CN101541924A - Process and reactor for upgrading heavy hydrocarbon oils - Google Patents
Process and reactor for upgrading heavy hydrocarbon oils Download PDFInfo
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- CN101541924A CN101541924A CNA2007800443169A CN200780044316A CN101541924A CN 101541924 A CN101541924 A CN 101541924A CN A2007800443169 A CNA2007800443169 A CN A2007800443169A CN 200780044316 A CN200780044316 A CN 200780044316A CN 101541924 A CN101541924 A CN 101541924A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
Abstract
A process using supercritical water to upgrade a heavy hydrocarbon feedstock into an upgraded hydrocarbon product or syncrude with highly desirable properties (low sulfur content, low metals content, lower density (higher API) lower viscosity, lower residuum content, etc.) is described. The process does not require external supply of hydrogen nor does it use externally supplied catalysts. A reactor design to carry out the process is also described.
Description
Invention field
The present invention relates to use supercritical water to hydrocarbon, especially for example full cut heavy oil of heavy hydrocarbon, pitch etc. carry out upgrading.
Background of invention
To such an extent as to the oil that is produced by all over the world big gauging deposit has weighed simply very much under envrionment conditions and can not flow.This makes remote heavy oil resources more become challenge near market.The Hamaca field with "nine squares" that typical example is Venezuela.For making this type of mink cell focus to flow, one of prevailing method known in the art is by mink cell focus and competent mixing diluents are reduced viscosity and density.Described thinner can be petroleum naphtha or have any other logistics of the api gravity (be much lower density) significantly higher than described mink cell focus.
For the situation of for example Hamaca, the crude oil that has diluted is delivered to the upgrading equipment via pipeline from production wellhead.Have two key operations in described upgrading equipment: (1) is reclaimed described diluent stream and in independent pipeline it is looped back production wellhead, and (2) make described heavy-oil modifiedly with suitable technique as known in the art (coking, hydrocracking, hydrotreatment etc.), is that market produces the product of higher value.Some characteristic features of the product of these higher values comprise: lower sulphur content, lower metal content, lower total acid value (TAN), lower residue content, higher api gravity and lower viscosity.By making described mink cell focus and hydrogen in the presence of catalyzer, react the major part that obtains in these features of wanting under the high temperature and high pressure.Under the situation of Hamaca, the crude oil of upgrading further is transported to end user location via tank car.
These thinners add/remove method and hydrogenation or other method for modifying and have many shortcomings:
1. the needed Infrastructure of processing, recovery and recycle diluent is expensive, especially for the situation of growing distance.The availability of thinner is another potential problem.
2. for example hydrotreatment or hydrocracking need a large amount of investments to method of hydrotreating on capital and Infrastructure.
3. method of hydrotreating also has high running cost, because the cost that produces hydrogen is extremely sensitive for the price of Sweet natural gas.The mink cell focus deposit that some are remote even the low-cost Sweet natural gas that may keep clear of q.s are to support hydrogen device.These method of hydrotreating also need expensive catalysts and resource-intensive catalyst treatment technology usually, comprise catalyst regeneration.
4. in some cases, nearest refining and/or the upgrading equipment in the described production of distance place may neither have the equipment that the ability that receives described mink cell focus does not have the described mink cell focus of reception yet.
5. usually in refining or upgrading equipment, use coking technology.Abandon a large amount of by-product solid coke in described process of coking, this causes lower liquid hydrocarbon yield.In addition, the liquid product from coking plant usually needs further hydrotreatment.In addition, from the volume of the product of process of coking significantly less than the volume of feed crude oil.
The method according to this invention has overcome these shortcoming with the heavy hydrocarbon feedstocks upgrading as the hydrocarbon product of upgrading or synthetic crude with performance (low sulfur content, low-metal content, lower density (higher API), lower viscosity, lower residue content etc.) of high desirability by using supercritical water.Described method neither needs outside hydrogen supply neither use catalyzer.In addition, method of the present invention does not produce considerable coke by-product.
Compare with traditional synthetic crude production method, the advantage that can obtain by enforcement the present invention comprises high liquid hydrocarbon yield; The hydrogen that does not need outside supply; Do not need to provide catalyzer; Improve the api gravity of the hydrocarbon product of upgrading greatly; Significantly reduce the viscosity of the hydrocarbon product of upgrading; And significantly reduce sulphur, metal, nitrogen, TAN and MCR (little carbon residue) in the hydrocarbon product of upgrading.
The several different methods of using the supercritical water treatment heavy hydrocarbon is disclosed in the patent documentation.Example comprises United States Patent (USP) sequence number 3,948,754; 3,948,755; 3,960,706; 3,983,027; 3,988,238; 3,989,618; 4,005,005; 4,151,068; 4,557,820; 4,559,127; 4,594,141; 4,840,725; 5,611,915; 5,914,031 and 6,887,369 and European patent 671454.
United States Patent (USP) sequence number 4,840,725 discloses uses supercritical water that the high boiling liquid organic materials is converted into the more method of lower boiling material in tubular flow reactor.Described water and hydrocarbon preheating respectively also just mixed in the high pressure feedstock pump before described reactor is given in charging.
United States Patent (USP) sequence number 5,914,031 discloses three district's reactor design so that make the maximization respectively that is separated of reactant activity, reactant solubility and product by controlled temperature and pressure.Yet all embodiment that provide in this patent are to use periodical operation to obtain.
