阅读说明：本技术 包含烷氧基化醇的注入流体和该流体在采油过程中的用途 (Injection fluid comprising alkoxylated alcohol and use of the fluid in oil recovery processes ) 是由 R·罗默斯基兴 T·索托曼 H·比尔吉利 J·菲舍尔 于 2020-02-18 设计创作，主要内容包括：本发明涉及一种包含液态二氧化碳或超临界二氧化碳(CO-2)和烷氧基化醇的注入流体和这种流体在采油过程中的用途。更具体地,本发明涉及在CO-2注入采油过程中通过使用烷氧基化醇来降低混相压力。此外,本发明涉及注入CO-2和烷氧基化醇的采油过程。(The invention relates to a process for the preparation of a composition comprising liquid carbon dioxide or supercritical carbon dioxide (CO) 2 ) And an alkoxylated alcohol injection fluid and the use of such a fluid in an oil recovery process. More particularly, the invention relates to the CO 2 The miscible pressure is reduced by using an alkoxylated alcohol during injection oil recovery. Furthermore, the invention relates to CO injection 2 And oil recovery processes for alkoxylated alcohols.)

1. an injection fluid for recovering a hydrocarbon-containing fluid from a reservoir, the injection fluid comprising at least

-liquid carbon dioxide or supercritical carbon dioxide, and

-one or more alkoxylated alcohols having the structure:

R-O-(AO)_m+n-H (I)

wherein

R is a straight chain alkyl group having C4 to C9 carbon atoms, and/or a branched chain alkyl group having C4 to C18 carbon atoms;

AO is Ethoxy (EO) and/or Propoxy (PO), in any order and independently of one another, m or n, respectively;

m is 0 to 12;

n is 0 to 12;

m + n is at least 1;

and is

The miscible pressure between the injection fluid and the hydrocarbon-containing fluid is preferably reduced by at least 4.9%, more preferably by at least 8.2%, most preferably by at least 16.3% compared to the miscible pressure between the hydrocarbon-containing fluid and carbon dioxide alone;

and/or

The injection fluid preferably increases the expansion coefficient of the hydrocarbon-containing fluid by at least 4% compared to the expansion coefficient of a hydrocarbon-containing fluid comprising only carbon dioxide.

2. The injection fluid of claim 1, wherein

R-O-(A’O)_m-(A”O)_n-H (I)

Wherein

m is 1 to 12;

n is 1 to 12;

a 'O is Ethoxy (EO) and A' O is Propoxy (PO), or

A 'O is Propoxy (PO) and A' O is Ethoxy (EO); and is

Preferably, A' O is Ethoxy (EO) and A "O is Propoxy (PO).

3. Injection fluid according to any one of claims 1 and 2, wherein

m is 1 to 8; and is

n is 1 to 8.

4. Injection fluid according to claims 1, 2 and 3, wherein R is a linear C4 to C9 alkyl group, preferably a linear C4 to C8 alkyl group.

5. Injection fluid according to any one of claims 1 to 4, wherein R is a branched alkyl group having 4 to 18 carbon atoms, preferably 8 to 14 carbon atoms.

6. Injection fluid according to any one of claims 1, 4 and 5, wherein AO is EO.

7. Injection fluid according to any one of claims 1, 4 and 5, wherein AO is PO.

8. Injection fluid according to any one of claims 1 to 7, wherein m + n is 1 to 8, preferably m + n is 1 to 6.

9. Injection fluid according to any one of claims 1 to 8, wherein the alkoxylated alcohol is added to the carbon dioxide in a range of 0.1 to 10.0 wt.%, preferably 0.1 to 2.0 wt.%, each relative to the weight of the carbon dioxide.

10. A method of modifying an oil well by carbon dioxide injection, the method comprising

i) Injecting the injection fluid of any of the preceding claims into a reservoir comprising a hydrocarbon-containing fluid,

wherein

The miscible pressure between the injection fluid and the hydrocarbon-containing fluid is preferably reduced by at least 4.9%, more preferably by at least 8.2%, most preferably by at least 16.3% compared to the miscible pressure between the hydrocarbon-containing fluid and carbon dioxide alone; and/or

The injection fluid preferably increases the expansion coefficient of the hydrocarbon-containing fluid by at least 4% compared to the expansion coefficient of the hydrocarbon-containing fluid comprising only carbon dioxide;

ii) recovering a hydrocarbon-containing fluid from the reservoir.

