CN101484550A - Process for simultaneous recovery and cracking/upgrading of oil from solids - Google Patents
Process for simultaneous recovery and cracking/upgrading of oil from solids Download PDFInfo
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- CN101484550A CN101484550A CNA2007800174764A CN200780017476A CN101484550A CN 101484550 A CN101484550 A CN 101484550A CN A2007800174764 A CNA2007800174764 A CN A2007800174764A CN 200780017476 A CN200780017476 A CN 200780017476A CN 101484550 A CN101484550 A CN 101484550A
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- oil
- sand
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- cracking
- upgrading
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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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a process for the simultaneous recovery and cracking/upgrading of oil from solids such as tar sand and oil shale. With this process a number of the obstacles with the existing technology are solved, and the process upgrades the oil into a lighter product than the existing technology, remove sulphur in the order of 40% and heavy metals in the order of 90%.
Description
The present invention relates in same process the method for from Tar sands (also being oil-sand) and/or resinous shale refiltered oil and the described oil of upgrading (upgrading).
All found a large amount of Tar sands in many countries, maximum resource discovering is formed in Canada and by heavy oil in the natural resources of different depths and sand (heavy oil and sand).These resources have become the theme of big quantity research, and purpose is the technology of exploitation refiltered oil from described sand.Therefore, there are many different technology.
The most important mineral wealth in Alberta (Alberta) are oil and gases, and the income of Alberta about 90% is from mining industry.The Alberta produces the oil of Canada about 2/3 and greater than 3/4 Sweet natural gas.Almost half oil exploitation of Alberta is from a large amount of oil-sands, and it is the heavy crude mineral deposit of (being called pitch).The oil-sand of Alberta is the pitch mineral deposit of known maximum in the world.Oil-sand is present in three main region of this province: the area, peaceful river (Peace River) in the Athabasca river valley of northeast (Athabasca River Valley), the north and cold air lake (Cold Lake) area of east, center, Alberta.Compare with conventional crude, the bituminous cost of winning is higher, and wherein conventional crude flows or naturally from the earth pumping.This is because must further purified is slightly oily with preparation with heavy-gravity dirty oil and on every side sand and water sepn.
During the twentieth century fifties and the sixties, found oil field in other area, area, for example peaceful river and Swan Hills, Lesser Slave Hunan portion.To the twentieth century latter stage sixties, last main oil field all is found.
Pitch, it is opposite with the ordinary crude oils that is found in dark oil bearing reservoir, does not have identical lighting end, because these lighting ends have been evaporated in the process in thousands of years.Therefore, pitch is made up of weight molecule, and density surpasses 1.000kg/dm
3(less than 10API), viscosity is 1000 times of light crude.In addition, Tar sands comprise above the sulphur of 4 weight % and the heavy metal of hundreds of ppm.The content of organic substance can be 5 weight %-20 weight % in the Tar sands, and therefore, extract oil relates to huge mass transfer from Tar sands.
Because bituminous is formed, equally with light crude can must carry out upgrading to it in a refining unit before the refining at it.
Because the economic potential of these huge resources, thus exist many different from Tar sands the method for refiltered oil.These technology relate to biological process, solvent method, calorimetry and wherein wash out the method for oil by superheated water from sand.
Because extract relevant a large amount of sand (tailings (tailings)) with Tar sands, these diverse ways face many environmental restraint.
Opposite with Tar sands, resinous shale is the shale that comprises the organic substance that is called petrologen (keorgens), and petrologen is washed can not the pitch in Tar sands or dissolves.For refiltered oil from resinous shale, it must be heated to 500-600 ℃ temperature, and organism is a liquid product by cracking thus.The same with Tar sands, resinous shale comprises the composition of not expecting in a large number that causes environmental restraint.The same with the technology of refiltered oil from Tar sands, exist many from resinous shale the different technologies of refiltered oil.