United States Patent (USP) sequence number 6,887,369 discloses the preferred supercritical water pretreatment process that uses hydrogen or carbon monoxide to carry out and has come hydrotreatment and hydrocracking carbonaceous material in deep well reactor.Described deep well reactor transformation is from underground oil wells, and is made up of a plurality of concentric tubes.The deep well reactor of describing in this patent is by being incorporated into feed stream the core pipe and operating at outer ring shape part Returning reactor effluent.
Although above-mentioned patent disclosure and the claimed supercritical water that uses carry out heavy-oil modified several different methods and technology; the for example operating restraint of temperature and pressure, water/oil ratio etc., but do not have the public use supercritical water to carry out heavy-oil modified reactor design or the design relevant with process control.In fact, disclosed most embodiment can obtain by the batch test that uses autoclave in the described patent.Although many reference that are used to relate to the reactor design of supercritical water process are arranged, but the major part in them is used for offal treatment, and there is not one piece of argumentation to be used for the reactor design of mink cell focus and supercritical water in these reference, as following discussion, this fundamentally is different from the refuse processing method that uses supercritical water to carry out.
Know for a long time in this area that supercritical water can be used for the processing of waste, be particularly useful for handling the waste water that contains organic pollutant.Therefore, have in the document in a large number, tend to discuss following problem about using supercritical water to carry out the disclosing of reactor design of offal treatment:
(1) solids treatment.Waste material logistics generally contain organic and inorganic material.Though organic materials can be destroyed apace by supercritical water oxidation, inorganic material is insoluble in supercritical water.Several patents has been discussed this misgivings.United States Patent (USP) sequence number 5560823 and 5567698 for example, be hereby incorporated by, reversible flow reactor with two reaction zones is disclosed, these two reaction zones alternately are used for supercritical water oxidation, and remaining reaction zone uses the subcritical outflow thing from described active reaction district to wash.United States Patent (USP) sequence number 6264844 is hereby incorporated by, and discloses the tubular reactor that is used for supercritical water oxidation.The speed of described reaction mixture is enough to prevent the solid sedimentation.Inorganic salt in the effusive mixture, it is soluble under the supercritical temperature of water and pressure condition, is dissolved in the liquid aqueous phase at effusive mixture in the process of cooling at the exit end place of described reactor.
(2) oxidant management.United States Patent (USP) sequence number 5384051 and 5558783 is hereby incorporated by, and discloses the reactor design that is used for supercritical wastewater oxidation.It contains at the reaction zone of closed container inside and the permeable lining around reaction zone.Make oxygenant and carrier fluid for example water mix.To described mixture heating up and be forced into super critical condition, and then by forcing it radially inwardly to pass permeable lining and the orientating reaction district is incorporated into described reaction zone gradually and equably with it.Described permeable liner allows reactant continuously, gradually, disperse equably, and therefore promotes steadily and effectively reaction.Described lining is also kept apart the high temperature and the oxidizing condition that exist in pressurized vessel and the described reaction zone, allows to reduce the cost of pressurized vessel.EP1489046 discloses the twin containers design that reaction vessel is placed on pressurized vessel inside.Being reflected at reactor vessel takes place under high temperature, high pressure and corrosive atmosphere.Outside pressurized vessel is only seen water.
(3) sealing of poisonous material.Some waste material logistics contain human and the very deleterious pollutent of environment, and the possibility that therefore discharges this type of deleterious material must be discussed in reactor design.United States Patent (USP) sequence number 6168771 is hereby incorporated by, and discloses a kind of reactor design, and it comprises the autoclave that is in pressurized vessel inside.Pressure between autoclave and the pressurized vessel is substantially equal to described autoclave pressure inside, has therefore eliminated the possible leakage of the poisonous material of described autoclave inside.
Although can think use supercritical water to carry out heavy-oil modified similar in some aspects with the offal treatment of using supercritical water to carry out, and can use a plurality of elements of the reactor that designs as offal treatment to implement, but the reactor design that is used for the heavy hydrocarbon upgrading have different significantly with the reactor design that is used for offal treatment on requiring.Especially, some in the many problems that will discuss when below being reactor design, in this reactor, implement to use supercritical water to carry out heavy-oil modified effective means:
(1) importance optionally.For offal treatment, unique performance objective is a transformation efficiency.In other words, described reaction is nonselective complete oxidation and does not need to worry selectivity that this makes DESIGN OF REACTOR much simple.For heavy-oil modified, described raw material is the mixture that contains broad range of materials, and the reaction complexity that relates to many.We not only need to consider transformation efficiency, and the more important thing is the pursuit highly selective, because nonselective reaction can cause low-value byproducts, and for example solid coke or gas.Obviously, for the reactor design of the selective reaction in the complex system a great difference is arranged, and have more challenge than nonselective complete oxidation.
(2) high concentration of feed.Organic constituent concentration in the general waste material logistics is low, and described under many circumstances concentration is only in the ppm scope.For oily upgrading, preferably use minimum possible water-oil ratio to carry out described reaction with reduction fund and running cost.Usually, the oil concentration in the upgrading is than the high several magnitude of oil concentration of offal treatment.
(3) high-density and high viscosity.Notable attribute of mink cell focus is high-density and high viscosity.In fact, this is the one of the main reasons that described oil has to carry out upgrading.The density of mink cell focus and the density of liquid water are very approaching, and viscosity can be up to 10000cp.High-density and high viscosity make mink cell focus be distributed to high density becomes important consideration in the supercritical water.