11. The method of claim 10, wherein

a) The injection fluid comprises less than 1 wt% water, preferably no water; or

b) The injection fluid consists solely of the components defined in any one of claims 1 to 9, optionally further comprising a linear C4 to C9 alcohol or an optional branched alcohol having 4 to 18 carbon atoms or both.

12. Use of one or more alkoxylated alcohols having the structure:

R-O-(AO)_m+n-H (I)

wherein

R is a straight chain alkyl group having C4 to C9 carbon atoms, and/or a branched chain alkyl group having C4 to C18 carbon atoms;

AO is EO and/or PO, independently of one another m or n, respectively;

m is 0 to 12;

n is 0 to 12; and is

m + n is at least 1;

the injection fluid is used to recover a hydrocarbon-containing fluid from a reservoir; and is

The miscible pressure between the injection fluid and the hydrocarbon-containing fluid is preferably reduced by at least 4.9%, more preferably by at least 8.2%, most preferably by at least 16.3% compared to the miscible pressure between the hydrocarbon-containing fluid and carbon dioxide alone; and/or

The injection fluid preferably increases the expansion coefficient of the hydrocarbon-containing fluid by at least 4% compared to the expansion coefficient of a hydrocarbon-containing fluid comprising only carbon dioxide.

13. Use according to claim 12, wherein the alkoxylated alcohol has the structure

R-O--(A’O)_m-(A”O)_n--H (II)

Wherein

m is 1 to 12;

n is 1 to 12;

a 'O is Ethoxy (EO) and A' O is Propoxy (PO); or

A 'O is Propoxy (PO) and A' O is Ethoxy (EO);

and is

Preferably, A' O is Ethoxy (EO) and A "O is Propoxy (PO).

14. Use according to any one of claims 12 or 13, wherein

m is 1 to 8; and is

n is 1 to 8.

15. Use according to any one of claims 12 to 14, wherein the injection fluid increases the expansion coefficient of the hydrocarbon-containing fluid by at least 6% compared to the expansion coefficient between the hydrocarbon-containing fluid and pure carbon dioxide.

16. Use according to any one of claims 12 to 15, wherein R is a linear C4 to C9 alkyl group, preferably a linear C4 to C8 alkyl group.

17. Use according to any one of claims 12 to 16, wherein R is a branched alkyl group having 4 to 18 carbon atoms, preferably a branched alkyl group having 8 to 14 carbon atoms.

18. Use according to any one of claims 12, 15 to 17, wherein AO is EO.

19. Use according to any one of claims 12, 15 to 17, wherein AO is PO.

20. Use according to any one of claims 12 to 19, wherein m + n is 1 to 8, preferably m + n is 1 to 6.

21. Use according to any one of claims 12 to 20, wherein the hydrocarbon-containing fluid is crude oil and the reservoir is a well.

Technical Field

The invention relates to a process for the preparation of a liquid or supercritical carbon dioxide (CO)₂) And an alkoxylated alcohol injection fluid and the use of such a fluid in an oil recovery process. More particularly, the invention relates to the CO₂The miscible pressure is reduced by using an alkoxylated alcohol during injection oil recovery. The invention also relates to CO injection₂And oil recovery processes for alkoxylated alcohols.

Background

Using CO₂Flooding has two main effects-firstly swelling the crude oil and secondly reducing the viscosity of the crude oil. Thereby achieving increased mobility and more efficient scanning of the formation. For successful flooding, the interaction between the crude oil and the injection fluid is the determining factor. In order for the crude oil to pass through the rock pores, it must be associated with injected CO₂Mixing is carried out. The difference in miscible behavior defines the flooding scenario that occurs under defined reservoir conditions. It is closely related to the crude oil composition. The lighter part of the crude oil is evaporated to CO₂Phase, and generates balanced CO-rich₂And (4) phase(s). At the same time, by condensing CO to crude oil₂The heavier portion of the crude oil is extracted, thereby forming a transition zone. At constant temperature and pressure, the miscible behavior can be visualized using a ternary phase diagram.

Fig. 1a shows primary contact miscible (FCM). The crude oil composition, denoted "Petroleum A", is closer to the lighter component (C1-6) side. For "oil A" and CO₂In each composition of the mixture of (1), there is a single phase (1) which is completely mixed. From pure CO₂The initial injection path bypasses the miscibility gap (grey zone 2) which defines the separation into two phases (CO-rich)₂Evaporation phase and petroleum-rich condensate extract phase).

