CN109415634A

CN109415634A - The method of pitch is extracted from oil-sand with aromatic amine

Info

Publication number: CN109415634A
Application number: CN201780041598.0A
Authority: CN
Inventors: M·L·图尔齐因斯基; N·秋也; B·慕克吉; C·A·威瑟姆
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2016-07-18
Filing date: 2017-06-16
Publication date: 2019-03-01
Also published as: EA201990322A1; WO2018017221A1; CA3031205A1; US20190225889A1

Abstract

The present invention relates to a kind of improved methods that pitch is recycled from oil-sand.Processing region can be exploited through earth's surface and be transported to the oil-sand, or can and too deep to position cannot opencast oil sand deposit carry out processing in situ directly to handle.In particular it relates to the step of handling oil-sand with aromatic amine.

Description

The method of pitch is extracted from oil-sand with aromatic amine

Technical field

The present invention relates to pitch is recycled from oil-sand.More precisely, the present invention [is a kind of by earth's surface exploitation or in situ Recycling recycles the improved method of pitch from oil-sand.The improvement is to use aromatic amine as used in bitumen recovery process Extraction auxiliary agent in water and/or steam.

Background technique

Oil sand deposit has been had been found that all over the world, but most outstanding is Canada, Venezuela and the U.S..These oil Sand contains a large amount of heavy oil deposits, commonly referred to as pitch.Pitch from these oil-sands can be extracted and be refined into synthetic oil Or directly it is refined into oil product.It is usually very sticky that the difficulty of processing pitch is it, it is that liquid is not so good as sometimes Say it is solid.Therefore, pitch will not usually flow or light crude oil lower as viscosity.

Due to the sticky property of pitch, cannot be generated from the well for pierce oil-sand as light crude oil.This is because Pitch does not flow in the case where not heating, diluting and/or upgrading first.Since conventional oil probing practice is not enough to generate Pitch, if therefore having been developed that drying method in the past few decades to extract and process oil-sand to remove pitch.For oil-sand Shallow deposit, typical method include surface extraction or exploitation, carry out the subsequent processing of oil-sand then to remove pitch.

The exploitation of surface extraction method has most widely appeared in the oil field Canadian Athabasca (Athabasca). In these methods, oil-sand usually via strip mining transformation (strip mining/open pit mining) with dragline, Bucket-wheel excavator and nearest spades and truck operations are exploited.Then oil-sand is transported in an equipment and is processed simultaneously Pitch is removed from sand.These methods are usually directed to certain type of solvent, and the most commonly used is water or steam, but have also used Other solvents, such as hydrocarbon solvent.

After excavation, usually using hot water extraction procedure in Athabasca oil field, wherein oil-sand and water are about 35 DEG C to mixing at a temperature in the range of 75 DEG C, wherein being newly improved the lower part for making required temperature be reduced to the range.It can will mention Agent is taken, as sodium hydroxide (NaOH), surfactant and/or air are mixed with oil-sand.

Add water into oil-sand and generate oil-sand slurry, can add the additive such as NaOH thereto, then usually via Pipeline is transported to extract equipment.In separation vessel, stirs slurry and water and NaOH discharge pitch from oil-sand.Entrainment There are the air of water and NaOH to be attached to pitch, pitch is made to float to the top of slurry mix and generates foam.It is further processed Asphalt foam is usually small sand and clay particle to remove remaining water and particulate.Then bituminous pitch storing is used for further It handles or immediately treats, chemically or with oils mix, and is former at synthesis for upgrading by pipeline Oil.Regrettably, this method cannot be used for deeper tar layer of sand.For being recycled for deep-seated oil in well produces, In-situ techniques are required.It is estimated that about 80% Alberta (Alberta) Tar sands and almost all of Venezuela are burnt Oil-sand is at too deep position under earth's surface and is not available surface mining.