Summary of the invention
The present invention relates to hydrocarbon is carried out the method for upgrading, comprising: with hydrocarbon with comprise the fluid of water that temperature has been heated to above its critical temperature and in the mixing zone, be unfavorable for mixing under the condition that thermally splitting and coke form with the formation mixture; Described mixture is passed to reaction zone; Described mixture is reacted in described reaction zone, described reaction zone have that basic uniform temperature distributes and for reduce solid in described reaction zone sedimentation and dispose, described be reflected under the condition of supercritical water do not have outer hydrogenation in the presence of take place, the residence time is controlled in the definite scope that allows upgrading reaction generation; Take out the homogeneous reaction product from described reaction zone; And the hydrocarbon phase that described reaction product is divided into gas phase, effluent water and upgrading.
The accompanying drawing summary
Fig. 1 is the process flow sheet of one embodiment of the invention.
Fig. 2 is the process flow sheet of another embodiment of the invention.
Fig. 3 is the process flow sheet of another embodiment of the invention.
Fig. 4 is the process flow sheet of another embodiment of the invention.
Fig. 5 is the process flow sheet of another embodiment of the invention.
Embodiment preferred is described
Reactant
Water and hydrocarbon, preferred heavy hydrocarbon is two kinds of reactants that use in the method according to this invention.
Any hydrocarbon can carry out suitable upgrading by the method according to this invention.Preferred api gravity is less than 20 ° heavy hydrocarbon.Wherein preferred heavy hydrocarbon is heavy crude, (is commonly referred to tar sand bitumen from Tar sands, for example obtain from Canadian Athabasca tar sand bitumen) in the heavy hydrocarbon, heavy crude crude oil example such as the thick Boscan mink cell focus of Venezuela Orinoco mink cell focus band that extract, acquisition is from the heavy hydrocarbon fractions of petroleum crude oil heavy vacuum gas oil particularly, vacuum residuum and petroleum tar, Tar sands and coal tar.Other example of operable heavy hydrocarbon feedstocks is resinous shale, shale oil and bituminous matter.
Water
Can in the aqueous fluid of described bag, use the water in any source in the embodiment of this invention.The source of water includes but not limited to waste water tap water, processing or not processed, river, lake water, seawater, generation water etc.
Mix
According to the present invention, with heavy hydrocarbon feedstocks with comprise the fluid that temperature has been heated to above the water of its critical temperature and before entering described reaction zone, in the mixing zone, contact.According to the present invention, can finish in many ways and mix and preferably finish by the technology of not using mechanical displacement means.This type of mixing device can include but not limited to the use of static mixer, spray nozzle, sound or ultrasonic agitation.Should heat and mix described oil and water so that the logistics that has mixed reaches condition of supercritical water in reaction zone.
Should heat and mix described oil and water so that the described logistics that has mixed reaches super critical condition in reaction zone.
Discovery has significantly reduced for example formation of solid residue of by product by avoiding the described stock oil of superheated.An aspect of of the present present invention is to use heating sequence so that the temperature and pressure of described hydrocarbon and water reaches supercritical reaction conditions with controllable mode.This can be avoided the local excessive heating of oil, and the local excessive heating can cause solid to form and more inferior product.For obtaining better properties, described oil should only lean on the water of the q.s that exists around the described hydrocarbon molecule to heat.Can reach this requirement by before heating, oil being mixed with water.
In one embodiment of the invention, water is heated to above the temperature of its critical temperature, and mixes with oil then.It is interior to avoid thermally splitting that the temperature of heavy oil feed should maintain about 100 ℃～200 ℃ scopes, still still enough high to keep rational pressure drop.The temperature of described water logistics should be enough high with guarantee with oily the mixing after, the temperature of described oil-water mixture is still than the supercritical temperature height of water.In this embodiment, in fact heat described oil by water.Can suppress condensation reaction greatly and therefore reduce the formation of coke and solid product around large quantity of moisture of described hydrocarbon molecule.
The temperature T of desired supercritical water stream
SCW, can be according to temperature of reaction T
RAnd water/oil ratio is estimated.Because the thermal capacitance of water is very big in the scope inner conversion near its critical condition, for given temperature of reaction, the temperature of desired supercritical water stream is along with the reduction of water/oil ratio almost raises by exponential relationship.Water/oil ratio is low more, T
SCWHigh more.Yet described relation is very nonlinear, because higher T
SCWCause lower thermal capacitance (away from stagnation point).
In another embodiment, water is heated under the super critical condition.In mixing tank, described supercritical water is mixed with heavy oil feed then.The temperature of described heavy oil feed should maintain in about 100 ℃～200 ℃ scopes, and is to avoid thermally splitting, still still enough high to keep rational pressure drop.After mink cell focus mixed, the temperature of water-oil mixture can be lower than the critical temperature of water; Therefore need second well heater so that the temperature of described mixture stream passes is increased to the critical temperature that is higher than water.In this embodiment, at first heat mink cell focus, by second well heater water-oil mixture is heated to super critical condition then with water section.
It will be recognized by those skilled in the art, can use based on the mixing of above instruction and other method of heating sequence and finish these targets.
Reaction conditions
After described reactant mixes, make it enter reaction zone, in reaction zone, allow them under the temperature and pressure condition of supercritical water, promptly under the condition of supercritical water, do not have outer hydrogenation in the presence of react, the residence time is enough to make upgrading reaction generation.Preferred allow the described existence generation down that is reflected at no extra catalyst or promotor, although the use of this type of catalyzer and promotor allows according to the present invention.