In FIG. 1b, the reaction is carried out from pure CO₂The injection path to the oil composition "oil B" passes through the miscibility gap. Thus, a separation process occurs that produces the transition region as described above.

Each separation process produces a new equilibrium rich CO₂The composition of the injection phase and the new petroleum-rich extract phase will gradually approach until complete miscibility is achieved. This Multiple Contact Miscible (MCM) flooding is possible for crude oils where the injection path passes through the miscibility gap, but still has a hydrocarbon composition on the right side of the critical connecting line (near C1-6), which is defined by the critical point (cp) of the miscibility gap.

In FIG. 1C, the crude oil designated "Petroleum C" contains a high proportion of heavier components (C7 +). The composition of which is located to the left of the critical connection line. Thus, for each newly generated CO-rich₂Phase from pure CO₂The initial injection path always passes through the miscibility gap and each point of the injection path is separated. The result is an immiscible process in which only the hydrocarbons of the formed transition zone are recoverable, while the crude oil is not CO-contaminated₂The extracted heavier fraction remains in the formation. Complete miscibility will not be achieved.

In addition to the crude oil composition, pressure also has an effect on the miscible behaviour. The range of the miscibility gap shrinks with increasing pressure. Therefore, the critical point (cp) and its critical connecting line are oriented towards the CO of the triangular phase diagram₂the/C7 + side moves. This is schematically shown in fig. 2. After the critical connection line passes through the composition "oil C" (fig. 2b), the previous immiscible process (fig. 2a) will convert to MCM-type flooding. Further increase in pressure causes the miscibility gap to be small enough that it no longer affects the injection path, and the process becomes FCM (fig. 2 c).

In view of the above, it is apparent that CO₂The efficiency and economy of flooding is closely related to the pressure that needs to be applied when injecting carbon dioxide. The Minimum Miscible Pressure (MMP) defines the minimum pressure that must be applied to inject the carbon dioxide fluid to achieve the miscible MCM process. For more efficient FCM flooding, the injection pressure must be above the physical Minimum Miscible Pressure (MMP)_P). Formation fracture pressure, on the other hand, limits injection pressure. Thus, MMP_PMust be below the formation fracture pressure so that there is CO₂Can be implemented at any ratio with crude oilAnd (3) completely miscible FCM flooding. Thus, lowering the miscible pressure allows CO to be produced₂Injection Enhanced Oil Recovery (EOR) is suitable for previously immiscible reservoirs. FIG. 3 shows improved CO₂Schematic representation of the miscible behaviour of a crude oil system.

Increase of CO₂Miscibility with crude oil has more than one beneficial effect. With the same amount of injected carbon dioxide, CO increases with oil recovery₂The utilization rate is increased. Furthermore, if MMP_PBelow the reservoir pressure itself, it is the most economically advantageous process. In addition, as injection pressure increases, operating costs also increase. Thus, for miscible or near miscible reservoirs, low MMP_PMore economic benefits are brought.

Using CO₂Another important factor in the recovery of crude oil is the swelling behavior of residual oil trapped in the formation. At low pressure, CO₂Has condensed to the liquid petroleum phase, causing the petroleum phase to expand. As the volume of the expanded petroleum phase increases, it is subsequently squeezed out of the tight rock pores of the formation rock trapping the petroleum. At the same time, the viscosity of the oil is reduced, which enables it to flow better through the reservoir, even in low permeability zones. In CO₂Near the critical pressure of (a) and below MMP, the oil has already begun to swell. As the pressure increases, the extraction process begins to dominate. This is the supercritical CO that is subsequently produced from the crude oil components₂(scCO₂) Is caused by evaporation in (1). Increasing migration of crude oil to scCO₂Phase until in MMP_PComplete miscibility is achieved and only one homogeneous phase exists. By recording the volume of excess petroleum phase, the swelling and extraction can be easily measured visually. The coefficient of expansion (SF) describes the efficiency of the expansion effect of a given system, i.e. involving the same composition at a constant temperature. The calculation method is the volume of the petroleum phase (V) under the pressure of maximum expansion_oil) Initial volume of petroleum phase at ambient pressure (V)⁰ _oil) The ratio of (A) to (B):

