonstrate the ability that is separated or flocculates in the transporting fluid process.Measure physical stability by ASTM method D7060.
" chemical stability " is meant that it did not have component reaction to form the polymkeric substance of blocking pipeline, valve and/or container and/or the ability of composition when resident fluid betransported.
Fig. 1 has described the synoptic diagram of the embodiment of a part of situ heat treatment system that handles hydrocarbon containing formation.The situ heat treatment system can comprise barrier wells 200.Use barrier wells around treatment zone, to form screen layer.The screen layer suppression fluid flows out and/or the inflow treatment zone.Barrier wells includes but not limited to dewatering well, vacuum well, capture well, injector well, mud well, freezing well or their combination.In some embodiments, barrier wells 200 is dewatering wells.Dewatering well can be removed liquid water and/or suppress liquid water and enter in a part of stratum to be heated or in the stratum of heating.In the embodiment that Fig. 1 describes, provided the barrier wells 200 of only extending, but barrier wells is typically surrounded whole thermals source 202 of the treatment zone on heating stratum employed or to be used along a side of thermal source 202.
Thermal source 202 places at least a portion stratum.Thermal source 202 can comprise well heater, for example the conductor heater in the insulated conductor, conduit, surface combustion burner, aphlogistic distribution/or the burner of NATURAL DISTRIBUTION.Thermal source 202 also can comprise the well heater of other type.Thermal source 202 provides heat to arrive at least a portion stratum with the hydrocarbon in the heating stratum.Can be by supply line 204 supplying energies to thermal source 202.Supply line 204 structurally can be different, and this depends on the type of heating employed a kind of thermal source in stratum or multiple thermal source.The supply line 204 that is used for thermal source can transmit the electricity that is used for electric heater, can transport the fuel that is used for burner, perhaps can transport the heat exchanging fluid at the stratum internal recycle.
When the heating stratum, the heat that is input in the stratum can cause that expand in the stratum and the geomechanics motion.But the computer simulation simulated formation is to the response of heating.The analog development that can use a computer is used for activating the pattern and the time series of thermal source in the stratum, so that the motion of the geomechanics on stratum can not influence the function of the miscellaneous equipment in thermal source, recovery well and the stratum negatively.
The heating stratum can cause that the rate of permeation on stratum and/or porosity increase.Rate of permeation and/or porosity increase can come from the stratum material and reduce, this be because the gasification of water and remove, the removing and/or producing due to the fracture of hydrocarbon.Because the rate of permeation on stratum and/or porosity increase, fluid may flow in the hot spots on stratum easilier.Because the rate of permeation and/or the porosity that increase, the fluid in the hot spots on stratum can move sizable distance by the stratum.Sizable distance can be to surpass 1000m, and this depends on various factors, for example the temperature on the rate of permeation on stratum, fluidic performance, stratum and the pressure gradient that allows fluid to move.Advance in the stratum ability of sizable distance of fluid allows recovery well 206 to be arranged in the stratum at interval relatively far.
Use recovery well 206 from the stratum, to remove resident fluid.In some embodiments, recovery well 206 comprises thermal source.Thermal source in recovery well can heat at the recovery well place or near one or more parts on the stratum it.In some situ heat treatment method embodiments,, be fed to heat in the stratum less than being fed to the heat on stratum from the thermal source on heating stratum in every meter thermal source from recovery well in every meter recovery well.The heat that is fed to the stratum from recovery well can and be removed the liquid phase fluid adjacent with recovery well by evaporation, and/or increase the rate of permeation on the stratum adjacent, thereby the rate of permeation on the increase stratum adjacent with recovery well with recovery well by forming the fracture of macroscopic view and/or microcosmic.
Multiple thermal source can be arranged in the recovery well.When the heat stack heating stratum from adjacent thermal source is enough to weaken the recovery well heating benefit that the stratum provided, can be closed in the thermal source of recovery well bottom.In some embodiments, when the thermal source inactivation of recovery well bottom, the thermal source on recovery well top can keep work.Can suppress the condensation and the backflow of resident fluid at the thermal source of this aboveground portion.
In some embodiments, the thermal source in recovery well 206 allows to remove the gas phase resident fluid from the stratum.Provide at the recovery well place or by recovery well heat can: (1) when produce fluid with overlying strata adjacent production well in when mobile, suppress condensation of this production fluidic and/or backflow, (2) increase the heat that is input in the stratum, (3) compare with the recovery well that does not have thermal source, increase is from the productivity of recovery well, (4) suppress higher carbon compounds (C6 and more than) condensation in recovery well, and/or (5) are increased in the recovery well place or near the rate of permeation on stratum it.
The hydrodynamicpressure that subsurface pressure in the stratum can be equivalent to generate in the stratum.When the temperature in the hot spots on stratum increases, generate and the result of the gasification of water as the fluid that increases, the pressure in hot spots can increase.The control speed that fluid shifts out from the stratum can allow to control the pressure in the stratum.Can be at many different positionss, for example near recovery well place or its, near thermal source place or its, perhaps be determined at pressure in the stratum at monitoring Jing Chu.
In some hydrocarbon containing formations, produce hydrocarbon by the stratum and be suppressed, up at least some hydrocarbon in the stratum by pyrolysis.When resident fluid has the quality of selection, can be by grown place, stratum layer fluid.In some embodiments, the quality of selection comprises the API Gravity at least about 20 °, 30 ° or 40 °.Suppress to produce and to be increased the transformation efficiency that heavy hydrocarbon changes into light hydrocarbon by pyrolysis up at least some hydrocarbon.The inhibition initial production can minimize the output from the heavy hydrocarbon on stratum.Producing significantly, a large amount of heavy hydrocarbons can require the equipment of costliness and/or the life-span of reducing production unit.
In some hydrocarbon containing formations, in the time of can producing significantly big rate of permeation in the hot spots on stratum, the hydrocarbon in the heating stratum is to pyrolysis temperature.The fluid that initial rate of permeation can not suppress to be generated completely is transported to recovery well 206.In initial heat-processed, the hydrodynamicpressure around thermal source 202 in the stratum can increase.Can discharge, monitor, change and/or control the hydrodynamicpressure that is increased by one or more thermals source 202.For example thermal source 202 of Xuan Zeing or independent pressure reduction well can comprise dropping valve, and described dropping valve allows to remove some fluids from the stratum.
In some embodiments, can the pressure that pyrolyzation fluid or other fluid produced that allows to generate in the stratum by expanding increases, may not be present in the stratum yet although lead to the open access of recovery well 206 or any other diffusing kill-job.Can allow hydrodynamicpressure to increase towards lithostatic pressure power.For example in the hot spots on stratum, can 206 formation rupture from thermal source 202 to recovery well.The generation fracture can discharge some pressure in this part in hot spots.Pressure in the stratum may must be kept and be lower than selective pressure suppressing the fracture of undesired production, overlying strata or underlying formation, and/or the coking of hydrocarbon in the stratum.
After reaching pyrolysis temperature and allowing from the stratum, to produce, can change the pressure in the stratum, to change and/or to control the composition of the resident fluid of being produced, control is compared condensable fluidic percentage ratio with the uncondensable fluid in the resident fluid, and/or controls the API Gravity of the resident fluid of being produced.For example reduce pressure and can cause producing more condensable fluid component.Condensable fluid component can contain the alkene of big percentage ratio.
In some situ heat treatment method embodiments, the pressure that can keep in the stratum is enough high, with the resident fluid of promotion production API Gravity greater than 20 °.Keeping in the stratum pressure that increases can be suppressed in the situ heat treatment process and form throw out.The pressure of keeping increase can quicken production gaseous fluid from the stratum.Gas phase is produced and can be allowed to reduce the size of conveying by the employed collecting duct of fluid of stratum production.The pressure of keeping increase can reduce or need not compress resident fluid in the surface, so that conveyance fluid is to handling in the facility in collecting duct.
Keeping the pressure that increases in the hot spots on stratum can allow the quality of production to improve and the low relatively a large amount of hydrocarbon of molecular weight astoundingly.Can keep pressure, have the compound more than the selection carbon number of minimum with the resident fluid of toilet production.It can be maximum 25 selecting carbon number, maximum 20, maximum 12, or maximum 8.The compound of some high carbon numbers can be entrained in the steam in the stratum, and can use steam to shift out from the stratum.Keep compound and/or polycyclic hydrocarbon compounds that the pressure that increases in the stratum can be suppressed at entrainment of high carbon number in the steam.In the significantly long time period, high carbon number compound and/or polycyclic hydrocarbon compounds can be retained in the liquid phase in the stratum.The significant time period can provide the competent time for the compound of compound pyrolysis formation than low carbon number.
It is believed that the low-molecular-weight relatively hydrocarbon of generation partly be since in a part of hydrocarbon containing formation hydrogen automatic generation and the reaction due to.The hydrogen that the pressure of for example keeping increase can be forced to generate in pyrolytic process enters in the liquid phase in the stratum.But heat the hydrocarbon generation liquid phase pyrolyzation fluid in the temperature pyrolysis stratum of this part in the pyrolysis temperature range.The liquid phase pyrolyzation fluid component that is generated can comprise two keys and/or free radical.Hydrogen (H in liquid phase 2) can reduce the two keys in the pyrolyzation fluid that is generated, thus reduce by pyrolyzation fluid polymerization that is generated or the possibility that forms long-chain compound.In addition, H 2The interior free radical of pyrolyzation fluid that also can neutralize and be generated.Therefore, the H in liquid phase 2The pyrolyzation fluid that can suppress to be generated react each other and/or with the stratum in the reaction of other compound.
The resident fluid of being produced by recovery well 206 can be transported in the treatment facility 210 by conduit 208.Also can be by thermal source 202 grown place layer fluid.For example can produce fluid, with the pressure in the control stratum adjacent with thermal source by thermal source 202.The fluid of being produced by thermal source 202 can be transported in the gathering line 208 by pipeline or pipeline, and perhaps the fluid of being produced can be delivered directly in the treatment facility 210 by pipeline or pipeline.Treatment facility 210 can comprise separating unit, reaction member, upgrading unit, fuel cell, turbine, storage vessel and/or other system and the unit that resident fluid that processing is produced is used.Treatment facility can form transfer the fuel by at least a portion hydrocarbon that the stratum produces.
In some embodiments, the resident fluid of being produced by the situ heat treatment method is transported to separator, and resident fluid is divided into the liquid fluid of one or more in-situ treatment methods and/or the gas stream of one or more situ heat treatment methods.Further treatment liq logistics and gas stream obtain required product.
Heating partially, sub-surface can cause that the mineral structure on stratum changes and form particle.Particle can disperse and/or be partly dissolved in the resident fluid.Particle can comprise the metal on periodictable 1-2 hurdle and 4-13 hurdle and/or the compound of metal (for example aluminium, silicon, magnesium, calcium, potassium, sodium, beryllium, lithium, chromium, manganese, copper, zirconium or the like).In some embodiments, particle comprises tiny balloon.In some embodiments, particle is applied, for example is coated with the hydrocarbon in the resident fluid.In some embodiments, particle comprises zeolite.
The endocorpuscular concentration range of resident fluid can be 1-3000ppm, 50-2000ppm, or 100-1000ppm.The scope of particle size can be the 0.5-200 micron, 5-150 micron, 10-100 micron, or 20-50 micron.
In some embodiments, resident fluid can comprise that particulate distributes.The particulate distribution can be but be not limited to three peaks or multimodal distribution.For example particulate three peaks distribute and can comprise that 1-50ppm is of a size of the particle of 5-10 micron, and 2-2000ppm is of a size of the particle of 50-80 micron and the particle that 1-100ppm is of a size of the 100-200 micron.The particulate bimodal distribution can comprise that 1-60ppm is of a size of the particle of 50-60 micron and the particle that 2-2000ppm is of a size of the 100-200 micron.
In some embodiments, particle contiguously layer fluid and catalysis to form carbon number be maximum 25, maximum compound of 20, maximum 12 or maximum 8.In some embodiments, but zeolite granular assisted oxidation and/or reduction resident fluid, with production method common compound that can not occur in the fluid of being produced of producing common use routine.In the presence of zeolite granular, catalytically layer fluid internal double bond compound reduction of layer fluid and hydrogen contiguously.
In some embodiments, can from the fluid of being produced, remove at intravital all or part of particle of the stream of being produced.Can be centrifugal by using, by washing, by pickling, by filter, by electrostatic precipitation, by pneumatic flotation and/or the separation method that passes through other type except that degranulation.
The resident fluid of being produced by the situ heat treatment method can be transported in the separator, and logistics is divided into situ heat treatment method liquid stream and situ heat treatment method gas stream.Further treatment liq logistics and gas stream obtain desired product.When using common known condition treatment liq logistics to produce commerical prod, but the negative impact processing units.For example processing units can stop up.The example of producing the method for commerical prod includes but not limited to alkylation, distillation, catalytic reforming, hydrocracking, hydrotreatment, hydrogenation, hydrogenating desulfurization, catalytic cracking, delayed coking, gasification or their combination.At " Refining Processes 2000 ", HydrocarbonProcessing, Gulf Publishing Co. discloses the method for producing commerical prod among the pp.87-142, and the document is introduced by reference at this.The example of commerical prod includes but not limited to diesel oil, gasoline, appropriate hydrocarbon gas, jet fuel, kerosene, petroleum naphtha, vacuum gas oil (" VGO ") or their mixture.
Processing unit can be stopped up or fouling by the intravital composition of situ heat treatment method liquid.The occlusion group compound can include but not limited to hydrocarbon and/or the solid by the production of situ heat treatment method.Can in the process of heating situ heat treatment method liquid, form the composition that causes obstruction.Said composition can adhere on the equipment unit and suppress liquid stream and flow by machining cell.
The solid that causes obstruction can include but not limited to organometallic compound, mineral compound, mineral, mineral compound, tiny balloon, coke, half coal ash (semi-soot) and/or their mixture.The solid granularity can make conventional filtration can not remove this solid from liquid stream.The hydrocarbon that causes obstruction can include but not limited to contain heteroatomic hydrocarbon, aromatic hydrocarbons, cyclic hydrocarbon, cyclodiene and/or acyclic dienes hydrocarbon.In some embodiments, it is solvable or be insoluble in the situ heat treatment method liquid to be present in the solid that causes obstruction in the situ heat treatment method liquid and/or hydrocarbon part.In some embodiments, before the heating or among, conventional filter liquide logistics is not enough and/or can not remove all or some compositions of clog up process equipment effectively.
In some embodiments, by liquid stream is washed and/or desalination, from liquid stream, remove the occlusion group compound to small part.In some embodiments, by filtering the obstruction that at least a portion liquid stream suppresses processing unit through nanofiltration system.In some embodiments, suppress the obstruction of processing unit by hydrotreatment at least a portion liquid stream.In some embodiments, nanofiltration and the liquid stream of hydrotreatment at least a portion then, removing may clog up process equipment and/or make the composition of processing unit fouling.Can further process the liquid stream of hydrotreatment and/or nanofiltration, produce commerical prod.In some embodiments, the good antiscale property additive is joined inhibition processing unit obstruction in the liquid stream.People such as people's such as Mansfield United States Patent (USP) 5648305, Wright 5282957, people such as Miller 5173213, Reid 4840720,4810397 and the Fern of Dvoracek 4551226 in the good antiscale property additive is disclosed, all these at this by with reference to introducing.The example of commercially available additive includes but not limited to that Chimec RO 303, Chimec RO304, Chimec RO305, Chimec RO306, Chimec RO307, Chimec RO308 are (available from Chimec, Rome, Italy), GE-BetzThermal Flow 7R29, GE-Betz ProChem 3F28, Ge-Betz ProChem 3F18 are (available from GE Water and Process Technologies, Trevose, PA, U.S.A.).
Fig. 2 has described the synoptic diagram by the embodiment of the system of situ heat treatment method liquid stream and/or situ heat treatment method gas stream production crude oil products and/or commerical prod.Resident fluid 212 enters fluid separation element 214 and is divided into situ heat treatment method liquid stream 216, situ heat treatment method gas 218 and aqueous stream 220.In some embodiments, fluid separation element 214 comprises sudden cold-zone.When the resident fluid of being produced enters sudden cold-zone, sudden cold fluid for example water, undrinkable water and/or other component can join in the resident fluid sudden cold and/or the cooling resident fluid to the temperature that is suitable in downstream processing equipment, handling.Sudden cold resident fluid can suppress to promote the compound formation compound formation of precipitation, accelerated corrosion and/or fouling from the solution of upstream device and/or pipeline (for example suppress can) of fluidic physics and/or chemical instability.Sudden cold fluid can be used as sprays and/or the liquid stream form is incorporated in the resident fluid.In some embodiments, resident fluid is incorporated in the sudden cold fluid.In some embodiments, from resident fluid, remove some heats by making resident fluid flow through interchanger, thereby cool off this fluid.When the temperature of resident fluid for or when approaching the dew point of sudden cold fluid, sudden cold fluid can be joined in the refrigerative resident fluid.Sudden cold resident fluid can improve salt (for example ammonium salt) dissolving that may cause sudden cold fluid chemistry and/or physical instability during under the dew point of sudden cold fluid or near its dew point.In some embodiments, sudden cold in employed water yield minimum so that the salt of mineral compound and/or other component can not be separated with this mixture.In separating unit 214, the sudden cold fluid of at least a portion can be separated with sudden cold mixt, and the cycle of treatment of utilizing minimum is in sudden cold-zone.Can be captured and be used for other facility by the sudden cold heat that produces.In some embodiments, can in sudden cold process, produce steam.The steam that is produced can be transported in the gas separation unit 222 and/or be transported in other facility for processing.
In the heat treating process, gas 218 can enter gas separation unit 222 in position, with divided gas flow hydrocarbon stream 224 from situ heat treatment method gas.In some embodiments, gas separation unit is rectifying absorption and high pressure fractionation unit.Carburet hydrogen logistics 224 comprises carbon number and is at least 3 hydrocarbon.
In the heat treating process, liquid stream 216 enters liquid separation unit 226 in position.In some embodiments, liquid separation unit 226 not necessarily.In liquid separation unit 226, the liquid stream 216 that separates the situ heat treatment method produces carburet hydrogen logistics 228 and saliferous process liquid logistics 230.Carburet hydrogen logistics 228 can comprise carbon number and be 5 hydrocarbon at the most.Part carburet hydrogen logistics 228 can make up with carburet hydrogen logistics 224.Saliferous process liquid logistics 230 can form liquid stream 234 by desalination unit 232 processing.Use known desalination and water-eliminating method, desalination unit 232 is removed mineral salt and/or water from saliferous process liquid logistics 230.In some embodiments, desalination unit 232 is in the upstream of liquid separation unit 226.
Liquid stream 234 is including but not limited to the hydrocarbon of carbon number at least 5 and/or contain heteroatomic hydrocarbon (hydrocarbon that for example contains nitrogen, oxygen, sulphur and phosphorus).Liquid stream 234 can comprise: 0.001g at least, and 0.005g at least, or 0.01g boiling Range Distribution Analysis under 0.101MPa is 95-200 ℃ a hydrocarbon at least; At least 0.01g, 0.005g at least, or 0.001g boiling Range Distribution Analysis under 0.101MPa is 200-300 ℃ a hydrocarbon at least; At least 0.001g, 0.005g at least, or 0.01g boiling Range Distribution Analysis under 0.101MPa is 300-400 ℃ a hydrocarbon at least; At least 0.001g, 0.005g at least, or 0.01g boiling Range Distribution Analysis under 0.101MPa is 400-650 ℃ a hydrocarbon at least.In some embodiments, liquid stream 234 contains the water of maximum 10wt%, the water of maximum 5wt%, the water of 1wt%, or the water of maximum 0.1wt% at most.
After flowing out desalination unit 232, liquid stream 234 enters in the filtering system 236.In some embodiments, filtering system 236 links to each other with the outlet of desalination unit.Filtering system 236 is separated at least a portion and is stopped up compound from liquid stream 234.In some embodiments, the filtering system 236 that is slidingly installed.The filtering system that is slidingly installed 236 can allow filtering system to move on to another from a machining cell.In some embodiments, filtering system 236 comprises one or more membrane separation apparatuss, for example one or more nanofiltration membrane or one or more reverse osmotic membrane.
Film can be ceramic membrane and/or polymeric film.Can to be the molecular weight cutoff value be 2000 dalton (Da) at the most, 1000Da or the ceramic membrane of 500Da at most at most to ceramic membrane.Ceramic membrane needn't swelling be removed required material (for example removing the occlusion group compound from liquid stream) so that operate from matrix under top condition.In addition, ceramic membrane can at high temperature use.The example of ceramic membrane includes but not limited to middle pore titanium oxide, mesopore gama-alumina, mesopore zirconium white, mesoporous silica and their combination.
The bottom (supporting layer) that polymeric film comprises the top layer of being made by dense film and made by porous-film.The dense film top layer passes through bottom then but arranged polymeric film permission liquid stream (penetrating fluid) is at first flowed through, and fits on the bottom so that the pressure reduction on the film promotes top layer.Polymeric film is the organic or hydrophobic film of parent, so that the water that exists in liquid stream is retained or be retained in basically and ooze in the masking liquid.
Compact film can separate at least a portion or all basically occlusion group compounds from liquid stream 234.In some embodiments, by dissolving in its structure with by the diffusion of its structure, the performance of fine and close polymeric film makes liquid stream 234 film of flowing through.At least a portion plugging particle may not can dissolve and/or diffuses through dense film, therefore removes them.Plugging particle may not can dissolve and/or diffuses through dense film, and this is because complex structure and/or its molecular weight height of plugging particle.Compact film can be included in the crosslinking structure described in people's such as Schmidt the WO96/27430, the document at this by with reference to introducing.The thickness range of compact film can be 1-15 micron, 2-10 micron or 3-5 micron.
Can make dense film by polysiloxane, polydimethylsiloxane, poly-prestox siloxanes, polyimide, aramid, poly-trimethyl silyl propine or their mixture.Can make the porous bottom by the material that the film physical strength is provided, and it can be the employed any porous-film of ultrafiltration, nanofiltration or inverse osmosis.The example of this material is polyacrylonitrile, polyamidoimide combination titanium dioxide, polyetherimide, poly(vinylidene fluoride), tetrafluoroethylene or their combination.
Separating in the process of occlusion group compound from liquid stream 234, the pressure differential range on the film can be 5-60bar, 10-50bar or 20-40bar.The separation temperature scope can be from the pour point to 100 of liquid stream ℃ ,-20 to about 100 ℃ approximately, 10-90 ℃ or 20-85 ℃.In the operate continuously process, the circulation of penetrating fluid can be the fore flow flux maximum 50%, fore flow flux maximum 70% or fore flow flux maximum 90%.Weight recovery scope at the raw material penetrating fluid can be 50-97wt%, 60-90wt% or 70-80wt%.
Filtering system 236 can comprise one or more membrane separation apparatuss.Membrane separation apparatus can comprise one or more membrane modules.When using two or more membrane separation apparatuss, they can be arranged according to parallel construction, flow in second membrane separation apparatus with the raw material (seepage remaining liquid) of permission from first membrane separation apparatus.The example of membrane module includes but not limited to assembly, plate-and-frame module, tubular fibre and the tubular assembly that spiral twines.In Encyclopedia of Chemical Engineering, 4 ThEd., 1995, John Wiley ﹠amp; Sons Inc., Vol.16 discloses membrane module among the p158-164.The U.S. Patent No. 5102551 of people's such as for example Boestert WO/2006/040307, Pasternak, Pasternak 5093002, people such as Feimer 5275726, the people such as 5458774 and Finkle of Mannapperuma 5150118 in the example of the assembly that spiral twines is disclosed, all these at this by with reference to introducing.
In some embodiments, when dense film is used for filtering system 236, the assembly that uses spiral to twine.The assembly that spiral twines can comprise the penetrating fluid dividing plate be clipped in therebetween two diaphragm-operated film assemblies and described film assembly in three side seals.The 4th side links to each other with the penetrating fluid delivery channel, so that the zone between film is communicated with the catheter interior fluid.Arrange raw material dividing plate (feed spacer) at the top of a film, and reel around the delivery channel of penetrating fluid and to have the assembly of raw material dividing plate, forms the membrane module of columnar basically spiral winding.The thickness of raw material dividing plate can be 0.6mm, 1mm or 3mm at least at least at least, to allow in the assembly that enough film surfactant packages twine to spiral.In some embodiments, the raw material dividing plate is woven raw material dividing plate.In operating process, raw mix can flow through along the raw material dividing plate between the feeding side that is clipped in film from an end of the circle tube assembly between the film assembly.Flow through arbitrary diaphragm of part raw mix arrives per-meate side.The gained penetrating fluid flow in the penetrating fluid delivery channel along the penetrating fluid dividing plate.
In some embodiments, membrane sepn is a successive technology.Liquid stream 234 flows through on film owing to pressure reduction, to obtain filtered liquid logistics 238 (penetrating fluids) and/or circulating liquid logistics 240 (seepage remaining liquid).In some embodiments, filtered liquid logistics 238 can have the composition and/or the granule density of the system of processing obstruction that causes the downstream of reduction.The turnout that circulating liquid logistics 240 can increase filtered liquid logistics 238 through the continuous circulation of nanofiltration system reach liquid stream 234 initial volume 95%.Under the situation of the feeding side of unclean film, the membrane module that circulating liquid logistics 240 can be twined by spiral is circulation at least 10 hours, at least 1 day or at least 1 week continuously.In case finish filtration, then waste streams 242 (seepage remaining liquid) can comprise the composition that may cause obstruction and/or the particle of high density.Waste streams 242 outflow filter systems 236 also are transported to other machining cell, for example delayed coking unit and/or gasification unit.
But filtered liquid logistics 238 outflow filter systems 236 also enter one or more technique units.The technique unit of production crude oil products described herein and/or commerical prod can be operated under following temperature, pressure, sources of hydrogen flow, liquid stream flow or their combination, perhaps in other cases according to those conditional operations known in the art.Temperature range is about 200-900 ℃, about 300-800 ℃, or about 400-700 ℃.Pressure range is about 0.1-20MPa, about 1-12MPa, about 4-10MPa or about 6-8MPa.The liquid hourly space velocity degree scope of liquid stream is about 0.1-30h -1, about 0.5-25h -1, about 1-20h -1, about 1.5-15h -1, or about 2-10h -1
In Fig. 2, filtered liquid logistics 238 and hydrogen source 244 enter hydrotreatment unit 248.In some embodiments, hydrogen source 244 in entering hydrotreatment unit 248 before, can join in the filtered liquid logistics 238.In some embodiments, enough hydrogen is present in the liquid stream 234 and does not need hydrogen source 244.In hydrotreatment unit 248, in the presence of one or more catalyzer, filtered liquid logistics 238 contacts with hydrogen source 244 and produces liquid stream 250.Can operate hydrotreatment unit 248, so that change the liquid stream 250 of all or at least a portion fully, with the composition of removing the equipment that may be blocked in hydrotreatment unit 248 arranged downstream and/or suppress to form this composition.Employed catalyzer can be commercially available catalyzer in hydrotreatment unit 248.In some embodiments, do not need hydrotreatment liquid stream 234.
In some embodiments, in the presence of one or more catalyzer, contact liq logistics 234 and hydrogen to change one or more required performances of crude oil material, are carried and/or the refining specification requirement thereby satisfy.U.S. Patent application 20050133414 in people's such as Bhan announcement, the title that submit to people's such as Wellington 7,20050133405 and 2006 on April is the U.S. Patent Application Serial Number 11/400542 of " Systems; Methods; and Catalysts for Producing aCrude Product ", the title that Bhan submitted on June 6th, 2006 be " Systems; Methods; and Catalysts forProducing a Crude Product " 11/425979, the title of submitting on June 6th, 2006 with people such as Wellington be " Systems; Methods; and Catalysts forProducing a Crude Product " 11/425992 in the method that changes one or more desired properties of crude oil material is disclosed, all these at this by with reference to introducing.
In some embodiments, hydrotreatment unit 248 is to select hydrogenation unit.In hydrotreatment unit 248, select hydrogenated liquid logistics 234 and/or filtered liquid logistics 238, so that diolefine is reduced into monoolefine.For example at DN-200 (Criterion Catalysts ﹠amp; Technologies, Houston Texas U.S.A.) exists down, under the total pressure of 100-200 ℃ temperature range and 0.1-40MPa, liquid stream 234 and/or filtered liquid logistics 238 is contacted with hydrogen produce liquid stream 250.With respect to diolefine in the liquid stream 234 and monoolefine content, liquid stream 250 comprises the diolefine of reduction amount and the monoolefine of increasing amount.In some embodiments, under these conditions, the transformation efficiency that diolefine changes into monoolefine is at least 50%, at least 60%, at least 80% or at least 90%.Liquid stream 250 flows out hydrotreatment unit 248 and enters in one or more machining cells of hydrotreatment unit 248 arranged downstream.Be arranged in hydrotreatment unit 248 downstream units and can comprise distillation unit, catalytic reforming unit, hydrocracking unit, hydrotreatment unit, hydrogenation unit, hydrogenating desulfurization unit, catalytic cracking unit, delayed coking unit, hydrogenation unit or their combination.
Liquid stream 250 can flow out hydrotreatment unit 248 and enter in the rectification cell 252.Rectification cell 252 produces one or more crude oil products.Rectifying can include but not limited to normal atmosphere distil process and/or vacuum distilling technology.Crude oil products includes but not limited to C3-C5 hydrocarbon stream 254, naphtha stream 256, kerosene stream 258, diesel stream 262 and tower base stream 264.Tower base stream 264 is generally comprised within boiling Range Distribution Analysis under the 0.101MPa and is at least 340 ℃ hydrocarbon.In some embodiments, tower base stream 264 is vacuum gas oils.In other embodiments, tower base stream comprises boiling Range Distribution Analysis and is at least 537 ℃ hydrocarbon.Gasoline or other commerical prod can be sold and/or further be processed into to one or more crude oil products.
In order to improve the purposes of the logistics of being produced by resident fluid, hydrocarbon of producing in rectifying liquid stream process and the appropriate hydrocarbon gas formation capable of being combined of producing in separating technology gas process have the hydrocarbon of higher carbon number.The appropriate hydrocarbon gas logistics of being produced can comprise the acceptable olefin(e) centent of alkylated reaction.
In some embodiments, the liquid stream of hydrotreatment and the logistics (for example distillate and/or petroleum naphtha) and situ heat treatment method liquid and/or resident fluid blend of producing, the fluid of production blend by cut.Compare with resident fluid, this blend fluid can have the physical stability and the chemical stability of raising.With respect to resident fluid, the fluid of blend can have the reactive materials (for example diolefine, other alkene and/or contain oxygen, sulphur and/or nitrogen compound) of reduction amount, thereby improves blend fluidic chemical stability.With respect to resident fluid, the fluid of blend can reduce asphalt content, thereby improves blend fluidic physical stability.Compare with resident fluid and/or liquid stream that the situ heat treatment method is produced, the blend fluid may be more alternative raw material.Compare with resident fluid, the fluid of blend can be more suitable for transportation, uses in the chemical process unit and/or use in refinery unit.
In some embodiments, the fluid of being produced by oil shale formation by method described herein can flow intravital mink cell focus/Tar sands blend with situ heat treatment method (IHTP).Because resinous shale liquid is paraffinic hydrocarbons basically, and mink cell focus/Tar sands IHTP fluid is aromatic hydrocarbons basically, so the fluid of this blend demonstrates the stability of raising.In some embodiments, situ heat treatment method fluid can obtain the raw material be suitable for using with the pitch blend in refinery unit.Blend IHTP fluid and/or pitch and the fluid of being produced can improve the chemistry and/or the physical stability of blend product, thereby this blend can transport and/or be assigned in the machining cell.
C by rectification cell 252 productions 3-C 5Hydrocarbon stream 254 and appropriate hydrocarbon gas logistics 224 enter in the alkylation 266.In alkylation 266, alkene in appropriate hydrocarbon gas logistics 224 (for example propylene, butylene, amylene or their combination) and C 3-C 5Isoparaffin reaction in the hydrocarbon stream 254 produces hydrocarbon stream 268.In some embodiments, the olefin(e) centent in appropriate hydrocarbon gas logistics 224 is acceptable, and does not need additional source olefins.Hydrocarbon stream 268 comprises carbon number and is at least 4 hydrocarbon.Carbon number is at least 4 hydrocarbon and includes but not limited to butane, pentane, hexane, heptane and octane.In some embodiments, the octane value of the hydrocarbon of being produced by alkylation 266 is greater than 70, greater than 80 or greater than 90.In some embodiments, hydrocarbon stream 268 is suitable for without further processing as gasoline.
In some embodiments, but hydrocracking tower base stream 264 is produced petroleum naphtha and/or other products.Yet the gained petroleum naphtha may need to reform to change octane value, makes product in the commercial gasoline sales that can be used as.Alternatively, can be in cat cracker treating column bottoms stream 264, produce the petroleum naphtha and/or the raw material that are used for alkylation.In some embodiments, naphtha stream 256, kerosene stream 258 and diesel stream 262 have unbalanced paraffinic hydrocarbons, alkene and/or aromatic hydrocarbons.These logistics may not have the alkene and/or the aromatic hydrocarbons of the appropriate amount of using in commerical prod.Can form boiling Range Distribution Analysis by these logistics of combination at least a portion is 38 ℃ of extremely about 343 ℃ combined stream 266, changes this imbalance.The logistics 266 of catalytic cracking combination can produce and be suitable for alkene and/or other logistics used in alkylation and/or other machining cell.In some embodiments, hydrocracking naphtha stream 256 is produced alkene.
In Fig. 2, the logistics 266 of combination and enter in the catalytic cracking unit 270 from the tower base stream 264 of rectification cell 252.Under the cracking conditions of control (for example Kong Zhi temperature and pressure), the additional C3-C5 hydrocarbon stream 254 of catalytic cracking unit 270 generations ', gasoline hydrocarbon logistics 272 and additional kerosene stream 258 '.
Additional C 3-C 5Hydrocarbon stream 254 ' can be transported in the alkylation 266, with C 3-C 5Hydrocarbon stream 254 makes up, and/or makes up with appropriate hydrocarbon gas logistics 224, produces the gasoline that is suitable for selling.In some embodiments, the olefin(e) centent in appropriate hydrocarbon gas logistics 224 is acceptable and does not need additional source olefins.
In some embodiments, the amount of the tower base stream of being produced (for example VGO) is too low, so that can't keep the operation of hydrocracking unit or catalytic cracking unit, with the concentration at the gas stream internal olefin of producing by rectification cell and/or catalytic cracking unit (for example by rectification cell among Fig. 2 252 and/or catalytic cracking unit 270) may be too low so that can't keep the operation of alkylation.Can handle the petroleum naphtha of from rectification cell, producing, produce alkene for for example further handling in the alkylation.When by the liquid stream of situ heat treatment method liquid production during as feed stream, the reprovision gasoline of the naphtha reforming explained hereafter by routine may not satisfy the commercial formats requirement, for example mandatory provision of California Air Resources Board.Before reformed naphtha technology, in the hydrotreatment process of routine, can make the amount of alkene in the petroleum naphtha saturated.Therefore, the reform petroleum naphtha of all hydrotreatments can cause being higher than required aromaticity content in the gasoline product (gasoline pool) that is used for reprovision gasoline.Can change in the petroleum naphtha internal olefin of reforming and the imbalance of aromaticity content by produce competent alkylide by alkylation, to produce reprovision gasoline.The alkene that generates by rectifying and/or pressure naphtha, for example propylene and butylene, can with Trimethylmethane combinations produce gasoline.In addition, find that the petroleum naphtha that catalytic cracking is produced in rectification cell and/or other rectifying logistics require additional heat, this is to descend because of the turnout with respect to coke for employed other raw material in the catalytic cracking unit.
Fig. 3 has described and has handled the synoptic diagram that the liquid stream of being produced by the logistics of situ heat treatment method is produced alkene and/or liquid stream.Disclose the similar approach of producing middle distillate and alkene in people's such as International Publication No. WO 2006/020547 and Mo. U.S. Patent Application Publication Nos.20060191820 and 20060178546, all these are introduced by reference at this.Liquid stream 274 enters catalytic cracking system 278.Liquid stream 274 can include but not limited to liquid stream 250, filtered liquid logistics 238, naphtha stream 256, kerosene stream 258, diesel stream 262 and the tower base stream 264 of liquid stream 234, hydrotreatment from the described system of Fig. 2, any hydrocarbon stream that boiling Range Distribution Analysis is 65-800 ℃ or their mixture.In some embodiments, logistics 276 enters catalytic cracking system 278 and aerosolizable and/or promote liquid stream 274, to strengthen contacting of liquid stream and catalytic cracking catalyst.The steam of atomized liquid logistics 274 can be 0.01-2w/w, perhaps 0.1-1w/w with the scope of the ratio of raw material.
In catalytic cracking system 278, liquid stream 274 is contacted with catalytic cracking catalyst, produce one or more crude oil products.The catalyzer of catalytic cracking comprises catalytic cracking catalyst, at least a portion exhausted regeneration cracking catalyst logistics 280, at least a portion regenerated cracking catalyst logistics 282 or their mixture of selection.Exhausted regeneration cracking catalyst 280 is included in the regenerated cracking catalyst of using in second catalytic cracking system 284.Can use second catalytic cracking system, 284 crackenes to produce alkene and/or other crude oil products.Be provided to hydrocarbon, biofuel or their combination that hydrocarbon in second catalytic cracking system 284 can comprise the C3-C5 hydrocarbon produced by recovery well, gasoline hydrocarbon, hydrogenation wax (hydrowax), be produced by Fischer-tropsch process.Can improve the turnout of C3-C5 alkene to the mixture that uses the inhomogeneity hydrocarbon feed in second catalytic cracking system, to satisfy the alkylation demand.Therefore, can improve the integrated of product and refinery practice.Second catalytic cracking system 284 can be known any unit or a structure in close facies unit, fixed fluid-bed unit, riser tube, above-mentioned unitary combination or the crackene field.
Catalytic cracking catalyst contacts with liquid stream 274 and will produce crude oil products and useless cracking catalyst in catalytic cracking system 278.Crude oil products can include but not limited to hydrocarbon, a part of liquid stream 274 or their mixture of boiling point distribution less than the boiling point distribution of liquid stream 274.Crude oil products and useless catalyzer enter separation system 286.Separation system 286 can comprise for example distills unit, stripper, filtering system, whizzer or any device that can separate crude oil products and spent catalyst known in the art.
Isolating waste cracking catalyst logistics 288 flows out separation system 286 and enters regeneration unit 290.In regeneration unit 290, useless cracking catalyst contacts under the carbon burning condition with the oxygen source 292 such as oxygen and/or air, produces regenerated cracking catalyst logistics 282 and combustion gases 294.Can be used as the by-product form of removing the carbon that in the catalytic cracking process process, on catalyzer, forms and/or other impurity and form combustion gases.
Temperature range in the regeneration unit 290 can be about 621-760 ℃ or 677-715 ℃.Pressure range in the regeneration unit 290 can be to be pressed onto 0.345MPa or 0.034-0.345MPa from atmosphere.The residence time scope of isolating waste cracking catalyst is about 1-6 minute in regeneration unit 290, or about 2 minutes, perhaps about 2-4 minute, or about 4 minutes.In the coke content on the regenerated cracking catalyst less than the coke content on isolating waste cracking catalyst.This coke content is less than 0.5wt%, wherein wt percentage ratio with do not comprise coke content the weight of regeneration cracking catalyst be benchmark.Coke content scope in the regenerated cracking catalyst can be 0.01-0.5wt%, 0.05-0.3wt% or 0.1-0.1wt%.
In some embodiments, regenerated cracking catalyst logistics 282 can be divided into two bursts of logistics, wherein at least a portion regenerated cracking catalyst logistics 282 ' leave regeneration unit 290 and enter second catalytic cracking system 284.At least another part regenerated cracking catalyst logistics 282 is left revivifier 290 and is entered in the catalytic cracking system 278.Regulate the relative quantity of exhausted regeneration cracking catalyst and regenerated cracking catalyst, so that required cracking conditions to be provided in catalytic cracking system 278.But regulate the cracking conditions of ratio subcontrol in catalytic cracking system 278 of exhausted regeneration cracking catalyst and regenerated cracking catalyst.The weight ratio scope of exhausted regeneration cracking catalyst and regenerated cracking catalyst can be 0.1: 1 to 100: 1,0.5: 1 to 20: 1 or 1: 1 to 10: 1.For operated system under stable state, the weight ratio of exhausted regeneration cracking catalyst and regenerated cracking catalyst approach to be passed at least a portion regenerated cracking catalyst of second catalytic cracking system 284 and with being incorporated into catalytic cracking system 278 weight ratio of the regeneration cracking catalyst of interior liquid stream 274 blended rest parts, so aforementioned range also can be applicable to this weight ratio.
Crude oil products 296 leaves separation system 286 and enters in the liquid separation unit 298.Liquid separation unit 298 can be recovery known to those skilled in the art and separate crude oil products become product stream for example gas stream 228 ', any system of gasoline hydrocarbon logistics 300, turning oil logistics 302 and tower base stream 304.In some embodiments, tower base stream 304 is recycled in the catalytic cracking system 278.Liquid separation unit 298 can comprise assembly and/or unit, for example resorber and stripper, rectifier, compressor and separator or reclaim any combination with the known system of product separation from crude oil products.In some embodiments, at least a portion light-weight turning oil logistics 302 is left liquid separation unit 298 and is entered in second catalytic cracking system 278.In some embodiments, there is not the light cycle logistics to be transported in second catalytic cracking system.In some embodiments, at least a portion gasoline hydrocarbon logistics 300 is left liquid separation unit 298 and is entered in second catalytic cracking system 284.In some embodiments, there is not the gasoline hydrocarbon logistics to be transported in second catalytic cracking system.In some embodiments, gasoline hydrocarbon logistics 300 is suitable for selling and/or using in other technology.
Gasoline hydrocarbon logistics 306 (for example vacuum gas oil) and/or a part of gasoline hydrocarbon logistics 300 and light cycle logistics 302 are transported in the catalytic cracking system 284.Logistics 276 ' in the presence of these logistics of catalytic cracking produce thick olefin stream 308.Rough system logistics 308 can comprise carbon number and be at least 2 hydrocarbon.In some embodiments, thick olefin stream 308 contains the C of 30wt% at least 2-C 5The C of alkene, 40wt% 2-C 5Alkene, the C of 50wt% at least 2-C 5Alkene, the C of 70wt% at least 2-C 5Alkene or the C of 90wt% at least 2-C 5Alkene.Can in whole process system, provide gas oil hydrocarbon stream 306 to change into C in recycle gasoline hydrocarbon stream 300 to second catalytic cracking systems 284 2-C 5The additional conversion of alkene.
In some embodiments, second catalytic cracking system 284 comprises intermediate reaction district and stripping zone, and the two fluid communication with each other and stripping zone are positioned at below, intermediate reaction district.Compare with its speed in the intermediate reaction district, for high velocity of steam is provided in stripping zone, the sectional area of stripping zone is less than the sectional area in intermediate reaction district.The sectional area of stripping zone can be 0.1: 1 to 0.9: 1,0.2: 1 to 0.8: 1 or 0.3: 1 to 0.7: 1 with the scope of the ratio of the sectional area in intermediate reaction district.
In some embodiments, the geometrical shape of second catalytic cracking system makes it be generally round shape, and the length-to-diameter ratio of stripping zone makes required high velocity of steam to be provided in stripping zone and to provide in stripping zone carries the exhausted regenerated catalyst that removes competent duration of contact from second catalytic cracking system for required ground vapour.Therefore, the length-to-diameter ratio scope of stripping zone can be 1: 1 to 25: 1,2: 1 to 15: 1 or 3: 1 to 10: 1.
In some embodiments, be independent of the operation or the control of catalytic cracking system 278, operate or control second catalytic cracking system 284.This independent operation or control second catalytic cracking system 284 and can improve gasoline hydrocarbon and change into for example total conversion rate of ethene, propylene and butylene of desired product.Adopt the independent operation of second catalytic cracking system 284, can reduce the cracking level of catalytic cracking unit 278, optimize C 2-C 5The productive rate of alkene.Temperature range in second catalytic cracking system 284 can be that 482 ℃ (900 °F) are to about 871 ℃ (1600), 510 ℃ (950)-871 ℃ (1600) or 538 ℃ (1000)-732 ℃ (1350).The working pressure scope of second catalytic cracking system 284 can be that atmosphere is pressed onto about 0.345MPa (50psig) or about 0.034-0.345MPa (5-50psig).
Join steam 276 in second catalytic cracking system 284 ' can assist the operation control of second catalytic cracking unit.In some embodiments, do not need steam.In some embodiments, with respect to other catalytic cracking process, for gasoline hydrocarbon transformation efficiency given in process system and in the gasoline hydrocarbon cracking, use steam that improved C can be provided 2-C 5The selectivity of olefins yield wherein increases propylene and butylene productive rate.The scope that is incorporated into steam and the weight ratio of gasoline hydrocarbon in second catalytic cracking system 284 can be to arrive always or be about 15: 1,0.1: 1 to 10: 1,0.2: 1 to 9: 1 or 0.5: 1 to 8: 1.
Thick olefin stream 308 enters in the olefin separation system 310.Olefin separation system 310 can be recovery well known by persons skilled in the art and separate 308 one-tenth C of thick olefin stream 2-C 5The olefin product logistics is any system of ethylene product stream 312, propylene product logistics 314 and butylene product logistics 316 for example.Olefin separation system 310 can comprise that system or known provide from fluid stream 308 such as resorber and stripper, rectifier, compressor and separator reclaim and separation of C 2-C 5Any combination of the system or equipment of olefin product.In some embodiments, olefin stream 312,314,316 enters alkylation 266 and generates hydrocarbon stream 268.In some embodiments, the octane value of hydrocarbon stream 268 is at least 70, at least 80 or at least 90.In some embodiments, one or more all or part of is transported to other machining cell in the logistics 312,314,316, for example in the polymerized unit, with for use as raw material.
In some embodiments, capable of being combined from catalytic cracking system crude oil products and from the thick olefin stream of second catalytic cracking system.The logistics of combination can enter in the single separating unit (for example combination of liquid separation system 298 and olefin separation system 310).
In Fig. 3, exhausted cracking catalyst logistics 280 is left second catalytic cracking system 284 and is entered in the catalytic cracking system 278.Compare with the carbon concentration on the catalyzer in regenerated cracking catalyst 282, the catalyzer in the exhausted cracking catalyst logistics 280 can comprise slightly high carbon concentration.High carbon concentration can make catalytic cracking catalysed partial inactivation on catalyzer, and described catalytic cracking catalyst provides the olefins yield from the raising of catalytic cracking system 278.Coke content in the exhausted regenerated catalyst can be 0.1wt% or 0.5wt% at least at least.Coke content scope in the exhausted regenerated catalyst can be 0.1 to about 1wt% or 0.1-0.6wt%.
But employed catalytic cracking catalyst can be any fluidizing cracking catalyst known in the art in the catalytic cracking system 278 and second catalytic cracking system 284.Dispersive has the molecular sieve of cracking activity in porous inorganic refractory oxide matrix or the tackiness agent but the fluidizing cracking catalyst can be included in." molecular sieve " is meant can separated atom or any material of molecule based on its size separately.Be suitable for comprising pillared clays, delamination clay and crystal aluminosilicate as the molecular sieve of the component in the cracking catalyst.In some embodiments, cracking catalyst comprises crystal aluminosilicate.The example of this silico-aluminate comprises Y zeolite, overstable Y zeolite, X zeolite, zeolite beta, zeolite L, saspachite, mordenite, faujusite and zeolite omega.In some embodiments, the crystal aluminosilicate that uses in cracking catalyst is X and/or Y zeolite.The U.S. Patent No. 3130007 of Breck discloses y-type zeolite.
Can be by using hydrogen ion, ammonium ion, multivalent metal cation, the positively charged ion, magnesium cation or the calcium positively charged ion that for example contain rare earth element, or the composition exchanging zeolite of hydrogen ion, ammonium ion and multivalent metal cation, thereby reduction sodium content, up to it less than about 0.8wt%, preferably less than about 0.5wt% with most preferably less than about 0.3wt%, with Na 2The O form is calculated, and increases stability and/or acidity as the zeolite of component in the cracking catalyst.The method of carrying out ion-exchange is well-known in the art.
Before using, zeolite or other molecular sieve component and porous inorganic refractory oxide matrix or tackiness agent in the combination cracking catalyst form finished catalyst.Refractory oxide component in finished catalyst can be one or more mixture and an analogue in silica-alumina, silicon-dioxide, aluminum oxide, natural or synthesis of clay, column or delamination clay, these components.In some embodiments, the inorganic refractory oxide matrix comprises for example mixture of kaolin, hectorite, sepiolite and attapulgite of silica-alumina and clay.Finished catalyst can contain the zeolite of the 5-40wt% that has an appointment or other molecular sieve and greater than the inorganic refractory oxide of about 20wt%.In some embodiments, finished catalyst can contain zeolite or other molecular sieve, the inorganic refractory oxide of about 10-30wt% and the clay of about 30-70wt% of the 10-35wt% that has an appointment.
Can be by any suitable method known in the art, comprising mixing, grinding or homogenizing, the crystal aluminosilicate in the assembly catalyze cracking catalyst or other molecular sieve component and porous inorganic refractory oxide component or its precursor.The example of spendable precursor includes but not limited to the polyoxy positively charged ion of aluminum oxide, alumina sol, silicon dioxide gel, zirconium white, alumina hydrogel, aluminium and zirconium and the aluminum oxide of granulation.In some embodiments, combined zeolite and silico-aluminate gel or colloidal sol or other inorganic refractory oxide component, and spraying drying gained mixture produce the finished catalyst particle that diameter range is generally about 40-80 micron.In some embodiments, zeolite or other molecular sieve can grind or mix, extrude, be ground into then required size range in other cases with refractory oxide component or its precursor.The average bulk density of finished catalyst can be about 0.30-0.90g/cm 3And pore volume is about 0.10-0.90cm 3/ g.
In some embodiments, the ZSM-5 additive can be incorporated in the middle cracking case in second catalytic cracking system 284.When using the ZSM-5 additive with the cracking catalyst of selecting in middle cracking case, the light alkene for example productive rate of propylene and butylene improves.The amount ranges of ZSM-5 is the maximum 30wt% that are incorporated into the regenerated catalyst weight in second catalytic cracking system 284, maximum 20wt% or maximum 18wt%.The amount ranges that is incorporated into the ZSM-5 additive in second catalytic cracking system 284 can be 1-30wt%, 3-20wt% or the 5-18wt% that is incorporated into the regeneration cracking catalyst weight in second catalytic cracking system 284.
The ZSM-5 additive is to be selected from the crystal aluminosilicate of intermediate pore size or the molecular sieve additive of zeolite series.The molecular sieve that can be used as the ZSM-5 additive includes but not limited at " Atlas ofZeolite Structure Types ", Eds.W.H.Meier and D.H.Olson, Butterworth-Heineman, the third edition, the mesopore zeolite described in 1992.The aperture of mesopore zeolite is generally about 0.5-0.7nm and comprises for example zeolite of MFI, MFS, MEL, MTW, EUO, MTT, HEU, FER and TON structure type (the IUPAC council of zeolite name).The non-limiting example of this mesopore zeolite comprises ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, silicalite and silicalite2.In the U.S. Patent No. 3770614 of people's such as Argauer United States Patent (USP) 3702886 and Graven, ZSM-5 has been described, these two pieces of documents at this by with reference to introducing.
ZSM-11 is disclosed in the U.S. Patent No. 3709979 of Chu, ZSM-12 is disclosed in people's such as Rosinski the U.S. Patent No. 3832449, with ZSM-21 and ZSM-38 are disclosed in people's such as Bonacci U.S. Patent No. 3948758, ZSM-23 is disclosed in people's such as Plank U.S. Patent No. 4076842, with ZSM-35 is disclosed in people's such as Plank U.S. Patent No. 4016245, all these at this by with reference to introducing.Other suitable molecular sieve comprises aluminosilicophosphate (SAPO), for example SAPO-4 and the SAPO-11 described in people's such as Lok the U.S. Patent No. 4440871; The silicochromium hydrochlorate; Silicic acid gallium, ferric metasilicate; Aluminum phosphate (ALPO) is for example at the ALPO-11 described in people's such as Wilson the U.S. Patent No. 4310440; Silicoaluminate titanium (TASO) is for example at the TASO-45 described in people's such as Pellet the U.S. Patent No. 4686029; At the borosilicate described in people's such as Frenken the U.S. Patent No. 4254297; Aluminum phosphate titanium (TAPO) is for example at the TAPO-11 described in people's such as Lok the U.S. Patent No. 4500651; With silicoaluminate iron, all these documents are introduced by reference at this.
It can be one group of zeolite of suitable ZSM-5 additive that people's such as Chester U.S. Patent No. 4368114 (at this by with reference to being introduced into) at length discloses.According to conventional methods, the ZSM-5 additive can keep together with the inorganic oxide matrix component of catalysis inactivation.
In some embodiments, the residue by Fig. 2 and 3 described unit productions can be used as the energy.Gasifiable this residue produces gas, and described gas burned (for example in the turbine internal combustion) and/or be injected in the subsurface formations (for example is injected into the carbonic acid gas that is produced in the subsurface formations).In some embodiments, make the residue diasphaltene produce pitch.Gasifiable described pitch.
Embodiment
Below listed situ heat treatment liquid stream filtration and produce the non-limiting example of alkene by the liquid stream of situ heat treatment.
The nanofiltration of embodiment 1. situ heat treatment method liquid streams
From the situ heat treatment method, obtain liquid sample (500ml, 398.68g).This liquid sample contains 0.0069g sulphur and 0.0118g nitrogen/g liquid sample.The final boiling point of this liquid sample is that the density of 481 ℃ and liquid sample is 0.8474.Filtering the employed film separation unit of this sample is the P28 of breadboard flat sheet membrane Setup Type, and it is available from CM CelfaMembrantechnik A.G. (Sweden).The polydimethylsiloxane film (GKSS Forschungszentrum GmbH, Geesthact, Germany) of single 2 micron thickness is used as filtration medium.Filtering system is operated under 50 ℃ and the pressure reduction on film is 10bar.At the pressure of permeate side near normal atmosphere.Collect penetrating fluid and cycle through filtering system with the simulation continuous processing.Protect penetrating fluid with nitrogen curtain, prevent to contact with ambient air.Also collect seepage remaining liquid for analysis.In filtration procedure, 2kg/m 2The average flow flux of/bar/h do not have can measure from initial circulation decline.Filtered liquid (298.15g, 74.7% rate of recovery) contains 0.007g sulphur and 0.0124g nitrogen/g filtered liquid; With the density of filtered liquid be 0.8459 and final boiling point be 486 ℃.Seepage remaining liquid (56.46g, the rate of recovery 14.16%) contains 0.0076g sulphur and 0.0158g nitrogen/g seepage remaining liquid; And the density of seepage remaining liquid be 0.8714 and final boiling point be 543 ℃.
Embodiment 2. filters and the fouling of unfiltered situ heat treatment method liquid stream is tested
Not filtering and the fouling behavior of filtered liquid sample of test implementation example 1.Use Alcor thermojunction dirt tester to measure the fouling behavior.Alcor thermojunction dirt tester is the small-sized tube and shell heat exchanger of being made by 1018 steels, and it used Norton R222 sand papering before using.In process of the test, the temperature out (T of monitoring sample Out) keep heat exchange temperature (T simultaneously c) under steady state value.As if fouling taking place and deposited material, then increase of the thermotolerance of sample and therefore temperature out decline on pipe surface.Temperature out decline is measuring of fouling severity after the given time period.Temperature after operating 2 hours descends as the indication of fouling severity.ΔT=t out(0)-t out(2h)。T Out (0)Be defined as maximum (stablizing) temperature out that when on-test, obtains, notice at first temperature out descend after 2 hours or when temperature out is stablized 2 hours, write down t at least Out (2h)
In process of the test each time, liquid sample under about 3ml/min continuously circulation through interchanger.The residence time in the interchanger is about 10 seconds.Operational condition is as described below: pressure 40bar, T SampleFor with 50 ℃, T cBe that 350 ℃ and test period are 4.41 hours.The Δ T of unfiltered liquid stream sample is 15 ℃, and the Δ T of filtered sample is 0.
This embodiment proves that the liquid stream that nanofiltration is produced by the situ heat treatment method is removed at least a portion occlusion group compound.
Embodiment 3. produces alkene by situ heat treatment method liquid stream
Use laboratory scale pilot test system to experimentize.This pilot test system comprises raw material supply system, catalyst cupport and transfer system, quick fluidizing riser reactor, stripper, product separates and gathering system and revivifier.Riser reactor is the adiabatic riser tube, and its internal diameter is that 11-19mm and length are about 3.2m.The riser reactor outlet is communicated with the stripper fluid, and described stripper operates under the temperature identical with riser reactor outlet stream and its mode provides 100% steam stripping efficiency basically.Revivifier is the employed multi-stage type cyclic regeneration of a regeneration of spent catalyst device.The flow of spent catalyst with control is fed in the revivifier, and in container, collects the regenerated catalyzer.In laboratory test process each time, obtain material balance at 30 minutes timed intervals place.By using online gas chromatographic analysis composite gas sample, and collect the liquid product sample and analysis is spent the night.Flow by measuring catalyzer and by measuring in the Δ coke on the catalyzer (this is during by this unit of operation under stable state, measure the spent catalyst that obtains in test each time and the coke on the regenerated catalyst sample and obtain), thus the productive rate of coke measured.
The liquid stream that fractionation is produced by the situ heat treatment method, acquisition boiling Range Distribution Analysis are 310-640 ℃ vacuum gas oil (VGO) logistics.Contact VGO logistics and the fluidizing cat cracker E-Cat that contains the 10%ZSM-5 additive at above-described catalysis system.The riser reactor temperature maintenance is under 593 ℃ (1100 °F).The product of being produced contains 0.1402gC in every gram product 3Alkene, 0.137gC 4Alkene, 0.0897gC 5Alkene, the different C of 0.0152g 5Alkene, 0.0505g iso-butylene, 0.0159g ethane, 0.0249g Trimethylmethane, 0.0089g normal butane, 0.0043g pentane, 0.0209g iso-pentane, 0.2728gC 6Mixture, the 0.0881g boiling Range Distribution Analysis of the hydrocarbon of hydrocarbon and boiling point maximum 232 ℃ (450) is that hydrocarbon, the 0.0769g boiling Range Distribution Analysis of 232-343 ℃ (450-650) is the hydrocarbon of 343-399 ℃ (650-750) and 0.0386g boiling Range Distribution Analysis hydrocarbon and the 0.0323g coke at least 399 ℃ (750).
This embodiment has proved the method for producing crude oil products, the liquid stream that this method is produced from the logistics of resident fluid separating liquid by rectifying, thus produce boiling point at the crude oil products more than 343 ℃; With the catalytic cracking boiling point at the crude oil products more than 343 ℃, thereby produce one or more additional crude oil products, wherein at least a additional crude oil products is second gas stream.
Embodiment 4. produces alkene by the liquid stream that the situ heat treatment method is produced
The boiling Range Distribution Analysis that the petroleum naphtha simulation of using thermally splitting is produced by the situ heat treatment method is 30-182 ℃ liquid stream.In every gram petroleum naphtha, petroleum naphtha contains 0.186g naphthalene, 0.238g isoparaffin, 0.328g n-paraffin, 0.029g cycloolefin, 0.046g isoolefine, the positive alkene of 0.064g and 0.109g aromatic hydrocarbons.In above-described catalytic cracking system, contact naphtha stream and the FCC E-Cat with 10%ZSM-5 additive are to produce crude oil products.The riser reactor temperature maintenance is under 593 ℃ (1100 °F).This crude oil products comprises in every gram crude oil products 0.1308g ethene, 0.0139g ethane, 0.0966g C4 alkene, 0.0343gC4 isoolefine, 0.0175g butane, 0.0299g Trimethylmethane, 0.0525gC5 alkene, 0.0309gC5 isoolefine, 0.0442g pentane, 0.0384g iso-pentane, 0.4943gC 6Mixture, the 0.0201g boiling Range Distribution Analysis of the hydrocarbon of hydrocarbon and boiling point maximum 232 ℃ (450) is that hydrocarbon, the 0.0029g boiling Range Distribution Analysis of 232-343 ℃ (450-650) is the hydrocarbon of 343-399 ℃ (650-750) and 0.00128g boiling Range Distribution Analysis hydrocarbon and the 0.00128g coke at least 399 ℃ (750).C 3-C 5The total amount of alkene is the 0.2799g/g petroleum naphtha.
This embodiment has proved the method for producing crude oil products, the liquid stream that this method is produced from the logistics of resident fluid separating liquid by rectifying, thus produce boiling point at the crude oil products more than 343 ℃; With the catalytic cracking boiling point at the crude oil products more than 343 ℃, thereby produce one or more additional crude oil products, wherein at least a additional crude oil products is second gas stream.

Claims (20)

1. produce the method for crude oil products, this method comprises:
By underground original position pyrolysis heat treating process grown place layer fluid;
Separate this resident fluid, produce the liquid stream and first gas stream, wherein first gas stream comprises alkene;
This liquid stream of rectifying is produced one or more crude oil products, and wherein the boiling Range Distribution Analysis of at least a crude oil products is 38-343 ℃, and this measures by ASTM method D5307; With
The catalytic cracking boiling Range Distribution Analysis is 38-343 ℃ a crude oil products, produces one or more additional crude oil products, and wherein at least a additional crude oil products is that second gas stream and the boiling point of this gas stream under 0.101MPa are 38 ℃ at the most.
2. the process of claim 1 wherein that second gas stream comprises the hydrocarbon of carbon number at least 3.
3. claim 1 or 2 method, wherein the boiling Range Distribution Analysis of at least a additional crude oil products is 38-200 ℃, this measures by ASTM method D5307.
4. each method of claim 1-3, wherein at least a additional crude oil products comprises gasoline hydrocarbon.
5. the method for claim 4, wherein the octane value of gasoline hydrocarbon is at least 70.
6. produce the method for hydrocarbon, this method comprises:
By underground situ heat treatment method grown place layer fluid;
Layer fluid is produced liquid stream discretely;
In first catalytic cracking system, this liquid stream of catalytic cracking by contacting this liquid stream and catalytic cracking catalyst is produced crude oil products logistics and useless catalytic cracking catalyst;
This useless catalytic cracking catalyst of regenerating is produced the regenerated cracking catalyst;
In second catalytic cracking system, this gasoline hydrocarbon logistics of catalytic cracking by contact gasoline hydrocarbon logistics and regenerated catalytic cracking catalyst is produced and is comprised carbon number and be the thick olefin stream of at least 2 hydrocarbon and the exhausted cracking catalyst of regenerating; With
Separate alkene from thick olefin stream, wherein the carbon number of alkene is 2-5; With
Provide exhausted regeneration cracking catalyst to first catalytic cracking system from second catalytic cracking system.
7. the method for claim 6, wherein catalytic cracking catalyst comprises unbodied silica alumina and zeolite.
8. claim 6 or 7 method, this method further comprises provides ZSM-5 in second catalytic cracking system.
9. each method of claim 6-8, wherein the coke content scope in the regenerated catalytic cracking catalyst is 0.01-0.5wt%.
10. each method of claim 6-9, wherein the weight ratio scope of exhausted regeneration cracking catalyst and regenerated cracking catalyst is 0.1: 1 to 100: 1.
11. each method of claim 6-10, wherein this method further comprises provides in the steam to the first and/or second catalytic cracking system.
12. each method of claim 6-11, this method comprise that further separating crude oil products becomes one or more hydrocarbon streams, wherein at least one hydrocarbon stream is the gasoline hydrocarbon logistics; With provide the logistics of at least a portion gasoline hydrocarbon in second catalytic cracking system.
13. the method for claim 12, wherein at least one hydrocarbon stream is the turning oil logistics; With provide the logistics of at least a portion turning oil in first catalytic cracking system.
14. each method of claim 6-13, this method comprise that further it is that the alkene of 3-5 is in alkylation that at least a portion carbon number is provided.
15. each method of claim 6-13, this method further comprise provide at least a portion carbon number be the alkene of 3-5 in alkylation, this alkene of alkylation is then produced and is suitable for the hydrocarbon of blend with production and transport fuel.
16. the method for claim 15, wherein transport fuel is a gasoline.
17. each method of claim 6-16, this method further comprises provides at least a portion alkene in polymerized unit.
18. each method of claim 1-17, this method further are included in hydrotreatment at least a portion liquid stream under the condition that is enough to remove the occlusion group compound.
19. make the method for transport fuel, this method comprises one or more crude oil products that use each method of claim 1-18 to produce.
20. transport fuel, it comprises the hydrocarbon of producing by each method of claim 1-19.
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CN104763396A (en) 2015-07-08
ZA200802758B (en) 2009-01-28
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