" hydrogen " meaning during phrase used herein " does not have outer hydrogenation " is a hydrogen.All hydrogen sources that can be used as reactant and obtain do not wanted to get rid of in this phrase.Other molecule for example stable hydrocarbon in reaction process by providing hydrogen to can be used as hydrogen source to other unsaturated hydrocarbons.In addition, steam reforming and the water-gas shift reaction by hydrocarbon can original position form H in described reaction process
2
Described reaction zone preferably comprises reactor, and this reactor is equipped with device and the preferred part in the bottom that is used for collecting reaction product (synthetic crude, water and gas), and this part can be gathered any metal or solid (" throw out logistics ").
Condition of supercritical water comprises 374 ℃ (critical temperatures of water)～1000 ℃, the temperature of preferred 374 ℃～600 ℃ and most preferably 374 ℃～400 ℃, 3205 (emergent pressure of water)～10000psia, preferred 3205～7200psia and the pressure of 3205～4000psia most preferably, and 1: 0.1～1: 10, the oil/water volume ratio of preferred 1: 0.5～1: 3 and most preferably from about 1: 1～1: 2.
Allowing described reactant to react under these conditions is enough to allow the time of upgrading reaction generation.Preferably, select the described residence time to allow described upgrading reaction preference ground and take place and to proceed to the degree of fullest and do not form the unacceptable side reaction of coke or residue.Reactor residence time can be 1 minute～6 hours, preferred 8 minutes～2 hours and most preferably 20～40 minutes.
Reactor
Design is used for using supercritical water to carry out heavy-oil modified reactor and preferably includes following feature according to the present invention:
Described reactor has suitable oil-water to be mixed and diverting device.Opposite with the thermally splitting of carrying out in uncontrollable mode (thereby the thermally splitting meeting causes generating too much light hydrocarbon and reduces liquid hydrocarbon yield under the temperature and pressure condition of supercritical water) of routine, it be lighter component that heavy hydrocarbon is understood the hydro-thermal cracking.In addition, the alkyl that forms of thermally splitting also can be once more in conjunction with and polymerization and finally become coke.Water molecules, especially under super critical condition, can chilling and stable alkyl, thus stop their overcrackings and polymerization.For avoiding overcracking is light hydrocarbon and formation coke, and described heavy hydrocarbon molecules preferably is surrounded by water molecules to greatest practical extent.Therefore, in order to obtain high liquid hydrocarbon yield, reactor comprises the well-mixed device of guaranteeing oil and water.Should select this type of device and have low api gravity and full-bodied heavy oil feed so that can under high oil/water ratio, handle.According to concrete application, this type of device can comprise, (a) nozzle, (b) static mixer, (c) stirred vessel; (d) microchannel apparatus; And sound and ultrasonic device etc.
According to the present invention, described reaction zone will be preferred:
(1) provide suitable residence time to obtain high conversion and high liquid yield.Controlling the described residence time, straitly to drop within definite scope for using supercritical water to carry out heavy-oil modified be important factors.Desirable heavy-oil modified product is a liquid hydrocarbon.The inadequate residence time can cause low-conversion and therefore cause low liquid hydrocarbon yield.On the other hand, the over-drastic conversion can cause low-value byproducts, for example light hydrocarbon gas and coke.For obtaining the conversion to liquid hydrocarbon of high selectivity, it is crucial keeping the suitable residence time.
(2) provide sufficient rate of heat transfer to distribute to keep uniform temperature.Use with other supercritical water and to compare, mink cell focus be much complicated raw material and heavy-oil modified be very complicated process.In addition, as what point out above, desirable liquid hydrocarbon is from the intermediate product of partial reaction optionally.Therefore, control reaction temperature is very important for obtaining high liquid hydrocarbon yield.By enough heat transfer area, feed distribution or can obtain suitable control to temperature of reaction by chilling uniformly are provided.
(3) solid that forms in can the processing reaction process.Can form a spot of solid by-product in the reaction process, mainly be inorganic material (metal, sulphur, coke etc.), and described reaction zone must be able to handle this type of solid, so that they can not cause operational issue and can the contaminated liquid hydrocarbon product.
The present invention also uses the disengaging zone to be used for the recovery of product.Contain water and solid under liquid hydro-carbon products, gas, the super critical condition from the effluent logistics of described reaction zone.Usually described liquid hydrocarbon and other component are separated to obtain high yield.Preferable methods is at first to remove solid, makes the fluid that contains hydrocarbon product, supercritical water and the gaseous by-product super critical condition that is separated by reducing temperature, pressure or reducing the two simultaneously then, so that hydrocarbon product and water condensation are liquid phase.Described solid mainly is the inorganic material that forms in the reaction process, and can use isolation technique as known in the art and described supercutical fluid to separate in mutually, described isolation technique can be disengaging zone or independent equipment, for example sedimentation container, strainer, the cyclonic separator etc. in the reactor.
The another kind selection that is used for separate solid is to make described product logistics break away from supercritical state by reducing temperature or pressure or reducing the two.So described solid can precipitate.The latent defect of this selection is that some inorganic components in the described solid may be dissolved in the water, and this may the contaminated liquid hydrocarbon product.Should be noted that according to concrete application, supercritical water used according to the invention carries out heavy-oil modified reactor can have more than in a kind of three key elements listing above each.