so-called CO formed in the reservoir₂Foam (which is understood to be CO)₂Dispersion in water (with internal CO)₂Phase may be gaseous, liquid or supercritical)) have previously been applied for enhanced oil recovery. The use of surfactants (particularly optimized to produce foam) provides CO with higher viscosity₂Fluid is injected so that better flow control can be achieved. According to WO 2010/044818A 1, due to crude oil and CO₂And its different viscosity, CO₂The foam helps to inject CO₂Transferred to an unserviced area previously bypassed in the formation. Typically, these foams are used even without the addition of the surfactant CO₂Also during miscible injection. In this type of application, the selection of the non-ionic surfactant is specifically optimized, as described in WO 2013/048860A 1, to form CO by the addition of water₂And (3) foaming. Purpose of non-ionic surfactant is CO generation₂Foaming (rather than improving CO)₂And miscibility between crude oils, which are already miscible).

The alkoxylated alcohol of the present invention is not intended to produce CO₂Foam, but for use in reservoirs operating at pressures lower than MMP. These types of conditions result in a majority of crude oil with CO₂Is immiscible. In the past, for these types of situations, CO₂EOR applications are considered uneconomical and in most cases impractical. The invention aims to make these reservoirs applicable to CO₂EOR, in particular, by selecting the claimed additives from the alkoxylated alcohol class to reduce MMP, brings the pressure-dependent miscible behavior into a range in which successful operation can be achieved under miscible conditions (FCM or MCM) (see fig. 3).

As a result, the miscible pressure is reduced, resulting in a higher expansion coefficient of the hydrocarbon-containing fluid (crude) by the injected fluid, thereby increasing the recovery of crude from the reservoir.

The Mobil Oil patent (US 4899817) previously reported that miscible pressures could be reduced by the addition of C1-C8 alcohols. In another study "Reduction of MMP use in organic chemistry" (International Journal of Chemical and Molecular Engineering, Vol.8, No. 4, 2014, p.351-. The study included ALFOL 1214, ISOFOL 12, ISOFOL 16, ISOFOL 28, LIAL 123, LIAL 167, and MARLIPAL O13. However, no clear trend was observed by the authors.

Chinese patent application CN 1046109530A also describes the use of alkoxylates for reducing the miscible pressure. The authors showed that by adding to CO₂The addition of linear C10-18 alkoxylated alcohol and its analog alkylphenol derivatives can significantly reduce the miscible pressure. However, according to this reference, co-solvents (typically C1-C5 carbon chain alcohols) are mandatory.

Disclosure of Invention

Objects of the invention

The object of the invention is to use CO₂CO enhancement during oil recovery by injection₂Miscibility with crude oil, thereby reducing miscible pressure and reducing crude oil viscosity.

Another object of the present invention is to provide a process for the preparation of CO₂The expansion behavior of the crude oil is improved, in particular the expansion of the crude oil is increased, during the injection of oil.

Description of the invention

In the following, an injection fluid according to the present invention is described that may be used for recovering a hydrocarbon-containing fluid from a reservoir. These fluids have been found to be very effective in expanding the crude oil and subsequently lowering the miscible pressure, even at high reservoir temperatures. This results in increased mobility of the crude oil and enables efficient scanning of the formation.

The injection fluid according to the invention, which provides improved miscible pressure, improved expansion coefficient or both, comprises liquid CO₂Or supercritical CO₂And at least one alkoxylated alcohol having a molecular structure as shown in Structure I

R-O-(AO)_m+n-H (I)

Wherein

R is a linear alkyl group having C4 to C9 carbon atoms and/or a branched alkyl group having C4 to C18 carbon atoms;

AO is Ethoxy (EO) and/or Propoxy (PO) wherein m and n may be the same or different, AO may be different for each m or n, and EO and PO may be, for example

-randomly distributed, or

-one or more blocks of EO bonded to one or more blocks of PO;

m is 0 to 12;

n is 0 to 12;

m+n≥1，

and the improved miscible pressure, the improved expansion coefficient, or both are further defined as follows:

-the miscible pressure between the injection fluid and the hydrocarbon-containing fluid is preferably reduced by at least 4.9%, more preferably by at least 8.2%, most preferably by at least 16.3% compared to the miscible pressure between the hydrocarbon-containing fluid and carbon dioxide alone;

the injection fluid preferably increases the expansion coefficient of the hydrocarbon-containing fluid by at least 4% compared to the expansion coefficient between the hydrocarbon-containing fluid and carbon dioxide alone.