The present invention relates to a kind of energy from the method for keeping (energy self sustained process), wherein solved the obstacle that exists in many prior aries, with its except recovery of oil, also be than the light product of any other prior art, remove about 40% sulphur and about 90% heavy metal described oily upgrading.In addition, described method is disposed tailings under limited environmental restraint, because inorganic substance (sand) are disposed under drying conditions.
Described method is " to do-wet " fluidizing method fast, and its medium sand is in the fluidized reactor of fuel by sneaking into the part organic constituent in the Tar sands.Combustion gases (combustion gases) come out oil stripping (strip) from described sand, they serve as together pneumatic carrier with sand and the gas delivery relevant with it in cyclone reactor, separate from gas streams at this sand, gas streams is transported to condenser system then.The oil that is condensed of part can be transferred via atomizing nozzle and get back in the described materials flow to carry out secondary cracking, can reclaim and upgrading oil in an operation thereby described method need not reforming unit.
For optimizing collision between the particle with the maximum shear stress between the solid that obtains the sand materials flow, combustion gases and appropriate hydrocarbon gas are accelerated in the standpipe (riser) of the diameter with variation and slow down.
Collision between the particle causes the mild hydrogenation of oil by the sonoluminescence effect of colliding the small steam bubble that captures between the solids.When being hunted down between unfairness place in steam bubble is rolling particle (unevenness), steam is subjected to adiabatic compression, thereby the temperature and pressure in the bubble is elevated to bulk temperature in this process and thousands of times of pressure.This causes water to enter supercritical state, and wherein water is cracked into hydrogen and oh group (hydrogen and hydroxyl radicals).The hydrogen that is absorbed by heavy oil chains reduces their combination, thereby can the cracking molecule and " blast " of described small steam bubble take place from the particulate surging force of rolling.Most of hydrogen be released then and again with the oh group water generation reaction, but part hydrogen causes the mild hydrogenation of product.
Very expectation as far as possible early and as quickly as possible realizes the well blend of sand/oil.In order to realize that the described present method of this purpose needs the acceleration and the deceleration of above-mentioned materials flow.Usually, steam is flowability and the standpipe medium of movement that is used for keeping Solid Bed.Yet steam has disadvantageous effect to the very hot solid that runs in residue cracking process (residue crackingprocesses).Under these conditions, steam causes the hydrothermal deactivation of catalyzer in FCC-cracker for example.
This is overcome by the carrier of the discharge gas (CO/CO2 and appropriate hydrocarbon gas) of the present invention by being used to self-fluidized type bed reactor regenerator (regenerator) as solid (its will as the catalyzer in the oily cracking).
In order to prove this method, set up the test set of 2.5 * a 2.5 * 3m, it is positioned at the SINTEF ENERGY RESEARCH AS of Trondheim, Norway, and peak power is 125kW.
The layout of device is shown in Figure 3.
Fig. 4 illustrates this device in the test process.
The energy requirement of processing 1kg oil-sand is provided by following formula:
Q＝x
s*c
s*dt+x
o(c
s*dt+r
o)+x
w*H
Wherein
x
sThe weight part of=sand (comprising metal and sulphur), for example 80%
x
oThe weight part of=oil, for example 15%
x
wThe weight part of=water, for example 5%
c
sThe specific heat kJ/kgK=1kJ/kgK of=sand
c
oThe about 2.25kJ/kgK of specific heat kJ/kgK=of oil under the=service temperature
r
oThe about 225kJ/kg of=vaporization heat kJ/kg=
The service temperature of dt=sand and the temperature difference K between the feeding temperature
The enthalpy kJ/h=3500kJ of water under the H=service temperature
360 ℃=633K of service temperature
90 ℃=363K of feeding temperature
dt＝270K
Q=516kJ/kg, its capacity that provides this test set is the 872kg/hr sand that contains 130kg oil, it provides capacity is about 20 barrels (bbl)/sky.
Test adopts the Tar sands from mineral deposit, Athabasca river valley to carry out, its character as mentioned above, wherein the results are as follows:
The density of the oil that reclaims by fluidisation device (fluidiser): 21API.
The density of the oil that reclaims in the standpipe: 29.3API.
The density of the oil of discharging in the oil cooling condenser: 25.15API.
Remaining coke (coke): 1.25W% in the exhausted sand.
The reduction of sulphur in the oil: 45%
The reduction of heavy metal: 87%
The about 12.5kg oil of energy expenditure %:93=of the oil that reclaims/hour=about 3.93USD/ bucket (bbl).(oil price 50USD/ bucket)
Fig. 5 illustrates the oil-sand from described test, the oil and the clean sand of recovery.
Further describe this method in the simplified flow chart in Fig. 1.
A) expression vertical fluidised reactor, it has the fluidised mesh B that is positioned at apart from container bottom a distance).Described bottom and fluidised mesh B) between the space be the C of pumping chamber (plenum)), it receives from burner D) combustion gases, this burner can act as a fuel with the oil of gas and/or recovery.These combustion gases will heat and fluidized reactor A) middle entrained solid (sand) E).The pressure of in reactor, setting up from combustion gases, to make solid and be passed through standpipe JJ by pneumatic transport) by the gas of carrying secretly that combustion gases, steam and appropriate hydrocarbon gas are formed, enter reactor cyclone G) in, the design of this reactor cyclone is feasible, opposite with common cyclonic separator, described solid is being fallen tapered section H) and get back in the fluidisation device before, rotation is hundreds of time in the cylindrical part of cyclonic separator.In the bottom of cyclonic separator tapered section, superheated vapour is via pipeline I) inject cyclonic separator and go out cyclone with stripping and fall into reactor A via dipleg (dip-leg)) the whereabouts solid between hydrocarbon.
Oil-sand is by feed system Cc) and Dd) injecting reactor A) in.With injecting reactor A) in the sand of equal amts must from reactor, be discharged.This is by piping arrangement K) finish, its medium sand is transported to fluidized bed combustion device L), at this by by M) inject the remaining coke of air and burnt.From L) waste gas in being discharged into air before by gas sweetening and heat recovery system N).
From L) " totally " solid be transported to solid-liquid heat exchanger O), this heat exchanger heats is come automatic heat-exchanger Z) water coolant, it is by working shaft P) carry.Hot water further is transported to and is arranged in burner L) vapour generator Q).This vapour generator produces steam, and wherein part steam is admitted to and is arranged in reactor A) the C of pumping chamber) superheater (super-heater) R).Superheated steam is transported to injection nozzle S) be used for oil steam atomizing, be transported to reactor cyclone H) on dipleg J) and separation cyclone U) on dipleg T).Refrigerative " totally " sand can be from heat exchanger O) be discharged to landfill yard (land fill) because described sand will be exsiccant and not have any volatile hydrocarbon.
The excess steam of not passing through Overheating Treatment is through pipeline V) carry and to be used for preheated feed, processing purpose or to be used for generating electricity by turbine system.
From reactor cyclone G) and separation cyclone U), gaseous stream is transported to and is set at about 95 ℃ condenser W), the major portion of oil gas body is condensed into liquid oils thus.Described gas is condensed by means of the oil that reclaims, because the oil of collecting in this condenser bottom is by pump X) pumping is through over-heat-exchanger Z) and by by pump P) water cooling of carrying.From heat exchanger Z), refrigerative oil is transported to the top of condenser and the oil gas body that condensation enters.Along with the rising of oil level in the condenser, product is by managing BB) discharge.Uncondensable gas and steam are transported to the second condenser CC), it is by by pump P) water cooling of injecting.The water of condensation is by pipeline DD) from this condenser, discharge and be collected in clarifying tank EE) in.At clarifying tank EE) in, from oil cooling condenser CC) light oil will be by pipeline FF) be decanted into from oil cooling condenser W) and the product pipeline and via managing AA) be transported to receptor.Water is via pipeline GG) discharge.
Condenser CC) uncondensable material is by pipeline HH in) drain in the air or the gas sweetening system in, this depends on local requirement to discharge.
Portioned product is by high-pressure pump LL) via pipeline NN) turn back to be connected to standpipe JJ) on atomizing nozzle S), thereby send standpipe JJ back to).
Atomizing nozzle S) from superheater R) receive the steam of the described oil that is used to atomize.
The combustion gases of excessive formation in the reactor, it is for standpipe JJ) transmission of medium sand is unwanted, can be via pipeline OO) discharge reactor, enter unshowned gas sweetening and heat recovery system.
When by burner D) when reactor is heated to service temperature, being used for incendiary gas or supply of oil can cut off gradually, the air of Zhu Ruing will cause reactor A thus) internal combustion of the appropriate hydrocarbon gas that forms, this method be kept oneself by the energy that is extracted by Tar sands itself thus.Selectively, this burner can use by pump LL) the partially recycled oil carried acts as a fuel.
For acceleration and the deceleration that obtains materials flow in the above-mentioned standpipe, this can realize by the diameter that makes standpipe have variation.One preferred embodiment is that the part standpipe is formed Laval nozzle, wherein said one or more atomizing nozzle S) be arranged in the narrowest part of this injector or be positioned at this injector and begin the expansible position.
Because the speed of gas and sand materials flow, so described entire method is the high-strength hot process with high-energy-density.Because the low dividing potential drop of strong heat exchange between speed, sand and the oil in this method and the appropriate hydrocarbon gas that caused by combustion gases and steam, this method can be at the temperature operation of 300-500 ℃ of scopes.Except the thermal stresses and energy expenditure that reduce, this low temperature has also reduced the polymerization of crackate.
Fig. 2 represents the figure of 10.000 barrels (bbl)/day device.
Claims (9)
1. from solid, for example from Tar sands and resinous shale, reclaim simultaneously and the method for cracking/upgrading of oil, it is characterized in that oil-containing solids is injected fluidized-bed reactor, hydrocarbon is evaporated and the heat that wherein is used for described evaporation is provided by the internal combustion of the part of the hydrocarbon of solid or provided by the burner of outside in this reactor, with be characterised in that combustion gases with the hydrocarbon of evaporation as the pneumatic carrier of described solid and reduce the dividing potential drop of appropriate hydrocarbon gas and wherein materials flow be transported to cyclone reactor, and further be transported to solid removing separator and further be transported to the condenser system that is used for condensable gases.
2. according to claim 1 from solid, for example from Tar sands and resinous shale, reclaim simultaneously and the method for cracking/upgrading of oil, it is characterized in that part carries via atomizing nozzle in the materials flow of getting back in standpipe from the product of condenser system, described thus stream of solids by shearing force, heat exchange and sonoluminescence effect as the cracking medium.
As described in claim 1 and 2 from solid, for example from Tar sands and resinous shale, the method of recovery and cracking/upgrading of oil is characterized in that described standpipe has the collision of different diameters to realize optimizing between the solid particulate in acceleration, deceleration and the described materials flow simultaneously.
4. according to claim 1 from solid, for example from Tar sands and resinous shale, the method for recovery and cracking/upgrading of oil is characterized in that the temperature in the revivifier is controlled by the wet oil sand that injects this revivifier simultaneously.
5. according to claim 1 from solid, for example from Tar sands and resinous shale, reclaim simultaneously and the method for cracking/upgrading of oil, it is characterized in that the sand that stripping is oily excessively is transported to the fluidized bed combustion device, wherein by in this burner, inject air with sand on remaining coke burning-off and the heat that wherein discharges be used to prepare steam, wherein selectively be transported to the pumping chamber of stripping reactor, thereby participate in the stripping of the oil of catching on the sand with heat and fluidizing agent from the waste gas of this burner.
6. according to claim 1 from solid, for example from Tar sands and resinous shale, the method for recovery and cracking/upgrading of oil is characterized in that part is mixed with oil-sand to reclaim heat and to make sand even, to improve the charging of reactor through steam stripped sand simultaneously.
7. according to claim 1 from solid, for example from Tar sands and resinous shale, the method for recovery and cracking/upgrading of oil is characterized in that fluidized-bed reactor has two diameters simultaneously, wherein in order to reduce the gas velocity in the revivifier top, the diameter of revivifier bottom is less than the revivifier upper part diameter.
8. according to claim 1 from solid, for example from Tar sands and resinous shale, reclaim simultaneously and the method for cracking/upgrading of oil, it is characterized in that discharging from revivifier continuously via pipeline in the revivifier through steam stripped sand, it can be " water " trap of U type that this pipeline has in this revivifier outside, steam or gas are injected this pipeline is used for the sand that pneumatic transport falls into this trap with wherein relative with this " water trap ".
9. according to claim 1 from solid, for example from Tar sands and resinous shale, reclaim simultaneously and the method for cracking/upgrading of oil, it is characterized in that receiving collector and heat recuperation fluidisation device (L) is provided with one group of revivifier around total charging system and total sand, wherein from shared total sand separation system of the discharge gas of described revivifier and total condenser device, and wherein refrigerative through the oil of condensation by deep fat gas and the direct contact of this refrigerative between the oil of condensation as the cooling medium in the oil cooling condenser.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2546940A CA2546940C (en) | 2006-05-15 | 2006-05-15 | Process for simultaneous recovery and cracking/upgrading of oil from solids |
| CA2546940 | 2006-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101484550A true CN101484550A (en) | 2009-07-15 |
Family
ID=38686899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800174764A Pending CN101484550A (en) | 2006-05-15 | 2007-05-10 | Process for simultaneous recovery and cracking/upgrading of oil from solids |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20090120844A1 (en) |
| EP (1) | EP2029695A4 (en) |
| CN (1) | CN101484550A (en) |
| AU (1) | AU2007250630B2 (en) |
| BR (1) | BRPI0711480A2 (en) |
| CA (1) | CA2546940C (en) |
| MX (1) | MX2008014630A (en) |
| NO (1) | NO20085143L (en) |
| RU (1) | RU2434049C2 (en) |
| WO (1) | WO2007133089A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO331801B1 (en) * | 2009-01-09 | 2012-04-02 | Tarblaster As | Process for simultaneous recovery and cracking of oil from oil / solid mixtures |
| GB201200155D0 (en) | 2012-01-06 | 2012-02-15 | Statoil Asa | Process |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2537153A (en) * | 1946-10-08 | 1951-01-09 | Standard Oil Dev Co | Fluidized carbonization process |
| US2534051A (en) * | 1946-11-22 | 1950-12-12 | Standard Oil Dev Co | Method for fluidized low-temperature carbonization of coal |
| US2729597A (en) * | 1949-04-30 | 1956-01-03 | Hydrocarbon Research Inc | Process for rendering solid carbonaceous materials non-agglomerative |
| US2764531A (en) * | 1952-08-01 | 1956-09-25 | Exxon Research Engineering Co | Process and apparatus for retorting oil shale |
| US3501394A (en) * | 1967-04-17 | 1970-03-17 | Mobil Oil Corp | Gas lift retorting process for obtaining oil from fine particles containing hydrocarbonaceous material |
| US4105502A (en) * | 1976-06-25 | 1978-08-08 | Occidental Petroleum Corporation | Simplified liquefaction pyrolysis process and apparatus therefor |
| US4094767A (en) * | 1976-11-10 | 1978-06-13 | Phillips Petroleum Company | Fluidized bed retorting of tar sands |
| US4369100A (en) * | 1977-09-27 | 1983-01-18 | Sawyer Harold T | Method for enhancing chemical reactions |
| US4264435A (en) * | 1978-04-05 | 1981-04-28 | The Dow Chemical Company | Crude oil cracking using partial combustion gases |
| US4276021A (en) * | 1979-08-08 | 1981-06-30 | Dravo Corporation | Method of recovering heat from hot granular solids |
| US4326944A (en) * | 1980-04-14 | 1982-04-27 | Standard Oil Company (Indiana) | Rapid hydropyrolysis of carbonaceous solids |
| DE3023670C2 (en) * | 1980-06-25 | 1982-12-23 | Veba Oel Entwicklungsgesellschaft mbH, 4660 Gelsenkirchen-Buer | Method and device for smoldering oil shale |
| US4412910A (en) * | 1981-10-21 | 1983-11-01 | Westinghouse Electric Corp. | Recovery of fuel from oil shale |
| US4415433A (en) * | 1981-11-19 | 1983-11-15 | Standard Oil Company (Indiana) | Fluid bed retorting process with multiple feed lines |
| US4507195A (en) * | 1983-05-16 | 1985-03-26 | Chevron Research Company | Coking contaminated oil shale or tar sand oil on retorted solid fines |
| US5076910A (en) * | 1990-09-28 | 1991-12-31 | Phillips Petroleum Company | Removal of particulate solids from a hot hydrocarbon slurry oil |
| US5914027A (en) * | 1994-09-12 | 1999-06-22 | Thermtech A/S | Thermo-mechanical cracking and hydrogenation |
| KR0171501B1 (en) * | 1996-08-28 | 1999-03-20 | 이성래 | Apparatus and process for reclaiming waste oil |
| US6709573B2 (en) * | 2002-07-12 | 2004-03-23 | Anthon L. Smith | Process for the recovery of hydrocarbon fractions from hydrocarbonaceous solids |
| NO20040615L (en) * | 2004-02-11 | 2005-08-12 | Ellycrack As | Low temperature catalytic cracking and conversion process for upgrading heavy crude oil |
-
2006
- 2006-05-15 CA CA2546940A patent/CA2546940C/en not_active Expired - Fee Related
-
2007
- 2007-05-10 MX MX2008014630A patent/MX2008014630A/en active IP Right Grant
- 2007-05-10 BR BRPI0711480-0A patent/BRPI0711480A2/en not_active IP Right Cessation
- 2007-05-10 CN CNA2007800174764A patent/CN101484550A/en active Pending
- 2007-05-10 US US12/300,549 patent/US20090120844A1/en not_active Abandoned
- 2007-05-10 RU RU2008149093/04A patent/RU2434049C2/en not_active IP Right Cessation
- 2007-05-10 WO PCT/NO2007/000170 patent/WO2007133089A1/en active Application Filing
- 2007-05-10 AU AU2007250630A patent/AU2007250630B2/en not_active Ceased
- 2007-05-10 EP EP07747631A patent/EP2029695A4/en not_active Withdrawn
-
2008
- 2008-12-10 NO NO20085143A patent/NO20085143L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO20085143L (en) | 2008-12-15 |
| AU2007250630A1 (en) | 2007-11-22 |
| MX2008014630A (en) | 2009-02-06 |
| CA2546940C (en) | 2010-09-21 |
| EP2029695A1 (en) | 2009-03-04 |
| RU2434049C2 (en) | 2011-11-20 |
| RU2008149093A (en) | 2010-06-20 |
| EP2029695A4 (en) | 2011-11-02 |
| WO2007133089A1 (en) | 2007-11-22 |
| AU2007250630B2 (en) | 2011-08-18 |
| US20090120844A1 (en) | 2009-05-14 |
| CA2546940A1 (en) | 2007-11-15 |
| BRPI0711480A2 (en) | 2011-11-16 |
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Application publication date: 20090715 |