Fig. 1 has shown embodiment of the present invention, and this embodiment is used in the laboratory.The on-line mixing device is used to mix mink cell focus and water.For this specific embodiment, it is a static mixer.Described reaction zone comprises helix tube type reactor with big length/diameter ratio to obtain the high-speed of described inside reactor, and this helps to keep oil-water-dispersion.Thereby this design also makes the fluid flow of inside reactor approach piston flow and obtains narrow residence time distribution optionally to be converted into desirable liquid hydrocarbon.The inoganic solids that forms in the bed blending reaction process can not be dissolved in the supercritical water.The high-speed sedimentation that also prevents those inoganic solids of inside reactor.The minor diameter of reactor body also provides big specific surface area to distribute to keep described inside reactor uniform temperature for heat passage.The length of reactor can design according to the needed residence time of concrete transformation efficiency.Increase by second container with the described solid of sedimentation.Temperature and pressure maintain the value identical with temperature and pressure in the spiral tube in case the fluid in second container still under condition of supercritical water.Because the bigger cross-sectional area of second container, fluid velocity is much lower.The result is, the inorganic material that separates with described fluid can sedimentation in container, and can remove from described system.The described fluid that contains hydrocarbon product, supercritical water and gaseous by-product is cooled, keep simultaneously with described reactor in identical pressure, the condensation in high-pressure separator of hydrocarbon product and water.
Have high length/diameter and can be used as reactor body than the spiral tube of (this is than being 50～10000, preferred 100～4000).The use of this type of reactor has that high-speed, narrow residence time distributes and the advantage of big heating surface.Described length/diameter is than being for definite useful parameter of preferred reactor configuration.Diameter can be by avoiding the needed speed of solid precipitation to determine, and can select described length so that the desirable residence time to be provided then.Can use other reactor configuration well known by persons skilled in the art to obtain similar effects, for example serpentine reactor.
In the embodiment that Fig. 1 shows, the disengaging zone that is used to remove solid and reclaim hydrocarbon product is the container with dip-tube.Can use other fluid-solid separating device as known in the art to obtain separating effect, these equipment include but not limited to cyclonic separator, strainer, ceramic membrane, slurry tank etc.
In the embodiment and other embodiment described herein that Fig. 1 shows, described mixing tank, reaction and disengaging zone separate.Such arrangement is easily for laboratory study, and as illustrative embodiment.It within the scope of the present invention and to be integrated into these three kinds of functions in the container in some applications be useful.
As above-mentioned, described reactor can comprise every kind of function device more than.Fig. 2 shows an embodiment.For avoiding the raw material overcracking to form unacceptable by product, for example light hydrocarbon gas and tar, heavy hydrocarbon molecules is preferably surrounded by suff water.In general, help to keep desirable environment than higher water/oil ratio.Yet Gao Shui/oil ratio also means high equipment and running cost.The embodiment that shows among Fig. 2 can obtain local Gao Shui/oil ratio rather than improve whole water/raw material ratio.This embodiment is used a plurality of oily inlets rather than is mixed all stock oils at the reactor inlet place and water is kept desirable water/oil ratio.Such design also helps control reaction temperature.By the stock oil that distributes more equably along reactor length, it is too many that temperature of reaction can not raise owing to the exothermal nature of described reaction.
Two inlets have only been shown among Fig. 2.This does not want as restriction.Also can use reactor with a plurality of inlets.In addition, can in reactor, increase one or more sedimentation containers with many inlets configuration, so as under super critical condition, to realize solids constituent from.
Fig. 3 shows another embodiment that has more than 1 mixing and reaction zone.Increase by second mixing tank between reaction zone, this mixing tank can be identical or different with first mixing tank, to strengthen the mixing of described oil/supercritical water.Also can use a plurality of mixing tanks and reaction zone.Described upgrading reaction is heat release.The uniform temperature that reactor with high surface area helps to keep inside reactor distributes.According to raw material properties, the heat exchange by the surface-area that provided by reactor can be enough or can be not enough.Thereby can make the described reactant flow of water quenching and control described temperature of reaction.
Fig. 4 shows the embodiment that makes the water quenching reactant flow between two reaction zones.The amount that is used for the water of chilling should be enough to reduce described temperature of reaction, and described reactant flow still maintains super critical condition after chilling.A plurality of reaction zones and water quick cooling are necessary for some raw materials.
As shown in Figure 5, described quenched water can also be used for the recovery of product.After the reaction, described product logistics is by the liquid water chilling.Water washes out described solid, and owing to the temperature that causes by quenched water descends, and described hydrocarbon can be condensed into liquid.
Reaction product is separated
After reaction has fully been carried out, take out the homogeneous reaction product from described reaction zone, cooling also is divided into the hydrocarbon phase of gas phase, effluent water and upgrading with it.Preferably by cooling off described logistics and using one or more two phase separators, triphase separator or other gas-oil as known in the art-water separation equipment to finish described separation.Yet,, can use any separation method according to the present invention.
The composition of the gaseous product that obtains by the method according to this invention treatment of heavy hydrocarbon depends on feedstock property, and generally contain light hydrocarbon, water vapour, sour gas (CO
2And H
2S), methane and hydrogen.Described effluent water can use, reuse or is discarded.It for example can be recycled to raw material water tank, raw water treatment system or be recycled to described reaction zone.
Can use the hydrocarbon product of the known method in hydrocarbon processing field with described upgrading, this paper is called " synthetic crude " sometimes, further upgrading or be processed into other hydrocarbon product.
Method of the present invention can be carried out with continuous or semicontinuous method or discontinuous method or with the successive method.In continuation method, described total system adopts the feed stream of oil and independent supercritical water feed product to operate and reaches stable state; The composition of all thus flows, temperature, pressure and inlet, outlet and recycle stream does not have big variation in time.
Though be not bound by any theory of operation, it is believed that many upgrading reactions take place under the condition of supercritical water that uses in the method simultaneously.In the preferred embodiment of the invention, main chemistry/upgrading reaction is considered to:
Heat cracking reaction: C
xH
y→ lighter hydrocarbon
Steam reforming reaction: C
xH
y+ 2xH
2O=xCO
2+ (2x+y/2) H
2
Water-gas shift reaction: CO+H
2O=CO
2+ H
2
Demetalization reaction: C
xH
yNi
w+ H
2O/H
2→ NiO/Ni (OH)
2+ lighter hydrocarbon
Desulphurization reaction: C
xH
yS
z+ H
2O/H
2=H
2The hydrocarbon that S+ is lighter
Reactor operating condition (temperature, pressure, O/W volume ratio) may be depended in definite path, reactor design (contact/blended mode, the order of heating) and described hydrocarbon feed.
Following examples are of the present invention illustrating, but do not want to exceed any way restriction the present invention of the content that comprises in the following claim.
Embodiment 1-processing condition
Oil contacted in mixing tank before entering described reactor with supercritical water.Described reactor is equipped with the inner tube that is used to collect product (synthetic crude, excessive water and gas) and can accumulates any metal or comprise character or form the solid base section of not clear " bottoms stream ".The shell-side of described reactor is kept isothermal with clamshell furnace and temperature regulator in reaction process.Preferred reactor residence time is 20～40 minutes, and preferred oil/water volume ratio is 1: 3 a rank.Preferred temperature is about 374～400 ℃, and pressure is 3200～4000psig.Described reactor product logistics is left with single-phase, and is cooled and is divided into gas, synthetic crude and effluent water.This reactor is returned in the recirculation of effluent water.Sulphur major part in the initial raw material accumulates in bottoms stream, less amount mainly with H
2The S form is present in gas phase and aqueous phase.
Show as next embodiment, produce very small amount of gas as a rule.Select suitable operational condition, also might reduce or almost eliminate described " bottoms stream ".Eliminate bottoms stream and mean that hydrocarbon is recovered as synthetic crude greatly, but it means that also metal and sulphur can for example in water and gas stream, accumulate in other place.
The character of embodiment 2-product synthetic crude
With ratio (thinners of 20 volume %s) the dilution Hamaca crude oil of thinner hydrocarbon with 5: 1.Measured its character make the Hamaca crude oil reaction of described dilution in the supercritical water process of being mentioned with embodiment 1 and Fig. 2 before.The character of described crude oil is as follows: at 60/60 time api gravity is that 12.8,40 ℃ of following viscosity are 1329CST; The C/H ratio of 7.66wt%; The MCRT of 13.04wt%; The sulphur of 3.54wt%; The nitrogen of 0.56wt%; 3.05mgKOH/gm acid number; The water of 1.41wt%; The vanadium of 371ppm; And the nickel of 86ppm.The Hamaca crude oil of described dilution is converted into synthetic crude after supercritical water treatment, this synthetic crude has following character: at 60/60 time api gravity is that 24.1,40 ℃ of following viscosity are 5.75CST; The C/H ratio of 7.40wt%; The MCRT of 2.25wt%; The sulphur of 2.83wt%; The nitrogen of 0.28wt%; 1.54mgKOH/gm acid number; The water of 0.96wt%; The vanadium of 24ppm; And the nickel of 3ppm.Observe metal and residue significantly reduces, improved api gravity simultaneously and significantly reduced the viscosity of original crude oil feedstock.Total acid value, sulphur concentration and nitrogen concentration have medium reduction, and this can improve by the further optimization of reaction conditions.
When the Hamaca of described dilution crude oil was directly delivered in the reactor and at first do not heated with supercritical water, described product synthetic crude has following character: at 60/60 time api gravity was that 14.0,40 ℃ of following viscosity are 188CST; The MCRT of 8.7wt%; The sulphur of 3.11wt%; The vanadium of 267ppm; And the nickel of 59ppm.This comparison shows that the importance of heating sequence of the present invention.
Except bottoms stream small amount of accumulation once in a while, in described supercritical water reaction, form considerably less coke or solid by-product.Material balance is carried out in two independent experiment operations.
In service in the experiment that does not have bottoms stream to form, the diluted Hamaca crude oil starting raw material of 60 grams produces 59.25 gram synthetic crude products, and this is corresponding to 99% high total yield.Think that the mass balance of experiment is subjected to the influence of the mensuration of sulphur and metal owing to there is not bottoms stream.Described gas phase is containing metal species and contain seldom sulphur compound not.Guess that a part of metal and sulphur may accumulate on the wall of reactor or downstream line.
In service in the experiment that has bottoms stream to form, the diluted Hamaca crude oil starting raw material of 30 grams produces 22.73 gram synthetic crude products.The bottoms stream that forms accounts for 5.5 grams.Add the above bottoms stream, total yield is 96.7%.In bottoms stream, sulphur accounts for 31% of whole sulphur, and all the other sulphur are in described oily product, water and gas phase.Metal content in the bottoms stream accounts for 82% of whole metals, and all the other metals are in described oily product.For commercial operation, the formation of bottoms stream is minimized, because on behalf of the synthetic crude product, it reduce 18%, and produce the more product logistics of low value, this can influence described method aspect economy and the processing.