Preference is given to block structures as shown in Structure II

R-O-(A’O)_m-(A”O)_n-H (II)

Wherein

A 'O is Ethoxy (EO) and A' O is Propoxy (PO); or

A 'O is Propoxy (PO) and A' O is Ethoxy (EO);

r, m, n and m + n have the same meanings as described above.

(AO) of structure (I) if one EO block and one PO block are present_m+nCan be described as- (A' O)_m-(A”O)_n-. Depending on whether the EO block precedes or the PO block precedes, structure (II) can be described as structures (IIa) and (IIb):

R-O-(EO)_m-(PO)_n-H (IIa)

or

R-O-(PO)_m-(EO)_n-H (IIb)

The injection fluid may comprise a mixture of alkoxylated alcohols of structure (I) or (II), or a mixture of alkoxylated alcohols of structure (IIa) or (IIb).

According to one embodiment, R is a linear C4 to C9 alkyl group, preferably a linear C4 to C8 alkyl group.

According to another embodiment, R is a branched alkyl group having from 4 to 18 carbon atoms, in particular a branched alkyl group having from 8 to 14 carbon atoms. The branch may be located at the 2-position (R group of 2-alkyl branch).

The alkoxylated alcohol may comprise only EO groups (according to one embodiment, n ═ 0 for structure (IIa) or only PO groups (according to one embodiment, m ═ 0 for structure (IIa)). In alkoxylates comprising an EO block and a PO block, the PO block is preferably located in an end position (see structure (IIa)).

The degree of alkoxylation (m + n) is preferably from 1 to 8, in particular from 2 to 6.

The amount of the above alkoxylated alcohol in the injected fluid is preferably in the range of 0.1 to 10.0 wt%, preferably 0.1 to 2.0 wt%, each relative to the weight of carbon dioxide.

The method according to the invention comprises injecting a fluid into an oil well, thereby passing a CO comprising at least as additive an alkoxylated alcohol as defined above₂To profile and drive the well.

Also claimed is the use of an alkoxylated alcohol as described above in an injection fluid comprising liquid carbon dioxide or supercritical carbon dioxide for recovering a hydrocarbon-containing fluid from a reservoir. The hydrocarbon-containing fluid is preferably crude oil and the reservoir is preferably an oil well.

After addition of the alkoxylated alcohol, the alkoxylated alcohol is reacted with CO in comparison to the coefficient of expansion without addition of the alkoxylated alcohol₂Together preferably increase the expansion coefficient of the hydrocarbon-containing fluid by at least 4%. The hydrocarbon-containing fluid is preferably crude oil and the reservoir is preferably an oil well.

The injection fluid according to an embodiment may also comprise a linear C4 to C9 alcohol, preferably a linear C4 to C8 alcohol. According to another embodiment, the injection fluid comprises a branched alcohol having 4 to 18 carbon atoms, in particular 8 to 14 carbon atoms. The alcohol may have a chain length and structure corresponding to the R group of the alkoxylate contained in the injected fluid.

According to one embodiment of the invention, the injection fluid consists of CO₂And an alkoxylated alcohol, optionally a linear C4 to C9 alcohol, and optionally a branched alcohol having 4 to 18 carbon atoms, each as defined above.

According to one embodiment of the invention, the injection fluid as defined herein comprises less than 1 wt% water, preferably no water.

Detailed Description

Suitable alcohols that may be used in the synthesis of the alkoxylated alcohols described above include, but are not limited to, linear alcohols (e.g., butanol, linear C6 and C8 alcohols (e.g., NACOL 6 and NACOL 8)), branched alcohols (e.g., 2-ethylhexanol, isononyl alcohol, 2-alkyl-1-alkanols (guerbet alcohols, e.g., ISOFOL 12, ISOFOL 16), and isotridecyl alcohol (e.g., MARLIPAL O13, a C13 oxo alcohol)). All examples, represented by trade names, are sold by Sasol Performance Chemicals. The alkoxylated alcohol is generally added to the CO in a percentage of 0.1% to 10.0% by weight, preferably 0.1% to 2.0% by weight₂In (1). The above alcohol then forms the group R of structure (I), (II), (IIa) or (IIb) as defined above.