In well production (recycling referred to as in situ), steam soak (Cyclic Steam Stimulation, CSS) is conventional " handling up " in-situ method, wherein by steam 250 DEG C to 400 DEG C at a temperature of injection well in.Steam rises and heated asphalt, drop Its low viscosity.So that well is stood a couple of days or several weeks, and the hot oil for being then blended with condensed steam pumps out, persistently carry out several weeks or The time of several months.Then repeat the process.Regrettably, method of " handling up " requires to close in place several weeks so that can The oil accumulation of pumping.Other than the high cost of injection steam, CSS method generally produces 20 to 25% available oil recovery rate.

Steam assisted gravity drainage (Steam Assisted Gravity Drainage, SAGD) is another original position side Method, wherein boring two horizontal wells in Tar sands, one is located at stratum bottom, another is positioned above at five meters.The well It is drilled out from center pad group.These wells can extend several miles to all directions.It injects steam into the well of top, to keep pitch molten Change, pitch subsequently flows into lower well.The resulting liquid oil for being mixed with condensed steam is then pumped into earth's surface.Oil can be used The typical rate of recovery is 40% to 60%.

The problem of in-situ method includes the low rate of recovery and high-energy and water demand.In addition, based on the method for steam for It is for shallow-layer reservoir with low maximum operating pressure or the reservoir with small property layer and not energy-efficient.

USP 5264118 describes a kind of for exploiting the pipeline adjusting method of oil-sand.The present invention relates to sufficient length Pipeline oil-sand and hot water and sodium hydroxide.During transportation, pitch is released from oil-sand particle surface, and The air of entrainment helps to discharge the ventilation of pitch.Caustic alkali is a kind of effective extraction auxiliary agent, but is difficult to control and was easy to Amount, this, which can be generated, is difficult to isolated stable emulsion.The high pH as caused by caustic alkali will lead to excessive from asphalt surface generation Naturally occurring surfactant and possible asphalt emulsification.In addition, generated surfactant can be at pitch/water termination It absorbs and prevents effectively coalescing and it is made to be difficult to be separated from water between asphalt liquid droplets.In addition, not only being deposited using a large amount of caustic alkali It is endangered in process safety, but also the stability of mud particles tiny in tailing can be facilitated, to the place of the mud particles Setting is a main Environmental Problems.The problem related with caustic alkali is used being discussed above can seriously affect bitumen recovery efficiency and Quality.

Canadian Patent 2004352, which is disclosed using kerosene and methyl-isobutyl methanol, to be solved and in extracting pitch Using the related above problem of caustic alkali, however, the demand to a large amount of chemicals substantially increases operating cost and makes coal The use of oil and methyl-isobutyl methanol is forbidden.

Canadian Patent 1022098 is disclosed one kind and is adjusted to lotion pH about by using inorganic salts and carbon dioxide 7.0 destroy the pitch-aqueous emulsion method generated in caustic alkali extraction process.However, carbon dioxide is not strong acid, therefore not It is effective pH depressant.On the other hand, unwanted salt can be generated in process water using inorganic acid, and can seriously limit The recycling of process water processed.

USP 4,357,230 is disclosed extracts pitch object using amide with preferred minimum rate 1: 2 from shale or sand Matter, and can carry out at ambient temperature and pressure.Preferred amide includes having connected linear chain or branched chain aliphatic The two of group replace sour amide.

USP 5,169,518 discloses the ex situ from Tar sands and recycles pitch, wherein being improved by using alkanolamine Flotation.The specific example of applicable alkanolamine includes monoethanolamine, diethanol amine and triethanolamine, isopropanolamine, butanolamine With hexanol amine and its mixture.

Canadian patent application 2,640,448, which is disclosed by adding lipid into ore-water slurry, to be enhanced from oil-sand The method of middle recycling pitch.

USP 7,938,183, which is disclosed using the ammonia of low dosage (1% or lower) form and aliphatic amine, enhances original position Bitumen recovery rate in production method.

USP 8,272,442 discloses the various additives with turpentine oil solvent combination.These classifications include lower aliphatic Race's alcohol, lower paraffin hydrocarbon, rudimentary aromatic compound, aliphatic amine, aromatic amine, carbon disulfide, vegetable oil and its mixture.

There is still a need for effective, safe and cost-effective methods to recycle from the oil-sand in the extraction operation of surface to improve Pitch, and injected by hot water or steam to improve the efficiency and productivity of pitch in produced in situ.

Summary of the invention

The present invention is a kind of improved bitumen recovery process, it includes oil-sand is handled with aromatic amine, wherein described Processing is carried out to the oil-sand exploited by earth's surface or progress produced in situ recycles in subsurface reservoir.

In one embodiment of bitumen recovery process described above, aromatic amine with flowering structure by being described:

R¹R²R³N

Wherein R¹And R²It is independently-H ,-AL, wherein-AL is unsubstituted C₁To C₂₀, preferably C₁To C₆Alkyl；C₆To C₁₂ The C that aromatic series replaces₁To C₂₀, preferably C₁To C₆Alkyl or combinations thereof, wherein-AL can contain one or more-COOR⁴, wherein R⁴ For-H, alkyl, aryl or alkaryl, CN ,-CHO ,-NR⁵R⁶Group, wherein R⁵And R⁶It is independently-H, alkyl or aryl ,-OH Group ,-O- group ,-S- group ,-N- group ,-Cl ,-Br ,-F or R¹And R²Unsubstituted or substituted imines can be formed, or Person R¹And R²The saturation or unsaturated cyclic part of 5 to 7 atoms can be formed, wherein there may be one or more carbon atoms, Oxygen atom, nitrogen-atoms or sulphur atom

And

R³For-H or-AR, wherein-AR is unsubstituted C₁To C₂₀, preferably C₁To C₆Alkyl；Unsubstituted C₆To C₁₄Fragrance Race's group；Or by one or more C₆To C₁₄The C that aromatic group replaces₁To C₂₀, preferably C₁To C₆Alkyl；Or by one or more A C₁To C₂₀, preferably C₁To C₆Alkyl-substituted C₆To C₁₄Aromatic group；Or by one or more C₁To C₂₀, preferably C₁To C₆ Alkyl and/or one or more C₆To C₁₄The C that aromatic group replaces₆To C₁₄Aromatic group, wherein-AR can contain one Or multiple-COOR⁴, wherein R⁴It is-H, alkyl, aryl or alkaryl, CN ,-CHO ,-NR⁵R⁶Group, wherein R⁵And R⁶Independently It is-H, alkyl or aryl ,-OH group ,-O- group ,-S- group ,-N- group ,-Cl ,-Br ,-F or R¹、R²And R³It can be formed The saturation of 5 to 7 atoms or unsaturated cyclic part, wherein there may be one or more carbon atoms, oxygen atom, nitrogen-atoms or Sulphur atom.

Preferably, aromatic amine 2,4,6- trimethylanilines, N- benzyl -2- phenyl ethylamine, N- butyl benzylamine, dibenzylamine, 2- Aminobphenyl, aminodiphenylmethane, aniline, 2- phenoxybenzamine, 9,10- diamino phenanthrene, 1- amino-2-methyl naphthalene, N, N- Bis- (salicylidene) ethylenediamines, N- phenyl-o-phenylenediamine, 2,4,6- tri-tert aniline, N-phenylglycine, the tertiary fourth of 3,5- bis- Base aniline, -1,1 '-dinaphthalene -2,2 '-diamines, 4 '-amino benzo -15- are preced with 5- ether, Alpha-Methyl benzylamine, 4- (dimethylamino) benzene Acetic acid, N- benzyl-ethylenediamine, N- Methylphenethylamine, 1,2- diphenyl ethylene diamine, triphenyl amine, N- phenylethylenediamine, pyridine, Toluidines, anisidine, methylaniline, diphenylamine, the halogen substituents of aromatic amine, indoles, indoline, quinoline, 1- amino- 4- alkyl amino benzene, Isosorbide-5-Nitrae-diaminobenzene, imidazoles, benzimidazole, benzotriazole, pyrroles, 4-dimethylaminopyridine or it is mixed Close object.

It in another embodiment of the present invention, include following step using the bitumen recovery process of earth's surface described above exploitation Rapid: i) earth's surface exploits oil-sand；Ii the aqueous slurry of oil-sand) is prepared；Iii) aqueous slurry is handled with aromatic amine；Iv) agitation treatment Aqueous slurry afterwards, v) by treated after agitation, aqueous slurry is transferred in separating tank；And vi) by pitch and containing water section Separation, it is preferable that aromatic amine is by based on the weight of oil-sand, the amount of 0.01 to 10 weight % is present in aqueous slurry.

It in another embodiment of the present invention, include following step using the bitumen recovery process of produced in situ described above It is rapid: i) by the way that underground oil-sand reservoir will be handled in the hot water containing aromatic amine and/or steam injection well；And ii) returned from well Receive pitch, it is preferable that the concentration of the aromatic amine in steam is in the amount of 100ppm to 10 weight %.

Specific embodiment

Pitch is separated from oil-sand and/or heavy oil is completed through but not limited to two methods: earth's surface exploitation or in situ time It receives (sometimes referred to as well production).Oil-sand can be recycled by earth's surface or strip mining transformation and be transported to processing region.Can article " Solve bitumen extraction (the Understanding Water-Based Bitumen based on water of Athabasca oil-sand Extraction from Athabasca Oil Sands) ", J.Masliyah et al., " Canadian chemical engineering magazine (Canadian Journal of Chemical Engineering) ", volume 82, one is obtained in Augusts, 2004 well It summarizes.It include: extraction, foam processing, tailings glass and upgrading via the basic step that earth's surface exploits recycling pitch.The step Suddenly it is mutually related；Extraction operation will affect extraction, and in turn, and extraction will affect updating operation.

In general, exploiting oil-sand using truck and spades in opencut in the operation of business bitumen recovery.By the oil of exploitation Sand is transported to processing region.Extraction step includes: to crush oil-sand block and by it in mixing tank, stirred tank, ring type feeder or rotation Turn to be mixed to form the oil-sand slurry through adjusting with (recirculating process) water in crusher.Oil-sand slurry through adjusting is introduced into water In power conveyance conduit or rotating cylinder, wherein oil-sand block is sheared and size reduces.In rotating cylinder and/or Hydraulic transportation pipeline, drip Blueness is recycled from sand grains or " release " or " releasing ".Chemical addition agent can be added during stock preparation stage；For affiliated The example of chemicals known to field, referring to US 2008/0139418, which is incorporated herein by reference in its entirety.In allusion quotation In the operation of type, slurry temperature is operated at 35 DEG C to 75 DEG C, within the scope of preferably 40 DEG C to 55 DEG C.

In roller and Hydraulic transportation pipeline, entrainment or the bubble introduced are attached to pitch, generate foam.In foam processing In step, inflation pitch is floated and is then skimmed from slurry.This step is completed in large-scale gravity separation vessel, the appearance Device is commonly referred to as primary separation container (primary separation vessel, PSV), separative unit (pond Sep) or first fraction From pond (primary separation cell, PSC).It is recycled using the air flotation of introducing in mechanical flotation pond and tailing oil Remaining a small amount of asphalt liquid droplets (usually unaerated in slurry is further recycled in container or ring type separator and hydrocyclone Pitch).In general, total bitumen recovery rate in commercial operation is about the 88 to 95% of original oil in situ.Recycling is in foam The pitch of form usually contains 60% pitch, 30% water and 10% solid.

Then the asphalt foam recycled like this is deaerated, and with solvent dilution (mixing) to provide foot between water and pitch Enough density contrasts simultaneously reduce asphalt viscosity.Facilitated by the dilution of solvent (such as naphtha or hexane) using inclined plate sedimentation Device, cyclone and/or centrifuge remove solid and water from asphalt foam.When with the use of the ratio between sufficiently high diluent and pitch When paraffinic diluent (solvent), partly precipitated occurs for asphaltene.This results in complex aggregates, captures institute's cut-back asphalt Water and solid in foam.In this way, Gravity Separation greatly enhances, it may not be necessary to cyclone or centrifuge.

In tailings glass step, the tailing stream from extract equipment, which enters in tailing pit, to be separated by solid-liquid separation.After purification Water extract equipment is recycled to from pond.In order to accelerate tailings glass, gypsum can be added into mature thin tailing, by particulate Non- separating mixture is consolidated together into coarse sand.This method is known as consolidating (compound) tailing (CT) technique.CT with promote its into The geotechnological mode that one step is dehydrated and finally recycles is disposed.Optionally, eddy flow is carried out to the tailing from extract equipment, wherein will overflow Stream (thin tailing) is pumped into thickener and eddy flow underflow (thick tailing) is pumped into tailing pit.At thin tailing flocculant Reason, then thickens and is pumped into tailing pit.In addition, using paste technology (addition flocculant/polyelectrolyte) or CT and paste The combination of technology can be used for quick release water and the water in CT be recycled to extract equipment to recycle pitch from oil-sand.

In a final step, the pitch of recycling is upgraded.Upgrading can add hydrogen, or removal carbon, to obtain more Balance light hydrocarbon that is valuable and being easier to refining.Upgrading process also removes pollutant, such as heavy metal, salt, oxygen, nitrogen And sulphur.Upgrading process includes one or more steps, such as: distillation, and many of compound is separated by physical characteristic；It is burnt Change；Hydro-conversion；Improve the solvent deasphalting of the ratio between hydrogen and carbon；And the hydrotreating of removal pollutant (such as sulphur).

In one embodiment of the invention, the improvements that the method for pitch is recycled from oil-sand are to prepare rank in slurry Aromatic amine is added during section.Pulp substance is added in slurry tank under agitation, and is merged with aromatic amine.Aromatic amine can be pure Net form, or with by the total weight of fragrant amine aqueous solution, fragrant amine concentration is the aqueous solution shape of 100ppm to 10 weight % Formula is added in oil-sand slurry.Preferably, aromatic amine is by based on the weight of oil-sand, the amount of 0.01 to 10 weight % is present in aqueous In oil-sand slurry.

In one embodiment of the method for the present invention, aromatic amine is added without organic solvent, such as aromatic organic solvent, such as Toluene, dimethylbenzene, benzene etc. or non-aromatic organic solvent, such as alkane (such as C₁To C₁₂Alkane) and alkene (such as C₁To C₁₂Alkylidene Hydrocarbon).Suitable organic solvent includes but is not limited to ethyl alcohol, propyl alcohol, isopropanol, butanol, pentane, heptane, hexane, benzene, diformazan Benzene, tetrahydronaphthalene, carbon disulfide, soybean oil, palm oil, rapeseed oil, corn oil, sunflower oil, rapeseed oil and its mixture.

Preferred fragrance amine of the invention is expressed from the next:

R¹R²R³N

And

Preferred aromatic amine is 2,4,6- trimethylanilines, N- benzyl -2- phenyl ethylamine, N- butyl benzylamine, dibenzylamine, 2- ammonia Base biphenyl, aminodiphenylmethane, aniline, 2- phenoxybenzamine, 9,10- diamino phenanthrene, 1- amino-2-methyl naphthalene, N, N- are bis- (salicylidene) ethylenediamine, N- phenyl-o-phenylenediamine, 2,4,6- tri-tert aniline, N-phenylglycine, 3,5- di-t-butyl Aniline, -1,1 '-dinaphthalene -2,2 '-diamines, 4 '-amino benzo -15- are preced with 5- ether, Alpha-Methyl benzylamine, 4- (dimethylamino) benzene second Acid, N- benzyl-ethylenediamine, N- Methylphenethylamine, 1,2- diphenyl ethylene diamine, triphenyl amine, N- phenylethylenediamine, pyridine, first Aniline, anisidine, methylaniline, diphenylamine, the halogen substituents of aromatic amine, indoles, indoline, quinoline, 1- amino -4- Alkyl amino benzene, Isosorbide-5-Nitrae-diaminobenzene, imidazoles, benzimidazole, benzotriazole, pyrroles, 4-dimethylaminopyridine or its mixing Object.

Usually by fragrant amine aqueous solution/oil-sand slurry agitation 5 minutes to 4 hours, preferably 1 hour or shorter.Preferably, fragrant Amine aqueous solution oil-sand slurry is heated to equal to or higher than 35 DEG C, more preferably equal to or above 40 DEG C, more preferably equal to or above 55 DEG C, More preferably equal to or above 60 DEG C.Preferably, fragrant amine aqueous solution oil sand slurry material is heated to be equal to or less than 100 DEG C, more preferably etc. In or be lower than 80 DEG C, and more preferably equal to or less than 75 DEG C.

As outlined above, the slurry handled through aromatic amine can be transferred to the separation for generally comprising dilute cleaning agent solution Slot, pitch and heavy oil are partially separated with aqueous in the separating tank.Solid can be further processed and appointed containing water section with removing What additional free matter matter.

In another embodiment of the present invention, pitch is recycled from oil-sand by well production, wherein as described above Aromatic amine can and too deep to position cannot opencast oil sand deposit carry out in-situ treatment to be added in oil-sand.It is former The most popular method of position production recycling is hot water injection, steam soak (CSS) and steam assisted gravity drainage (SAGD).CSS can To utilize both vertical well and horizontal well, the well is alternately injecting into steam and heated pitch is pumped into earth's surface, shape At the circulation of injection, heating, flowing and extraction.SAGD utilizes pairs of horizontal well, is placed in a well in pitch oil-producing area Above another well.Top well generates permanent heat room, the heated pitch in the permanent heat room for injecting steam It flows by gravitational force into the lower well for extracting pitch.However, new technique, as vapor recovery extracts (vapor recovery Extraction, VAPEX) and heavy oil Sand Production Cold Recovery (cold heavy oil production with sand, CHOPS) is just In research and development.

It include: in hot water and/or steam injection well from the basic step of the in-situ treatment of pitch is recycled in oil-sand；From well Recycle pitch；And, for example, the pitch with condensate dilution recycling, to be transported by pipeline.

According to the method, aromatic amine is used as hot water during the bitumen recovery of underground oil-sand reservoir and/or steam adds Agent.In individual well or more well schemes, the mode of hot water and/or steam injection may include steam drive, steam dipping or period One of steam injection is a variety of.In addition to one of steam method for implanting listed above or it is a variety of other than, can also make Use water flood.

In general, hot water and/or steam are injected in oil-sand reservoir by injection well, and wherein comprising reservoir and injection fluid Formation fluid by adjacent producing well or injection well returned by reflux produce.

In most of oil-sand reservoirs, at least 150 DEG C to 180 DEG C of water temperature is needed to keep pitch mobile.

In most of oil-sand reservoirs, need at least 180 DEG C (its pressure for corresponding to 150psi (1.0MPa)) or higher Vapor (steam) temperature keep the pitch mobile.Preferably, aromatic amine-steam injection stream is at 150 DEG C to 300 DEG C, and preferably 180 DEG C to 260 It is introduced into reservoir at a temperature of DEG C.It is special that specific vapor (steam) temperature used in the method for the present invention and pressure will depend on particular reservoir Property, it will be formulated for each reservoir such as depth, overburden pressure, oil-producing area thickness and asphalt viscosity, and therefore.

It is preferred that aromatic amine and hot water and/or steam are injected simultaneously, to ensure or maximize the practical virtue mobile with steam The amount of fragrant amine.In certain circumstances, it may be necessary to inject only steam injection stream before or after steam-aromatic amine injection stream. In this case, 260 DEG C can be risen above in only steam injection period vapor (steam) temperature.The term as used herein " steam " Mean to include superheated steam, saturated vapor and the steam less than 100% mass.

For clarity, term " less than the steam of 100% mass " refers to that there are the steam of liquid water phase.Quality of steam is fixed Justice is the weight percent of the dry saturated steam contained in the Unit Weight of vapour-linquid mixure." saturated vapor " and " 100% matter The synonymous use of the steam of amount "." superheated steam " is the steam having been heated to higher than vapor-liquid balance point.If used Hot steam, then preferably making steam superheating to higher than between 5 to 50 DEG C of vapor-liquid balance temperature before adding aromatic amine.

Aromatic amine can be pure form or be added in hot water and/or steam with concentration form.If with concentrate Form addition, then it can be added in the form of 1 to 99 weight % aqueous solution.

Aromatic amine is preferably intermittently or continuously injected with hot water and/or steam, so that hot water/steam-aromatic amine note It becomes a mandarin and down-hole formation is reached by common pipe.Aromatic amine adding rate is adjusted, to maintain 100ppm to 10 weights in steam Measure the preferred fragrant amine concentration of %.For typical oil sands reservoir hot water and/or steam charge velocity can for 1 to 3 foot/ It, so that about enough hot water and/or steam provide the propulsion by stratum.

In one embodiment of the method for the present invention, bitumen recovery rate at any time can be by injecting in the more than one stage Additive improves, such as: different additive (or the allotment injected together with hot water and/or steam (a) is used in different phase Object), and/or (b) different phase use injected together with hot water and/or steam various concentration same additives (or adjust With object).Other than aromatic amine of the invention, it is pre- in reservoir in the given stage that additive (or composite) can be based on it Enhance the performance of oil extraction in porous media within the scope of the oil saturation of phase to be selected (for example, initial well startup stage High oil saturation and the low oil saturation sandstone of decline stage).If, can using single additive (or composite) To inject oily recovery catalyst together with hot water and/or steam with low concentration, to help the oil recovery under high oil saturation, then It is reduced at any time with the oil saturation in stratum, with the same oil recovery catalyst of higher concentration injection reinforcing.

In one embodiment of the method for the present invention, by the way that total hot water and/or vapor composition injection stage are divided into two A or more stage can improve bitumen recovery rate variation over time, wherein different dense for the selection of each stage The aromatic amine of degree.

Example

Parallel pressure reactor (PPR) test.

For example 1 to 19, about 0.05g aromatic amine, 0.5g oil-sand and 5mL water are put into 12mL vial.Then Bottle is loosely covered, is then heated 45 minutes at 120 DEG C in convection oven.It is then shut off baking oven and keeps sample cooling To room temperature.After cooling, sample is placed in white background and is taken pictures.Example 20 carries out in a similar manner, but aromatic amine is not present.

For example 21-28, mixture is prepared as described above, but is tested under 200 DEG C and 150psi.These reaction conditions It represents and applies the minimum steam condition needed for mobile pitch in oilfield reservoir using steam assisted gravity drainage (SAGD).It will 0.05g aromatic amine is added in 15mL glass insert together with 0.5g oil-sand and 5mL deionization (DI) water, is then shifted simultaneously It is placed in the hole PPR and heats 1 hour.At the end of 1 hour, by sample cooling and take pictures.Example 29 carries out in a similar manner, but There is no aromatic amines.

If the free oil (being higher than liquid level) along the attachment of vial glass wall is higher than baseline, then it is assumed that additive is to pitch Release has positive influence from oil-sand.Observation and ImageJ analysis by visual observation, discharged oil is assessed based on color intensity (that is, higher color intensity means higher pitch burst size).In ImageJ, the image of bottle is initially converted into 32 Position gray level, and measure the color intensity for being higher than water level and be compared with baseline (only water).Color intensity " 0 " has indicated All black, " 255 " indicate white completely.Therefore, compared with baseline, the pitch amount discharged by additive is higher, mean intensity Than lower.

The mean intensity of example 1 to 29 is than as shown in table 1: table 1

It * is not present example

Claims

1. a kind of bitumen recovery process, it includes handling oil-sand with aromatic amine, wherein the processing is to passing through surface The oil-sand that exploitation or produced in situ are recycled carries out.

2. according to the method described in claim 1, wherein the aromatic amine with flowering structure by being described:

R¹R²R³N

Wherein R¹And R²It is independently-H ,-AL, wherein-AL is unsubstituted C₁-C₂₀Alkyl, C₆-C₁₂The C that aromatic series replaces₁-C₂₀ Alkyl or combinations thereof, wherein-AL can contain one or more-COOR⁴, wherein R⁴Be-H, alkyl, aryl or alkaryl, CN ,- CHO、-NR⁵R⁶Group, wherein R⁵And R⁶It is independently H, alkyl or aryl ,-OH group ,-O- group ,-S- group ,-N- base Group ,-Cl ,-Br ,-F or R¹And R²It is capable of forming unsubstituted or substituted imines or R¹And R²It is capable of forming 5 to 7 atoms Saturation or unsaturated cyclic part, wherein can have one or more carbon atoms, oxygen atom, nitrogen-atoms or sulphur atom

And

R³For-H or-AR, wherein-AR is unsubstituted C₁To C₂₀Alkyl；Unsubstituted C₆To C₁₄Aryl；Or it is one or more C₆To C₁₄The C that aromatic group replaces₁To C₂₀Alkyl；Or by one or more C₁To C₂₀Alkyl-substituted C₆To C₁₄Aromatic series base Group；Or by one or more C₁To C₂₀Alkyl and/or one or more C₆To C₁₄The C that aromatic group replaces₆To C₁₄Aromatic series Group, wherein-AR can contain one or more-COOR⁴, wherein R⁴For-H, alkyl, aryl or alkaryl, CN ,-CHO ,- NR⁵R⁶Group, wherein R⁵And R⁶Be independently-H, alkyl or aryl ,-OH group ,-O- group ,-S- group ,-N- group ,- Cl ,-Br ,-F or R¹、R²And R³It is capable of forming the saturation or unsaturated cyclic part of 5 to 7 atoms, wherein can have one Or multiple carbon atoms, oxygen atom, nitrogen-atoms or sulphur atom.

3. bitumen recovery process according to claim 1, is exploited using earth's surface, the method is comprised the steps of:

I) earth's surface exploits oil-sand,

Ii the aqueous slurry of the oil-sand) is prepared,

Iii the aqueous slurry) is handled with the aromatic amine,

Iv) the aqueous slurry after agitation treatment,

V) by treated described in after agitation, aqueous slurry is transferred in separating tank,

With

Vi) pitch is partially separated with aqueous.

4. bitumen recovery process according to claim 3, wherein the aromatic amine is by based on the weight of the oil-sand, 0.01 Amount to 10 weight % is present in the aqueous slurry.

5. bitumen recovery process according to claim 1, utilizes produced in situ, the method is comprised the steps of:

I) by the way that underground oil-sand reservoir will be handled in the hot water for containing the aromatic amine and/or steam injection well,

With

Ii the pitch) is recycled from the well.

6. bitumen recovery process according to claim 5, wherein the concentration of aromatic amine described in the steam is in 100ppm To the amount of 10 weight %.

7. according to the method described in claim 1, wherein amine is selected from 2,4,6- trimethylanilines, N- benzyl -2- phenyl ethylamine, N- fourth Base benzylamine, dibenzylamine, 2- aminobphenyl, aminodiphenylmethane, aniline, 2- phenoxybenzamine, 9,10- diamino phenanthrene, 1- ammonia Base -2- methyl naphthalene, N, bis- (salicylidene) ethylenediamines of N-, N- phenyl-o-phenylenediamine, 2,4,6- tri-tert aniline, N- phenyl Glycine, 3,5- di-tert-butyl aniline, -1,1 '-dinaphthalene -2,2 '-diamines, 4 '-amino benzo -15- are preced with 5- ether, Alpha-Methyl benzyl Amine, 4- (dimethylamino) phenylacetic acid, N- benzyl-ethylenediamine, N- Methylphenethylamine, 1,2- diphenyl ethylene diamine, triphenyl amine, N- phenylethylenediamine, pyridine, toluidines, anisidine, methylaniline, diphenylamine, the halogen substituents of aromatic amine, indoles, two Hydrogen indoles, quinoline, 1- amino-4-alkylamino benzene, Isosorbide-5-Nitrae-diaminobenzene, imidazoles, benzimidazole, benzotriazole, pyrroles or 4- Dimethyl aminopyridine.