Before making not diluted Boscan crude oil reaction, the supercritical water process with method of the present invention measures its character.The character of described crude oil is as follows: at 60/60 time api gravity is that 9,40 ℃ of following viscosity are 1140CST; The C/H ratio of 8.0wt%; The MCRT of 16wt%; The sulphur of 5.8wt%; Vanadium with 1280ppm.Described not diluted Boscan crude oil is converted into synthetic crude after supercritical water treatment, this synthetic crude has following character: at 60/60 time api gravity is that 22,40 ℃ of following viscosity are 9CST; The C/H ratio of 7.6wt%; The MCRT of 2.5wt%; 4.6% sulphur; Vanadium with 130ppm.
Contrast initial crude oil and simulation distil analysis, show that the prepared according to the methods of the invention synthetic crude obviously has the character more superior than initial crude oil from the synthetic crude product of different experiments operation.Especially, described synthetic crude contains the more low boiler cut of high score rate.51% diluted Hamaca crude oil seethes with excitement in less than 1000 temperature range, and use is according to the method for use supercritical water of the present invention, configuration according to method, seethe with excitement at the synthetic crude between 79% to 94% less than 1000 temperature range, 40% not diluted Boscan crude oil seethes with excitement in less than 1000 temperature range, and using method according to use supercritical water of the present invention, 93% synthetic crude seethes with excitement in less than 1000 temperature range.
According to instruction described herein and supportive embodiment, might carry out many variations to the present invention.Therefore be understandable that, in following claim scope, can by remove this paper institute specially the mode description or the illustration put into practice the present invention.
Claims (20)
1. hydrocarbon is carried out the method for upgrading, comprise
(a) hydrocarbon is heated to the fluid of water that temperature is higher than its critical temperature and is being unfavorable for mixing under the condition that thermally splitting and coke form with the formation mixture in the mixing zone with comprising;
(b) described mixture is passed to reaction zone;
(c) described mixture is reacted in described reaction zone, described reaction zone have that basic uniform temperature distributes and for reduce solid in described reaction zone sedimentation and dispose, described being reflected under the condition of supercritical water do not taken place under the situation of hydrogenation outside having, and the residence time is controlled in the definite scope that allows upgrading reaction generation;
(d) take out the homogeneous reaction product from described reaction zone; And
(e) described reaction product is divided into the hydrocarbon phase of gas phase, effluent water and upgrading.
2. according to the process of claim 1 wherein that described hydrocarbon is to be selected from full cut heavy crude crude oil, tar sand bitumen, the acquisition heavy hydrocarbon from heavy hydrocarbon fractions, heavy vacuum gas oil, vacuum residuum, petroleum tar, coal tar and their mixture of petroleum crude oil.
3. according to the process of claim 1 wherein that the aqueous fluid of described bag enters described mixing zone under the temperature of the critical temperature that fully is higher than water, so that resulting mixture has the temperature higher than the supercritical temperature of water.
4. according to the process of claim 1 wherein that the described heavy hydrocarbon temperature in the step (a) is 100 ℃～200 ℃.
5. according to the process of claim 1 wherein that described condition of supercritical water comprises that temperature is 374 ℃～1000 ℃, pressure is 3205psia～10000psia, and oil/water volume ratio is that 1: 0.1～1: 5 and the wherein said residence time are 1 minute～6 hours.
6. according to the method for claim 1.Wherein said condition of supercritical water comprises that temperature is 374 ℃～600 ℃, and pressure is 3205psia～7200psia, and oil/water volume ratio is that 1: 0.5～1: 3 and the wherein said residence time are 8 minutes～2 hours.
7. according to the process of claim 1 wherein that described condition of supercritical water comprises that temperature is 374 ℃～400 ℃, pressure is 3205psia～4000psia, and oil/water volume ratio is that 1: 1～1: 2 and the wherein said residence time are 20～40 minutes.
8. react under the situation of catalyzer that provides in no any outside according to the described mixture that the process of claim 1 wherein in described reaction zone or promotor.
9. according to the method for claim 1, also be included in described mixture is passed to the step that described reaction zone is higher than described mixture heating up to the temperature that forms in the step (a) critical temperature of water before.
10. according to the process of claim 1 wherein by controlling the heat transfer area in the described reaction zone, by distributing described hydrocarbon feed or obtain described uniform temperature by chilling and distribute equably.
11. heavy hydrocarbon is carried out the method for upgrading, comprising:
(a) with heavy hydrocarbon with comprise the fluid of supercritical water that temperature is higher than the critical temperature of water and in the mixing zone, be unfavorable for mixing the mixture that is higher than the critical temperature of water with formation temperature under the condition that thermally splitting and coke form;
(b) described mixture is passed to reaction zone;
(c) described mixture is reacted in described reaction zone, described reaction zone have that basic uniform temperature distributes and for reduce solid in described reaction zone sedimentation and dispose, described being reflected under the condition of supercritical water under the situation of not having outer hydrogenation and catalyzer reacted, and the residence time is controlled at and allows in definite scope that the upgrading reaction takes place;
(d) take out the homogeneous reaction product from described reaction zone; And
(e) described reaction product is divided into the hydrocarbon phase of gas phase, effluent water and upgrading.
12. according to the method for claim 11, wherein said hydrocarbon is to be selected from full cut heavy crude crude oil, tar sand bitumen, the heavy hydrocarbon of acquisition in heavy hydrocarbon fractions, heavy vacuum gas oil, vacuum residuum, petroleum tar, coal tar and their mixture of petroleum crude oil.
13. according to the method for claim 11, the aqueous fluid of wherein said bag is fully entering described mixing zone under the temperature greater than the supercritical temperature of water, so that resulting mixture has the temperature higher than the critical temperature of water.
14. according to the method for claim 11, wherein the heavy hydrocarbon temperature in the step (a) is 100 ℃～200 ℃.
15. according to the method for claim 11, wherein said condition of supercritical water comprises that temperature is 374 ℃～1000 ℃, pressure is 3205psia～10000psia, and oil/water volume ratio is that 1: 0.1～1: 5 and the wherein said residence time are 1 minute～6 hours.
16. method according to claim 11.Wherein said condition of supercritical water comprises that temperature is 374 ℃～600 ℃, and pressure is 3205psia～7200psia, and oil/water volume ratio is that 1: 0.5～1: 3 and the wherein said residence time are 8 minutes～2 hours.
17. according to the method for claim 11, wherein said condition of supercritical water comprises that temperature is 374 ℃～400 ℃, pressure is 3205psia～4000psia, and oil/water volume ratio is that 1: 1～1: 2 and the wherein said residence time are 20～40 minutes.
18., wherein react under the catalyzer that provides in no any outside of the described mixture in described reaction zone or the promotor situation according to the method for claim 11.
19., also be included in described mixture passed to the step that described reaction zone is higher than described mixture heating up to the temperature that forms in the step (a) critical temperature of water before according to the method for claim 11.
20. according to the method for claim 11, wherein by the heat transfer area of control in the described reaction zone, by distributing described hydrocarbon feed or obtain described uniform temperature by chilling and distribute equably.
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| US11/555,196 | 2006-10-31 | ||
| US11/555,196 US20080099378A1 (en) | 2006-10-31 | 2006-10-31 | Process and reactor for upgrading heavy hydrocarbon oils |
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| CN (1) | CN101541924A (en) |
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| CA2143404C (en) * | 1994-03-09 | 1999-05-04 | Michael Siskin | Process for removal of heteroatoms under reducing conditions in supercritical water |
| FR2727634A1 (en) * | 1994-12-06 | 1996-06-07 | Electrolyse L | CHEMICAL PROCESSING REDUCER PROCESS OF COMPLEX CHEMICAL STRUCTURES IN A SUPERCRITICAL FLUID |
| US5560823A (en) * | 1994-12-21 | 1996-10-01 | Abitibi-Price, Inc. | Reversible flow supercritical reactor and method for operating same |
| US5567698A (en) * | 1995-02-15 | 1996-10-22 | Bristol-Myers Squibb Company | Pyridinium thiomethyl substituted chepholosporin derivatives |
| JP3366820B2 (en) * | 1997-02-19 | 2003-01-14 | 株式会社日立製作所 | Oxidation treatment method and apparatus and reaction vessel |
| KR20040028622A (en) * | 2001-08-21 | 2004-04-03 | 미쓰비시 마테리알 가부시키가이샤 | Method and apparatus for recycling hydrocarbon resource |
| US6887369B2 (en) * | 2001-09-17 | 2005-05-03 | Southwest Research Institute | Pretreatment processes for heavy oil and carbonaceous materials |
| JP4098181B2 (en) * | 2003-08-05 | 2008-06-11 | 株式会社日立製作所 | Heavy oil treatment method and heavy oil treatment system |
-
2006
- 2006-10-31 US US11/555,196 patent/US20080099378A1/en not_active Abandoned
-
2007
- 2007-10-30 CN CNA2007800443169A patent/CN101541924A/en active Pending
- 2007-10-30 EA EA200970439A patent/EA200970439A1/en unknown
- 2007-10-30 CA CA002667261A patent/CA2667261A1/en not_active Abandoned
- 2007-10-30 WO PCT/US2007/083038 patent/WO2008055171A2/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104039434A (en) * | 2011-10-31 | 2014-09-10 | 沙特阿拉伯石油公司 | Supercritical water process to upgrade petroleum |
| CN104039434B (en) * | 2011-10-31 | 2015-11-25 | 沙特阿拉伯石油公司 | For the supercritical water technique of upgrading oil |
| CN104619947A (en) * | 2012-05-31 | 2015-05-13 | 原位升级技术有限公司 | In situ upgrading via hot fluid injection |
| CN103013550A (en) * | 2012-11-27 | 2013-04-03 | 西安交通大学 | System and method for preparing fuel oil by using supercritical water to modify tar residue |
| CN108495915A (en) * | 2015-12-15 | 2018-09-04 | 沙特阿拉伯石油公司 | The supercritical water upgrade method of alkane stream is prepared by heavy oil |
| CN109628134A (en) * | 2019-02-15 | 2019-04-16 | 华东理工大学 | Method for regulating and controlling heavy oil molecules structure |
| CN111665164A (en) * | 2019-03-05 | 2020-09-15 | 中国石油化工股份有限公司 | Determination of CO2Experimental device, system and method for mass transfer coefficient between oil and water |
| CN112680246A (en) * | 2020-12-28 | 2021-04-20 | 西安交通大学 | Direct-production crude oil ground modification supercritical hydrothermal reaction system |
Also Published As
| Publication number | Publication date |
|---|---|
| EA200970439A1 (en) | 2009-10-30 |
| WO2008055171A3 (en) | 2008-09-12 |
| WO2008055171A2 (en) | 2008-05-08 |
| CA2667261A1 (en) | 2008-05-08 |
| US20080099378A1 (en) | 2008-05-01 |
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