Drawings

The invention is further illustrated with reference to the accompanying drawings:

FIG. 1: CO at constant pressure and temperature₂Schematic diagram of triangular phase diagram in oil displacement process. The crude oil composition may be expressed as a blend of the heavier component (C7+) and the lighter component (C1-6). According to the proportion of the oil in crude oil, the oil displacement process is

a) A first contact miscible phase (FCM),

b) multiple Contact Miscible (MCM), or

c) Immiscible phases.

For crude oils containing a large amount of lighter components, the injection path leads to FCM (petroleum a) or MCM (petroleum B) processes. If the crude oil composition contains a higher proportion of heavier components, then for each new CO-rich₂Injecting the phase, the injection path will always pass through the miscibility gap, and each of the injection pathsThe points will separate. Miscible phases (oil C) are never reached.

FIG. 2: schematic of a triangular phase diagram with increasing pressure at constant temperature. Starting from the immiscible process (a, compare also fig. 1C), when the critical connecting line crosses the composition of oil C (b), increasing the pressure leads to smaller miscibility gap and MCM type process. Further increase in pressure will shift the process to FCM condition (c).

FIG. 3: system CO₂Schematic diagram of miscibility gap of crude oil illustrating addition of additives to miscibility gap and MMP_PThe influence of (c).

FIG. 4: CO at 65 ℃ and 75 ℃₂The miscibility gap with three kinds of petroleum.

FIG. 5: for CO without additives at 65 deg.C₂And in CO₂With 2 wt% of C6P3 or 2 wt% of ITDAE2, respectively, the coefficient of expansion at pressure of system aco 38.0.0 was increased.

Detailed Description

Experimental part

A readily available method was applied to demonstrate the efficiency of a fluid at a constant temperature to reduce the mixed phase pressure. Physical Minimum Miscible Pressure (MMP) unlike MMP_P) Is crude oil and CO₂Pressure at which the mixture is completely miscible in any ratio. The flooding under these conditions is FCM as described above. MMP can be determined using a visual pressure cell_P. MMP based on prior completions_PComparison with MMP (i.e., G.C. Wang, "Determination of Miscibility Pressure-Direct Observation Method", 1 month 1984, written by contract number DE-AC21-81MC 16140, US DOE, university of Alabama, Tascala Lusa, Alabama, and "Determination of Minimum Miscibility Pressure Using a High-Pressure Visual Sapphire Cell" of S.Hagen and C.A. Kossack, US DOE, U.S. DOE, university of Alabama, Tascala Lusa, and SPE/DOE 14927, 1986), the authors hypothesized that MMP was targeted_PThe same effects found apply to MMPs, and MMPs_PThe decrease in MMP is a strong sign of decrease.

Experiments were performed using a pressure-resistant visual observation cell equipped with a sapphire cylinder. The temperature was controlled using a water bath and the pressure was adjusted by a piston. Samples of the specified composition were loaded into the cell, all components were added by weight, and homogenized using a magnetic stir bar. Miscibility was then monitored at various temperatures over a typical reservoir pressure range. To ensure the presence of fully miscible conditions, it was visually verified that a homogeneous mixture was present and no excess phase was formed.

This procedure enables a simple screening of the pressure and temperature dependence of miscibility of each sample. In this way the additive pair CO was investigated₂And the miscible behaviour of petroleum. In addition, by recording the coexisting petroleum phase and CO-rich₂The volume of the phase, determines the swelling behaviour.

Three petroleum oils were used to demonstrate the performance of the alkoxylated alcohols according to the invention to reduce the miscible pressure during the recovery of petroleum from a reservoir:

two of the petroleums are synthetic model petroleums comprising paraffinic, naphthenic, aromatic structures and wax compounds (mco 47.0.0 and mco 38.8.8). In addition, crude oil (aco 38.0.0) was included to study the performance of the displacement fluid. Characterization of oil using API scale:

i) API of synthetic model oil mco 47.0.0 is 47.0 °. It is a paraffinic petroleum oil comprising about 41 wt% paraffins, 8 wt% aromatics, 21 wt% naphthenes, and 30 wt% waxes.

ii) API of second syncrude mco 38.8.8 ═ 38.8 °. It consisted of 16 wt% paraffin, 34 wt% aromatics, 20 wt% naphthenes and 30 wt% wax.

iii) crude oil aco 38.0.0 is asian petroleum with API 38.0 °. From the available analytical data it is known that it contains almost no asphaltenes (only 0.03%) and 7.6% wax. The remainder consists mainly of saturated hydrocarbons. Table 1 shows the composition.

TABLE 1

Synthetic petroleum mco 47.0.0 (more paraffinic), mco 38.8.8 (more aromatic), and aco 38.0.0 (asian crude).

	mco47.0	mco38.8	aco38.0
				Alkane hydrocarbons	41	16
Aromatic hydrocarbons	8	34	9
				Cycloalkanes	21	20
Wax	30	30	7
				Resin composition			12
Saturated hydrocarbons			67
				Asphaltenes			<0.05
Others			6

As can be seen from fig. 4, all three petrols showed enlarged miscibility gaps. The miscibility gap is CO-rich with increasing temperature from 65 ℃ to 75 ℃₂The side shifts to lower pressure and the side shifts to higher pressure at the oil rich side. Its shape remains almost unchanged. The shapes of the miscibility gap for the synthetic model oil and the crude oil are very similar, indicating that the synthetic oil accurately mimics the crude oil. Due to the rich CO in the mixture₂The highest pressure required to have complete miscibility (i.e., MMP) was recorded_P) The effect of the additives was therefore investigated at a petroleum proportion of 7.5% by weight in the mixture.

Table 2 shows petroleum and pure CO at a petroleum ratio of 7.5% by weight₂Miscible pressure (provided as absolute pressure) (i.e. maximum value of pseudo-binary miscibility gap):

table 2:

the fluid additives used herein are the alkoxylated alcohols listed in table 7. Alkoxylation is performed by reacting the selected alcohol with at least one alkylene oxide in the presence of a catalyst, which may be, but is not limited to, a base (e.g., KOH) or a Double Metal Cyanide (DMC) catalyst. For example, "Kinetics and mechanisms of fat alcohol hydrolysis.1. the interaction catalyzed by fat alcohol hydroxide" in e.santachearia, m.di series, r.garaffa and g.addino; typical synthesis methods for base-catalyzed alkoxylation are described in Ind. Eng. chem. Res.1992, 31(11), 2413-2418. "Chemistry and Technology of Polyols for Polyurethanes" in US3278457 and Mihai Ionescu; a process for alkoxylation using DMC Catalysts is described in Smithers Rapra Publishing, 2005, 2 nd edition, volume 1, page 177-196 (Chapter 5: Synthesis of High-Molecular Weight polyethylene with Double Metal Catalysts).

As shown in tables 4 and 5 (comparative examples), the alcohol alkoxylates clearly show a better reduction of the miscible pressure compared to the corresponding alcohols.

In order to demonstrate the improvement of the present application with respect to prior art CN 1046109530A, in which the addition of a solvent (C1-C5 alcohol) is mandatory and a linear alkoxylated alcohol C10-18+0-12EO +2-10PO is described, the compounds of the present invention are compared with CN 1046109530A under the same conditions in table 6.

As can be seen from the data shown below, the claimed alkoxylated alcohol is superior to the fluid claimed in CN 1046109530A.

The swelling behaviour was determined by visual observation. The sample was equilibrated at constant pressure and temperature in a pressure-resistant sapphire cuvette until the phases were completely separated. The volume of the bottom petroleum phase was then recorded. The coefficient of expansion SF is determined as the ratio of this volume to the initial volume of the petroleum phase at this temperature and ambient pressure (SF ═ V)_oil/V⁰ _oil)。

At 65 ℃ a system aco 38.0.0 comprising 25% by weight aco 38.0.0 and CO was recorded in the absence of additives and in the presence of 2% by weight of C6P3 and ITDAE2, respectively₂Coefficient of expansion as pressure increases.

Table 3:

in CO₂Swelling behaviour with additives:

pure CO2	+2％ITDAE2	+2％C6P3
			32％	38.5％	39％

It is clear that the addition of the additives described in the present invention leads to an increase in the expansion coefficient. Crude oil should exhibit an increase in the expansion coefficient of at least 4%. The expansion coefficients of the two above examples are increased by 6.5% to 7.0% -this is CO₂A very beneficial improvement in the injection recovery process.

Table 4: miscible pressures of displacement fluids and different petroleum oils and pressure reduction at different temperatures compared to systems without alcohol alkoxylates

Table 5:

table 6:

table 7: the compounds used were:

table 7 (above): the compounds used were: