Chemical agent composition containing sorbitan polyether carboxylate, preparation method thereof and CO reduction method thereof2Method for driving out minimum miscible pressure
阅读说明：本技术 含失水山梨醇聚醚羧酸酯的化学剂组合物及其制法和其降低co2驱最小混相压力的方法 (Chemical agent composition containing sorbitan polyether carboxylate, preparation method thereof and CO reduction method thereof2Method for driving out minimum miscible pressure ) 是由 吴春芳 李应成 何秀娟 李斌 于 2020-07-01 设计创作，主要内容包括：本发明涉及一种含失水山梨醇聚醚羧酸酯的化学剂组合物及其制法和其降低CO-(2)驱最小混相压力的方法,主要解决国内大多数油藏CO-(2)与原油最小混相压力高,无法实现CO-(2)混相驱而导致驱油效率低的问题。所述化学剂组合物包含如式(I)所示的失水山梨醇聚醚羧酸酯和如式(II)所示的助剂。所述化学剂组合物直接溶于超临界CO-(2)中注入地层,在地层条件下与CO-(2)、原油作用,降低两者的最小混相压力。本发明的技术方案不仅能帮助CO-(2)非混相驱油藏实现混相驱油,提高驱油采收率,还能解决低渗透和特低渗透油藏化学剂的注入问题。(The invention relates to a chemical agent composition containing sorbitan polyether carboxylate, a preparation method thereof and CO reduction of the chemical agent composition 2 The method for driving minimum miscible pressure mainly solves most of domestic oil deposit CO 2 The minimum mixed phase pressure with the crude oil is high, and CO can not be realized 2 The problem of low oil displacement efficiency caused by miscible flooding. The chemical agent composition comprises sorbitan polyether carboxylate shown as a formula (I) and an auxiliary agent shown as a formula (II). The chemical agent composition is directly dissolved in supercritical CO 2 Injected into the formation with CO at formation conditions 2 And the crude oil acts to reduce the minimum miscible pressure of the two. The inventionThe technical scheme can not only help CO 2 The immiscible oil displacement reservoir realizes miscible oil displacement, improves the oil displacement recovery ratio and can solve the injection problem of chemical agents of low-permeability and ultra-low-permeability oil reservoirs.)
1. A chemical agent composition containing sorbitan polyether carboxylate comprises sorbitan polyether carboxylate and auxiliary agent,
wherein the sorbitan polyether carboxylate is selected from at least one of the structures shown in the formula (I):
in the formula (I), R 'and R' are independently selected from (CH)2)eH and e are any integer of 0-4; x is the number of1、x2、x3、x4Is the number of polyether groups with substituents R1、y2、y3、y4Is the number of polyether groups with substituents R', z1、z2、z3、z4The number of polyether groups with substituent R' ″; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any number of 0 to 50, and x1+x2+x3+x4+y1+y2+y3+y4+z1+z2+z3+z4>0；M1，M2，M3，M4Independently selected from hydrogen atoms or compounds of formula- (C ═ O) -R1And M is1，M2，M3，M4Not being hydrogen atoms at the same time; r1Is selected from C6～C50A hydrocarbyl or substituted hydrocarbyl group of (a);
the auxiliary agent is selected from at least one of structures shown in a formula (II):
in the formula (II), R2Is selected from C1～C50A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from (CH)2)jH, j is any integer of 0-4; a. b and c are respectively a substituent R3、R4、R5The number of polyether groups of (a) is independently selected from any integer of 0-50, and a + b + c>0; y is selected from hydrogen atom or general formula- (C ═ O) R6One of the groups; r6Is selected from C6～C50A hydrocarbyl or substituted hydrocarbyl group of (a).
2. The chemical composition containing sorbitan polyether carboxylate as set forth in claim 1 wherein:
r ', R ' and R ' are independently selected from (CH)2)eH and e are any integer of 0-4, and R ', R ' and R ' are not simultaneouslyIs a hydrogen atom; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any integer of 0 to 50, and x1+x2+x3+x4>0，y1+y2+y3+y4>0，z1+z2+z3+z4>0；R1Is selected from C6～C50A hydrocarbyl or substituted hydrocarbyl group of (a); and/or the presence of a gas in the gas,
R2is selected from C1～C50A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from (CH)2)jH, j is any integer of 0-4; a. b and c are independently selected from any integer of 0-50, and a + b + c>0；R6Is selected from C6～C50A hydrocarbyl or substituted hydrocarbyl group of (a).
3. The chemical composition containing sorbitan polyether carboxylate as set forth in claim 2 wherein:
the R ', R ' and R ' are independently selected from hydrogen atoms, methyl or ethyl and are not hydrogen atoms at the same time; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any number of 0 to 35, and x1+x2+x3+x4>0，y1+y2+y3+y4>0，z1+z2+z3+z4>0；R1Is selected from C8～C40A hydrocarbyl or substituted hydrocarbyl group of (a); and/or the presence of a gas in the gas,
R2is selected from C5～C40A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from hydrogen atom, methyl or ethyl; a. b and c are independently selected from any integer of 0-30, and a + b + c>0；R6Is selected from C8～C40A hydrocarbyl or substituted hydrocarbyl group of (a).
4. The chemical composition containing sorbitan polyether carboxylate as set forth in claim 3 wherein:
x1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4independently selected from any integer of 0 to 25, and x1+x2+x3+x4>0，y1+y2+y3+y4>0，z1+z2+z3+z4>0；R1Is independently selected from C8～C25A hydrocarbyl or substituted hydrocarbyl group of (a); and/or the presence of a gas in the gas,
R2is selected from C8～C30A hydrocarbyl or substituted hydrocarbyl group of (a); a. b and c are independently selected from any number of 0-25, and a + b + c>0；R6Is selected from C8～C25A hydrocarbyl or substituted hydrocarbyl group of (a).
5. The chemical composition containing sorbitan polyether carboxylate as set forth in claim 1 wherein:
r ', R ' and R ' are independently selected from (CH)2)eH, e is any integer of 0-4, and R ', R ' and R ' at least comprise two different groups; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any number of 0 to 35, and x1+x2+x3+x4>0，y1+y2+y3+y4>0，z1+z2+z3+z4>0；R1Is independently selected from C8～C30A hydrocarbyl or substituted hydrocarbyl group of (a); and/or the presence of a gas in the gas,
R2is selected from C8～C30A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from (CH)2)jH, j is any integer of 0-2; a. b and c are independently selected from any integer of 0-35, and a + b + c>0；R6Is selected from C8～C30A hydrocarbyl or substituted hydrocarbyl group of (a).
6. The chemical composition containing sorbitan polyether carboxylate as set forth in claim 5 wherein:
the R ', R ", R'" are independently selected from a hydrogen atom, a methyl group or an ethyl group, and R ', R ", R'" comprise at least two different groups; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any integer of 0 to 25, and x1+x2+x3+x4>0，y1+y2+y3+y4>0，z1+z2+z3+z4>0；R1Is independently selected from C8～C25A hydrocarbyl or substituted hydrocarbyl group of (a); and/or the presence of a gas in the gas,
R2is selected from C8～C25A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from (CH)2)jH, j is any integer of 0-2; a. b and c are independently selected from any integer of 0-25, and a + b + c>0；R6Is selected from C8～C25A hydrocarbyl or substituted hydrocarbyl group of (a).
7. Chemical composition comprising sorbitan polyether carboxylate according to any one of claims 1 to 6, wherein:
the mol ratio of the sorbitan polyether carboxylate to the auxiliary agent is 1: (0.005 to 50), preferably 1: (0.01 to 30), more preferably 1: (0.1-10).
8. A method for preparing a chemical composition containing sorbitan polyether carboxylate according to any one of claims 1 to 7, comprising the steps of:
mixing sorbitan polyether carboxylate and an auxiliary agent.
9. The method for preparing a chemical composition according to claim 8, wherein:
the sorbitan polyether carboxylate is prepared by the following steps,
heating sorbitol and a dehydrating agent A for dehydrating and etherifying to obtain dehydrated sorbitol;
reacting sorbitan with an epoxy compound in the presence of a catalyst B to obtain a sorbitan polyether compound;
③ in the presence of a catalyst C, the sorbitan polyether compound obtained in the step II and R1And performing condensation reaction on COOH to obtain the sorbitan polyether carboxylate.
10. The method for preparing a chemical composition according to claim 9, wherein:
the first step is that the reaction temperature is 140-180 ℃; the dehydrating agent A is P2O5At least one of p-toluenesulfonic acid and phosphoric acid, wherein the amount of the dehydrating agent is preferably 0.5-2 wt% of the mass of sorbitol; the epoxy compound is at least one of ethylene oxide, propylene oxide and butylene oxide; and/or the presence of a gas in the gas,
secondly, the reaction temperature is 100-140 ℃; the catalyst B is at least one of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, and the dosage of the catalyst B is preferably 0.5-5 wt% of the mass of the sorbitan; and/or the presence of a gas in the gas,
thirdly, the reaction temperature is 180-220 ℃; the catalyst C is at least one of sodium bicarbonate and potassium bicarbonate, and the dosage of the catalyst C is preferably 0.5-3 wt% of the mass of the sorbitan polyether compound.
11. Reduce CO2A method for driving out the minimum miscible pressure, comprising mixing the chemical composition containing sorbitan polyether carboxylate as claimed in any one of claims 1 to 7 with liquid or supercritical CO2Mixed and injected together into the formation.
12. CO reduction according to claim 112A method of driving out a minimum miscible pressure, characterized by:
the chemical agent composition is used in an amount of CO at injection pressure20.1-5% by mass, preferably 0.5-3% by mass; and/or the presence of a gas in the gas,
the oil reservoir temperature is 40-180 ℃, and the injection temperature is 0-100 ℃.
Technical Field
The invention relates to the field of petroleum exploitation, in particular to a chemical agent composition containing sorbitan polyether carboxylate, a preparation method thereof and CO reduction of the chemical agent composition2Method for driving minimum miscible pressure.
Background
CO2The supercritical state is reached at a temperature above 31.26 ℃ and a pressure above 7.2 MPa. Supercritical CO2Has good dissolving capacity to crude oil, and is an ideal displacement medium. Thus, CO2The oil displacement technology plays a key role in the exploitation of crude oil, particularly the exploitation of low-permeability oil reservoirs. According to the American Oil&Journal of Gas Journal statistics, us CO 20142The oil displacement exceeds the steam displacement first-place, accounts for 43.1 percent of the total oil production of the American EOR, and improves the recovery rate by 7 to 20 percent. According to the results of 'second potential evaluation of enhanced oil recovery and development strategy research of developed oil field on land in China', the number of the evaluated 1.01 is multiplied by 1010In geological reserves, is suitable for CO2The gas flooding crude oil reserves are about 1.28X 109t, predicted utilization of CO2The oil displacement technology can increase the recoverable reserve by about 1.60 multiplied by 108t. For the proven 6.32 multiplied by 10 in China9t low permeability reservoir crude oil reserves, especially 50% unexplored reserves, CO2The oil displacement technology has great application prospect.
Since the last 90 s, with the increasing proportion of extra-low permeability reservoir reserves, domestic CO is added2The growing attention is paid to CO2The capture and purification technology makes a major breakthrough, which enables the oil field to obtain CO2The cost of the method is greatly reduced, and the method is suitable for the vigorous development of CO2The conditions are created. However, most of domestic oil fields have high oil deposit temperature and heavy oil in crude oilHigh content of components, CO2The minimum miscible pressure is generally higher. CO 22There are two ways for non-miscible flooding reservoirs to achieve miscible flooding. One approach is to raise the formation pressure above the minimum miscible pressure by water or gas injection. The second is to lower the minimum miscible pressure below the virgin formation pressure. The first approach is not applicable to reservoirs with formation fracture pressures below the minimum miscible pressure. Moreover, the water injection method has poor operability for low-permeability and ultra-low-permeability reservoirs, and the gas injection method has high cost and poor effect. Therefore, it is currently accepted that the minimum miscible pressure is reduced by injecting chemicals2The important way of realizing miscible flooding of the non-miscible flooding reservoir.
Since the 80 s of the 20 th century, Mobil oil company (U.S. Pat. No. 5, 4678036; U.S. Pat. No. 3, 4899817; U.S. Pat. No. 3, 4736793) successively disclosed the reduction of CO by using chemicals such as liquefied petroleum gas, low molecular weight aliphatic hydrocarbons, lower alcohols and tall oil2Minimum miscible pressure with crude oil. The chemical agents can effectively promote the crude oil and CO2The method achieves the miscible phase, but the method needs a large amount of use to obtain an ideal miscible phase pressure reduction effect, has low economic benefit and is difficult to popularize and apply. Moreover, the flash points of liquefied petroleum gas, low molecular weight alkanes and low carbon alcohols are all very low, and great potential safety hazards are generated in the processes of storage, transportation and use.
In recent years, domestic researchers have proposed the use of surfactants to reduce CO2Minimum miscible pressure with crude oil. An oil-soluble surfactant of citrate esters was invented by Fischery, Guo et al (Adv Mater Res (Durnten-Zurich, Switzerland) 2011,239; Petrol.Sci.Technol.2017,35(4),345.) of the oil university in southwest. The surfactant has obvious viscosity reduction effect on crude oil and oil-water emulsion, and can effectively reduce CO2The interfacial tension with the crude oil, thereby reducing the minimum miscible pressure between the two. However, the manner of injection has a great influence on the effect of such oil-soluble surfactants. The surfactant is injected in a slug mode, so that the minimum miscible pressure can be obviously reduced and the CO can be obviously improved2Displacing and recovering oil; surfactant and CO2Co-injection mode for reducing mixed phase pressure amplitude limitation and improving miningThe yield amplitude is very small. However, direct slug injection of surfactants into the reservoir can result in severe adsorption losses. Therefore, the oil-soluble surfactant and the injection method thereof are difficult to popularize and apply.
Disclosure of Invention
One of the technical problems to be solved by the invention is to reduce CO2The minimum miscible pressure chemical (such as liquefied petroleum gas and low molecular weight aliphatic hydrocarbon) is used in large amount, low economic benefit, low flash point and high safety risk, and the existing surfactant and CO are used2The problems of poor effect of co-injection, large absorption loss of slug injection and the like, and provides a chemical agent composition containing sorbitan polyether carboxylate. The chemical agent composition has CO2Is amphiphilic with crude oil, and can efficiently promote CO2The oil and the crude oil are mixed to reduce the minimum mixed phase pressure of the oil and the crude oil. It also has high flash point, good safety, and can be used in supercritical CO2Good solubility, and convenient transportation, storage and injection into oil field.
The second technical problem to be solved by the present invention is to provide a method for reducing CO corresponding to the first technical problem2Method for driving minimum miscible pressure.
In order to solve one of the above technical problems, it is an object of the present invention to provide a chemical composition containing sorbitan polyether carboxylate, comprising sorbitan polyether carboxylate and an auxiliary,
wherein the sorbitan polyether carboxylate is selected from at least one of the structures shown in the formula (I):
in the formula (I), R 'and R' are independently selected from (CH)2)eH and e are any integer of 0-4; x is the number of1、x2、x3、x4Is the number of polyether groups with substituents R1、y2、y3、y4Is the number of polyether groups with substituents R', z1、z2、z3、z4The number of polyether groups with substituent R' ″; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any integer of 0 to 50, and x1+x2+x3+x4+y1+y2+y3+y4+z1+z2+z3+z4>0；M1，M2，M3，M4Independently selected from hydrogen atoms or compounds of formula- (C ═ O) -R1And M is1，M2，M3，M4Not being hydrogen atoms at the same time; r1Is independently selected from C6～C50A hydrocarbyl or substituted hydrocarbyl group of (a).
The auxiliary agent is selected from at least one of structures shown in a formula (II):
in the formula (II), R2Is selected from C1～C50A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from (CH)2)jH, j is any integer of 0-4; a. b and c are respectively a substituent R3、R4、R5The number of polyether groups of (a) is independently selected from any integer of 0-50, and a + b + c>0; y is selected from hydrogen atom or general formula- (C ═ O) R6One of the groups; r6Is selected from C6～C50A hydrocarbyl or substituted hydrocarbyl group of (a).
In one embodiment of the present invention, preferably, R ', R ", R'" are independently selected from (CH)2)eH, e is any integer of 0-4, and R ', R ' and R ' are not hydrogen atoms at the same time; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any integer of 0-50,and x1+x2+x3+x4>0，y1+y2+y3+y4>0，z1+z2+z3+z4>0；M1，M2，M3，M4Independently selected from hydrogen atoms or compounds of formula- (C ═ O) -R1And M is1，M2，M3，M4Not being hydrogen atoms at the same time; r1Is independently selected from C6～C50A hydrocarbyl or substituted hydrocarbyl group of (a); r2Is selected from C1～C50A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from (CH)2)jH, j is any integer of 0-4; a. b and c are independently selected from any integer of 0-50, and a + b + c>0; y is selected from hydrogen atom or general formula- (C ═ O) R6One of the groups; r6Is selected from C6～C50A hydrocarbyl or substituted hydrocarbyl group of (a);
in the above technical solution, more preferably, R ', R ", R'" are independently selected from a hydrogen atom, a methyl group or an ethyl group, and are not simultaneously a hydrogen atom; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any integer of 0 to 35, and x1+x2+x3+x4>0，y1+y2+y3+y4>0，z1+z2+z3+z4>0；M1，M2，M3，M4Independently selected from hydrogen atoms or compounds of formula- (C ═ O) -R1And M is1，M2，M3，M4Not being hydrogen atoms at the same time; r1Is independently selected from C8～C40A hydrocarbyl or substituted hydrocarbyl group of (a); r2Is selected from C5～C40A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from hydrogen atom, methyl or ethyl; a. b and c are independently selected from any integer of 0-30, and a + b + c>0; y is selected from hydrogen atom or general formula- (C ═ O) R6One of the groups; r6Is selected from C8～C40A hydrocarbyl or substituted hydrocarbyl group of (a);
in the above technical solution, most preferably, R ', R ", R'" are independently selected from a hydrogen atom, a methyl group or an ethyl group, and are not simultaneously hydrogen atoms; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any integer of 0 to 25, and x1+x2+x3+x4>0，y1+y2+y3+y4>0，z1+z2+z3+z4>0；M1，M2，M3，M4Independently selected from hydrogen atoms or compounds of formula- (C ═ O) -R1And M is1，M2，M3，M4Not being hydrogen atoms at the same time; r1Is independently selected from C8～C25A hydrocarbyl or substituted hydrocarbyl group of (a); r2Is selected from C8～C30A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from hydrogen atom, methyl or ethyl; a. b and c are independently selected from any integer of 0-25, and a + b + c>0; y is selected from hydrogen atom or general formula- (C ═ O) R6One of the groups; r6Is selected from C8～C25A hydrocarbyl or substituted hydrocarbyl group of (a).
In another embodiment of the present invention, preferably, the R ', R ", R'" are independently selected from (CH)2)eH, e is any integer of 0-4, and R ', R ' and R ' at least comprise two different groups; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any integer of 0 to 35, and x1+x2+x3+x4>0，y1+y2+y3+y4>0，z1+z2+z3+z4>0；M1，M2，M3，M4Independently selected from hydrogen atoms or compounds of formula- (C ═ O) -R1And M is1，M2，M3，M4Not being hydrogen atoms at the same time; r1Is independently selected from C8～C30A hydrocarbyl or substituted hydrocarbyl group of (a); r2Is selected from C8～C30A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from (CH)2)jH, j is any integer of 0-2; a. b and c are independently selected from any integer of 0-35, and a + b + c>0; y is selected from hydrogen atom or general formula- (C ═ O) R6One of the groups; r6Is selected from C8～C30A hydrocarbyl or substituted hydrocarbyl group of (a);
more preferably, R ', R ", R'" are independently selected from hydrogen, methyl or ethyl, and R ', R ", R'" comprise at least two different groups; x is the number of1、x2、x3、x4、y1、y2、y3、y4、z1、z2、z3、z4Independently selected from any integer of 0 to 25, and x1+x2+x3+x4>0，y1+y2+y3+y4>0，z1+z2+z3+z4>0；M1，M2，M3，M4Independently selected from hydrogen atoms or compounds of formula- (C ═ O) -R1And M is1，M2，M3，M4Not being hydrogen atoms at the same time; r1Is independently selected from C8～C25A hydrocarbyl or substituted hydrocarbyl group of (a); r2Is selected from C8～C25A hydrocarbyl or substituted hydrocarbyl group of (a); r3、R4、R5Independently selected from (CH)2)jH, j is any integer of 0-2; a. b and c are independently selected from any integer of 0-25, and a + b + c>0; y is selected from hydrogen atom or general formula- (C ═ O) R6One of the groups; r6Is selected from C8～C25A hydrocarbyl or substituted hydrocarbyl group of (a).
In the technical scheme, the molar ratio of the sorbitan polyether carboxylate to the auxiliary agent is 1: (0.005 to 50), preferably 1: (0.01 to 30), more preferably 1: (0.1-10).
The invention also aims to provide a preparation method of the chemical agent composition containing the sorbitan polyether carboxylate, which comprises the following steps: mixing sorbitan polyether carboxylate and an auxiliary agent.
Preferably, the chemical agent composition containing the sorbitan polyether carboxylate is obtained by mixing and stirring the sorbitan polyether carboxylate and the auxiliary agent according to the required molar ratio.
In the technical scheme, the sorbitan polyether carboxylate and the auxiliary agent can be prepared by a common method in the prior art.
According to a preferred embodiment of the present invention, the method for preparing the chemical agent composition containing sorbitan polyether carboxylate according to the present invention may comprise the following steps:
(a) preparation of sorbitan polyether carboxylate:
heating sorbitol and a dehydrating agent A for dehydrating and etherifying to obtain dehydrated sorbitol;
reacting sorbitan with an epoxy compound in the presence of a catalyst B to obtain a sorbitan polyether compound;
③ in the presence of a catalyst C, the sorbitan polyether compound obtained in the step II and R1COOH is subjected to condensation reaction to obtain the sorbitan polyether carboxylate with the structure shown in the formula (I).
(b) Preparation of an auxiliary agent:
in the presence of a catalyst D, reacting R2OH reacts with a required amount of epoxy compound to obtain a polyether compound, namely a compound structure shown as a formula (II) and Y is a hydrogen atom;
furthermore, the auxiliary agent can also comprise a step II,
② in the presence of catalyst E, the polyether compound obtained in the step I and a certain proportion of R6COOH to obtain a compound represented by formula (II) wherein Y is- (C ═ O) R6The compound structure of the group;
(c) preparation of chemical agent composition containing sorbitan polyether carboxylate:
in the technical scheme, the reaction temperature in the first step of the step (a) is preferably 140-180 ℃, and the dehydrating agent A is preferably P2O5At least one of p-toluenesulfonic acid and phosphoric acid, wherein the amount of the dehydrating agent is preferably 0.5-2% of the mass of sorbitol; the epoxy compound is preferably at least one of ethylene oxide, propylene oxide and butylene oxide;
in the second step of the step (a), the preferable range of the reaction temperature is 100-140 ℃, the catalyst B is preferably at least one of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, and the dosage of the catalyst B is preferably 0.5-5% of the mass of the sorbitan;
the reaction temperature in the third step of the step (a) is preferably 180-220 ℃, the catalyst C is preferably at least one of sodium bicarbonate and potassium bicarbonate, and the dosage of the catalyst C is preferably 0.5-3 wt% of the mass of the sorbitan polyether compound;
the reaction temperature in the first step of the step (b) is preferably within the range of 100-140 ℃, the catalyst D is preferably at least one of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, and the dosage of the catalyst D is preferably R20.5-5% of the weight of OH;
in the second step (b), the reaction temperature is preferably 180-220 ℃, the catalyst E is preferably at least one of sodium bicarbonate and potassium bicarbonate, and the dosage of the catalyst E is preferably 0.5-3% of the mass of the polyether compound;
the molar ratio range of the sorbitan polyether carboxylate and the auxiliary agent in the step (c) is 1: (0.005 to 50), preferably 1: (0.01 to 30), more preferably 1: (0.1-10), the stirring time is preferably 1-5 hours.
To solve the second problem, the third object of the present invention is to provide a method for reducing CO2The method for driving minimum miscible pressure comprises the step of mixing the chemical agent composition containing the sorbitan polyether carboxylate with liquid or supercritical CO2Mixed and injected into the formation together with CO at formation conditions2Reducing CO by crude oil2Driving the minimum miscible pressure.
In the above technical scheme, the carboxylic ester containing sorbitan polyether is convertedThe chemical composition is dissolved in liquid or supercritical CO2Performing the following steps; the chemical agent composition is preferably used in an amount of CO under injection pressure20.1 to 5% by mass, more preferably 0.5 to 3% by mass;
the method is suitable for the oil reservoir temperature range of 40-180 ℃, and the preferred range is 80-150 ℃; the applicable injection temperature range is 0-100 ℃, preferably 0-75 ℃, and more preferably 25-75 ℃.
The chemical agent composition containing sorbitan polyether carboxylate has a highly branched structure and is reacted with CO2Polyether group and ester group with good affinity, and hydrocarbon chain with good affinity to crude oil, so that it has CO2Crude oil amphiphilicity, CO reduction2Interfacial tension with crude oil. After the sorbitan polyether carboxylate and the auxiliary agent are compounded, the mixture is put into CO2Has good solubility. The chemical agent composition does not contain organic solvents with low boiling points and low flash points, does not need to be dissolved by additional organic solvents, has good safety, and is convenient to transport, store and inject into oil fields.
CO reduction according to the invention2The chemical agent composition containing sorbitan polyether carboxylate can be directly dissolved in liquid or supercritical CO2Is injected into the formation to promote crude oil and CO under formation conditions2Mixing phases and efficiently reducing CO2Driving the minimum miscible pressure. The method has the advantages that the chemical agent has no electric charge and low injection concentration, and the adsorption loss ratio is low.
The technical scheme of the invention can help CO2The immiscible oil displacement reservoir realizes miscible oil displacement, improves the oil displacement recovery ratio and can solve the injection problem of chemical agents of low-permeability and ultra-low-permeability oil reservoirs.
The chemical agent composition and the method for reducing the minimum miscible phase pressure can be used for but not limited to CO with the formation temperature of 40-180 ℃ and the injection temperature of 0-100 DEG C2Driving oil reservoir and helping CO2The non-miscible flooding reservoir realizes miscible flooding and improves CO2And (5) displacing and recovering the oil. By CO at injection pressure2In percentage by mass, 0.1 to 5 percent of chemical is addedAgent for developing CO2+ chemical "flooding experiment. The thin tube experiment shows that after the chemical agent composition is added, CO is generated2The minimum miscible pressure with crude oil is reduced by 27.2 percent at most, and the recovery ratio is pure CO at most2The flooding is improved by 29.22 percent.
Drawings
FIG. 1 is an infrared spectrum of sorbitan polyoxypropylene ether laurate prepared in example 2.
The sorbitan polyether carboxylate prepared by the present invention can be characterized by the following method: performing infrared spectroscopy (scan range 4000-650 cm) by using Nicolet-5700 spectrometer and total reflection infrared spectroscopy (ATR)-1) And determining the chemical structure of the tested sample so as to achieve infrared characterization of the compound.
As can be seen from FIG. 1, the wavenumber is 3455.6cm-1Is characterized by a characteristic absorption peak of terminal O-H at a wave number of 2972.7cm-1、2923.3cm-1、2860.2cm-1Is in the form of-OCH2-and (C-H) characteristic peaks and C-H characteristic absorption peaks of methylene, methyl groups on the alkyl chain; 1741.7cm-1Characteristic absorption peak for ester carbonyl (C ═ O); 1253.3cm-1A characteristic absorption peak of (C-O) which is an ester group; 1091.4cm-1The peak is a characteristic absorption peak of an ether bond (C-O-C).
FIG. 2 is a diagram of a tubule experiment apparatus.
In fig. 2, 1 is a high-pressure plunger pump, 2 is a back-pressure valve, 3 is a receiving bottle, 4 is a buffer bottle, 5 is an HPLC pump, 6 is a high-pressure pump, 7 is a data acquisition system, 8 is an oven, and 9 is a tubule model.
Wherein the high-pressure plunger pump 1 is CO2The injection system, HPLC pump 5 is the chemical agent injection system, high-pressure pump 6 is the oiling system, oven 8 is the temperature control system.
Detailed Description
The present invention is further described with reference to specific examples in order to better understand the invention and to better demonstrate the beneficial effects of the present invention. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the teachings herein.
The starting materials used in the embodiments of the present invention are commercially available.
[ example 1 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 2g P to a reaction kettle2O5And removing oxygen in the reaction flask in vacuum. In N2Heating to 160 ℃ under protection, and reacting for 1.5h to obtain the sorbitan.
② adding 5.6g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle. N is a radical of2Under protection, the system is heated to 120 ℃, 232g (4mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 383.2g of sorbitan polyoxypropylene (n-4) ether, which was obtained in a yield of 96.5%.
③ 198.5g (0.5mol) of sorbitan polyoxypropylene (n-4) ether, 140g (0.7mol) of lauric acid and 2.5g of sodium hydrogen carbonate were added to the dry reaction vessel, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 317.3g of sorbitan polyoxypropylene (n ═ 4) ether lauric acid (m ═ 1.4) ester, yield 97.4%.
(b) Preparation of an auxiliary agent:
(. 1mol) of isomeric tridecanol 200g and 9.2g of potassium carbonate were added to a pressure reactor and the oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 174g (3mol) of propylene oxide is slowly pumped in, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 364.2g of isomeric tridecanol polyoxypropylene (n ═ 3) ether, with a yield of 97.4%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxypropylene (n-4) ether lauric acid (m-1.4) ester prepared in step (a) and the isomeric tridecanol polyoxypropylene (n-3) ether are mixed in a molar ratio of 1: 0.5, and stirring for 3 hours to obtain the chemical agent composition S01 containing the sorbitan polyether carboxylate.
[ example 2 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 2g P to a reaction kettle2O5And removing oxygen in the reaction flask in vacuum. In N2Heating to 160 ℃ under protection, and reacting for 1.5h to obtain the sorbitan.
② adding 5.6g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 120 ℃, 465g (8mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 610.4g of sorbitan polyoxypropylene (n-8) ether, which was obtained in a yield of 97.2%.
③ to a dry reaction kettle, 314g (0.5mol) of sorbitan polyoxypropylene (n-8) ether, 140g (0.7mol) of lauric acid, 2.5g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 423g of sorbitan polyoxypropylene (n ═ 8) ether lauric acid (m ═ 1.4) ester, yield 95.9%.
(b) Preparation of an auxiliary agent:
(. 1mol) of isomeric tridecanol 200g and 9.2g of potassium carbonate were added to a pressure reactor and the oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 174g (3mol) of propylene oxide is slowly pumped in, and the pressure is controlled to be less than or equal to 0.20 MPa. After completion of the reaction, the temperature was lowered to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 341.8g of isomeric tridecanol polyoxypropylene (n ═ 3) ether, with a yield of 96.0%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxypropylene (n-8) ether lauric acid (m-1.4) ester prepared in step (a) and the isomeric tridecanol polyoxypropylene (n-3) ether are mixed in a molar ratio of 1: 1, and stirring for 3 hours to obtain the chemical agent composition S02 containing the sorbitan polyether carboxylate.
[ example 3 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 2g P to a reaction kettle2O5And removing oxygen in the reaction flask in vacuum. In N2Heating to 160 ℃ under protection, and reacting for 1.5h to obtain the sorbitan.
② adding 5.6g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 120 ℃, 465g (8mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 610.4g of sorbitan polyoxypropylene (n-8) ether, which was obtained in a yield of 97.2%.
③ to a dry reaction kettle, 314g (0.5mol) of sorbitan polyoxypropylene (n-8) ether, 280g (1.4mol) of lauric acid, 3.5g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 553.4g of sorbitan polyoxypropylene (n ═ 8) ether lauric acid (m ═ 2.8) ester, yield 97.3%.
(b) Preparation of an auxiliary agent:
first, 200g (1mol) of isomeric tridecanol and 5.6g of potassium hydroxide were charged into a pressure reactor, and oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 174g (3mol) of propylene oxide is slowly pumped in, and the pressure is controlled to be less than or equal to 0.20 MPa. After completion of the reaction, the temperature was lowered to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 341.8g of isomeric tridecanol polyoxypropylene (n ═ 3) ether, with a yield of 96.0%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxypropylene (n-8) ether lauric acid (m-2.8) ester prepared in step (a) and the isomeric tridecanol polyoxypropylene (n-3) ether are mixed in a molar ratio of 1: 2 and stirring for 3 hours to obtain the chemical agent composition S03 containing the sorbitan polyether carboxylate.
[ example 4 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 2g P to a reaction kettle2O5And removing oxygen in the reaction flask in vacuum. In N2Heating to 160 ℃ under protection, and reacting for 1.5h to obtain the sorbitan.
② adding 5.6g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 120 ℃, 465g (8mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 610.4g of sorbitan polyoxypropylene (n-8) ether, which was obtained in a yield of 97.2%.
③ to a dry reaction kettle, 314g (0.5mol) of sorbitan polyoxypropylene (n-8) ether, 140g (0.7mol) of lauric acid, 2.5g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 423g of sorbitan polyoxypropylene (n ═ 8) ether lauric acid (m ═ 1.4) ester, yield 95.9%.
(b) Preparation of an auxiliary agent:
first, 200g (1mol) of isomeric tridecanol and 5.6g of sodium hydroxide were charged into a pressure reactor, and oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 174g (3mol) of propylene oxide is slowly pumped in, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction of the propylene oxide is finished, 132g (3mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 487.8g of isotridecanol polyoxypropylene (n ═ 3) polyoxyethylene (n ═ 3) ether, with a yield of 96.4%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxypropylene (n-8) ether lauric acid (m-1.4) ester prepared in step (a) and the isomeric tridecanol polyoxypropylene (n-3) polyoxyethylene (n-3) ether are reacted in a molar ratio of 1: 1.5, and stirring for 3 hours to obtain the chemical agent composition S04 containing the sorbitan polyether carboxylate.
[ example 5 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 2g P to a reaction kettle2O5And removing oxygen in the reaction flask in vacuum. In N2Heating to 160 ℃ under protection, and reacting for 1.5h to obtain the sorbitan.
② adding 5.6g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 120 ℃, 465g (8mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 610.4g of sorbitan polyoxypropylene (n-8) ether, which was obtained in a yield of 97.2%.
③ to a dry reaction kettle, 314g (0.5mol) of sorbitan polyoxypropylene (n-8) ether, 140g (0.7mol) of lauric acid, 2.5g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 423g of sorbitan polyoxypropylene (n ═ 8) ether lauric acid (m ═ 1.4) ester, yield 95.9%.
(b) Preparation of an auxiliary agent:
262.5g (1mol) of dodecylphenol and 5.6g of sodium hydroxide were added to a pressure reactor and oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 174g (3mol) of propylene oxide is slowly pumped in, and the pressure is controlled to be less than or equal to 0.20 MPa. After completion of the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 416.0g of dodecylphenol polyoxypropylene (n ═ 3) ether, with a yield of 95.3%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxypropylene (n-8) ether lauric acid (m-1.4) ester prepared in step (a) and dodecylphenol polyoxypropylene (n-3) ether are mixed in a molar ratio of 1: 1.2, and stirring for 3 hours to obtain the chemical agent composition S05 containing the sorbitan polyether carboxylate.
[ example 6 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 1g of p-toluenesulfonic acid into a reaction kettle, and removing oxygen in the reaction kettle in vacuum. In N2Heating to 120 ℃ under protection, and reacting for 15min to obtain the sorbitan.
② adding 5.4g of sodium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 120 ℃, 432g (6mol) of butylene oxide is slowly added, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 571g of sorbitan polyoxybutylene (n ═ 6) ether with a yield of 95.6%.
③ to a dry autoclave were added 298.5g (0.5mol) of sorbitan polyoxybutylene (n-6) ether, 282.5g (1mol) of oleic acid, 3g of potassium bicarbonate, and the oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, neutralization and dehydration gave 545g of sorbitan polyoxybutylene (n ═ 6) ether oleic acid (m ═ 2) ester in a yield of 96.8%.
(b) Preparation of an auxiliary agent:
(. 1mol) of lauryl alcohol 186g and 7.0g of potassium carbonate were added to a pressure reactor, and oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 132g (3mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After completion of the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 305g of laureth (n-3) ether in a yield of 95.9%.
② 159g (0.5mol) of polyoxyethylene lauryl (n ═ 3) ether, 72g (0.5mol) of octanoic acid and 2g of potassium hydrogencarbonate were charged into a dry reaction vessel, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 200 ℃ and reacted for 2 h. After cooling, neutralization and dehydration were carried out to obtain 215.5g of laureth octanoate (n ═ 3) in a yield of 97.4%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxybutylene (n ═ 6) ether oleic acid (m ═ 2) ester prepared in the step (a) and polyoxyethylene lauryl (n ═ 3) ether caprylate are mixed in a molar ratio of 1: 3 and stirring for 3 hours to obtain the chemical agent composition S06 containing the sorbitan polyether carboxylate.
[ example 7 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 2g P to a reaction kettle2O5And removing oxygen in the reaction kettle in vacuum. In N2Heating to 160 ℃ under protection, and reacting for 1.5h to obtain the sorbitan.
② adding 5.4g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 110 ℃, 176g (4mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10 MPa. After the reaction of ethylene oxide is finished, the temperature is raised to 120 ℃, 232g (4mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point product was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 558g of sorbitan polyoxyethylene (n ═ 4) polyoxypropylene (n ═ 4) ether, with a yield of 97.3%.
③ to a dry reaction vessel, 286.5g (0.5mol) of sorbitan polyoxyethylene (n-4) polyoxypropylene (n-4) ether, 179.5g (0.7mol) of palmitic acid, 2.5g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 436.2g of sorbitan polyoxyethylene (n ═ 4) polyoxypropylene (n ═ 4) ether palmitic acid (m ═ 1.4) ester in 96.2% yield.
(b) Preparation of an auxiliary agent:
the pressure reactor was charged with 158g (1mol) of isomeric dodecanol and 5.6g of potassium hydroxide and the oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 232g (4mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction was completed, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 375g of isomeric tridecanol polyoxypropylene (n ═ 4) ether, with a yield of 96.1%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxyethylene (n ═ 4) polyoxypropylene (n ═ 4) ether palmitate prepared in step (a) and the isomeric decyl alcohol polyoxypropylene (n ═ 4) ether are mixed in a molar ratio of 1: 1, and stirring for 3 hours to obtain the chemical agent composition S07 containing the sorbitan polyether carboxylate.
[ EXAMPLES 8 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 2g P to a reaction kettle2O5And removing oxygen in the reaction kettle in vacuum. In N2Heating to 160 ℃ under protection, and reacting for 1.5h to obtain the sorbitan.
② adding 5.4g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 110 ℃, 176g (4mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10 MPa. After the reaction of ethylene oxide is finished, the temperature is raised to 120 ℃, 232g (4mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point product was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 558g of sorbitan polyoxyethylene (n ═ 4) polyoxypropylene (n ═ 4) ether, with a yield of 97.3%.
③ to a dry reaction vessel, 286.5g (0.5mol) of sorbitan polyoxyethylene (n-4) polyoxypropylene (n-4) ether, 179.5g (0.7mol) of palmitic acid, 2.5g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 436.2g of sorbitan polyoxyethylene (n ═ 4) polyoxypropylene (n ═ 4) ether palmitic acid (m ═ 1.4) ester in 96.2% yield.
(b) Preparation of an auxiliary agent:
the pressure reactor was charged with 158g (1mol) of isomeric dodecanol and 5.6g of potassium hydroxide and the oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 232g (4mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction was completed, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 375g of isomeric tridecanol polyoxypropylene (n ═ 4) ether, with a yield of 96.1%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxyethylene (n ═ 4) polyoxypropylene (n ═ 4) ether palmitate prepared in step (a) and the isomeric decyl alcohol polyoxypropylene (n ═ 4) ether are mixed in a molar ratio of 1: 10, and stirring for 3 hours to obtain the chemical agent composition S08 containing the sorbitan polyether carboxylate.
[ example 9 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 2g P to a reaction kettle2O5And removing oxygen in the reaction kettle in vacuum. In N2Heating to 160 ℃ under protection, and reacting for 1.5h to obtain the sorbitan.
② adding 5.4g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 110 ℃, 132g (3mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10 MPa. After the reaction of the ethylene oxide is finished, the temperature is raised to 120 ℃, 360g (5mol) of butylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 637.3g of sorbitan polyoxyethylene (n ═ 3) polyoxybutylene (n ═ 5) ether, with a yield of 97.0%.
③ to a dry reactor, 328.5g (0.5mol) of sorbitan polyoxyethylene (n-3) butylene (n-5) ether, 284.5g (1mol) of stearic acid, and 3g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 567.8g of sorbitan polyoxyethylene (n ═ 3) polyoxybutylene (n ═ 5) ether stearic acid (m ═ 2) ester in 95.4% yield.
(b) Preparation of an auxiliary agent:
(. 1mol) of lauryl alcohol 186g and 7.0g of potassium carbonate were added to a pressure reactor, and oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 110 ℃, 132g (3mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10 MPa. After completion of the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 305g of laureth (n-3) ether in a yield of 95.9%.
② to a dry reaction kettle159g (0.5mol) of laureth (n ═ 3) ether, 72g (0.5mol) of octanoic acid and 2g of potassium hydrogencarbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 200 ℃ and reacted for 2 h. After cooling, neutralization and dehydration were carried out to obtain 215.5g of laureth octanoate (n ═ 3) in a yield of 97.4%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxyethylene (n ═ 3) butylene (n ═ 5) ether stearic acid (m ═ 2) ester prepared in step (a) and polyoxyethylene lauryl (n ═ 3) ether caprylate ester are mixed at a molar ratio of 1: 3 and stirring for 3 hours to obtain the chemical agent composition S09 containing the sorbitan polyether carboxylate.
[ example 10 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 1g of p-toluenesulfonic acid into a reaction kettle, and removing oxygen in the reaction kettle in vacuum. In N2Heating to 150 ℃ under protection, and reacting for 15min to obtain the sorbitan.
② adding 5.4g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 120 ℃, 348g (6mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the propylene oxide reaction is finished, 288g (4mol) of butylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 771g of sorbitan polyoxypropylene (n-6) polyoxybutylene (n-4) ether in a yield of 96.2%.
③ to a dry reaction vessel, 400.5g (0.5mol) of sorbitan polyoxypropylene (n-6) polyoxybutylene (n-4) ether, 140g (0.7mol) of lauric acid, 3g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 512.5g of sorbitan polyoxypropylene (n ═ 6) polyoxybutylene (n ═ 4) ether lauric acid (m ═ 1.4) ester, with a yield of 97.1%.
(b) Preparation of an auxiliary agent:
adding into a pressure reactor262.5g (1mol) of dodecylphenol and 5.6g of potassium hydroxide are added and the oxygen is removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 174g (3mol) of propylene oxide is slowly pumped in, and the pressure is controlled to be less than or equal to 0.20 MPa. After completion of the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 416.0g of dodecylphenol polyoxypropylene (n ═ 3) ether, with a yield of 95.3%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxypropylene (n ═ 6) butylene (n ═ 4) ether lauric acid (m ═ 1.4) ester and dodecylphenol polyoxypropylene (n ═ 3) ether prepared in step (a) were mixed in a molar ratio of 1: 2 and stirring for 3 hours to obtain the chemical agent composition S10 containing the sorbitan polyether carboxylate.
[ example 11 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 1g of p-toluenesulfonic acid into a reaction kettle, and removing oxygen in the reaction kettle in vacuum. In N2Heating to 150 ℃ under protection, and reacting for 15min to obtain the sorbitan.
② adding 5.4g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 120 ℃, 348g (6mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the propylene oxide reaction is finished, 288g (4mol) of butylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 771g of sorbitan polyoxypropylene (n-6) polyoxybutylene (n-4) ether in a yield of 96.2%.
③ to a dry reaction vessel, 400.5g (0.5mol) of sorbitan polyoxypropylene (n-6) polyoxybutylene (n-4) ether, 140g (0.7mol) of lauric acid, 3g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 512.5g of sorbitan polyoxypropylene (n ═ 6) polyoxybutylene (n ═ 4) ether lauric acid (m ═ 1.4) ester, with a yield of 97.1%.
(b) Preparation of an auxiliary agent:
262.5g (1mol) of dodecylphenol and 5.6g of potassium hydroxide were added to a pressure reactor and oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 174g (3mol) of propylene oxide is slowly pumped in, and the pressure is controlled to be less than or equal to 0.20 MPa. After completion of the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 416.0g of dodecylphenol polyoxypropylene (n ═ 3) ether, with a yield of 95.3%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxypropylene (n ═ 6) butylene (n ═ 4) ether lauric acid (m ═ 1.4) ester and dodecylphenol polyoxypropylene (n ═ 3) ether prepared in step (a) were mixed in a molar ratio of 1: 28 and stirring for 3 hours to obtain the chemical agent composition S11 containing the sorbitan polyether carboxylate.
[ example 12 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 1g of p-toluenesulfonic acid into a reaction kettle, and removing oxygen in the reaction kettle in vacuum. In N2Heating to 150 ℃ under protection, and reacting for 15min to obtain the sorbitan.
② adding 5.4g of potassium hydroxide into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 120 ℃, 576g (8mol) of butylene oxide is slowly added, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction was completed, the temperature was reduced to 90 ℃, and the low boiling point substance was removed under reduced pressure, and the reaction mixture was cooled, neutralized and dehydrated to obtain 702.5g of sorbitan polyoxybutylene (n ═ 8) ether, with a yield of 94.8%.
③ to a dry autoclave, 370.5g (0.5mol) of sorbitan polyoxybutylene (n ═ 8) ether, 153.6g (0.6mol) of palmitic acid, 4g of sodium bicarbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 485.5g of sorbitan polyoxybutylene (n ═ 8) ether palmitate (m ═ 1.2), yield 94.6%.
(b) Preparation of an auxiliary agent:
adding phenol 262 to the pressure reactor.5g (1mol) and 10.2g of potassium carbonate, oxygen being removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 176g (4mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After completion of the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 421.4g of phenolpolyoxyethylene (n ═ 4) ether, with a yield of 96.1%.
② to a dry reaction vessel 219.2g (0.5mol) of phenolpolyoxyethylene (n-4) ether, 100g (0.5mol) of lauric acid, 2g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, neutralization and dehydration were carried out to obtain 299.0g of phenolpolyoxyethylene (n ═ 4) ether laurate in a yield of 96.4%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxybutylene (n ═ 8) ether palmitic acid (m ═ 1.2) ester prepared in step (a) and phenol polyoxyethylene (n ═ 4) ether laurate were mixed in a molar ratio of 1: 1.5, and stirring for 3 hours to obtain the chemical agent composition S12 containing the sorbitan polyether carboxylate.
[ example 13 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 1g of p-toluenesulfonic acid into a reaction kettle, and removing oxygen in the reaction kettle in vacuum. In N2Heating to 150 ℃ under protection, and reacting for 15min to obtain the sorbitan.
② adding 7.2g of potassium carbonate into the reaction kettle, and removing the air in the reaction bottle in vacuum. N is a radical of2Under protection, the system is heated to 120 ℃, 348g (6mol) of propylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the propylene oxide reaction is finished, 176g (4mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10 MPa. After completion of the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 675.9g of sorbitan polyoxypropylene (n-6) polyoxyethylene (n-4) ether, with a yield of 98.1%.
③ to a dry autoclave were added 344.5g (0.5mol) of sorbitan polyoxypropylene (n-6) polyoxyethylene (n-4) ether, 179.5g (0.7mol)Palmitic acid, 3.0g potassium bicarbonate, oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to obtain 487.9g of sorbitan polyoxypropylene (n-6) polyoxyethylene (n-4) ether palmitic acid (m-1.4) ester in 95.4% yield.
(b) Preparation of an auxiliary agent:
phenol 262.5g (1mol) and 10.2g of potassium carbonate were added to the pressure reactor and the oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 174g (3mol) of propylene oxide is slowly pumped in, and the pressure is controlled to be less than or equal to 0.20 MPa. After completion of the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 422.1g of phenol polyoxypropylene (n ═ 3) ether, with a yield of 96.7%.
② to a dry reaction vessel 218.3g (0.5mol) of phenol polyoxypropylene (n-3) ether, 114g (0.5mol) of myristic acid, 2.5g of potassium hydrogencarbonate, oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, neutralization and dehydration were carried out to obtain 310.7g of phenol polyoxypropylene (n ═ 3) ether myristate with a yield of 96.2%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxypropylene (n ═ 6) polyoxyethylene (n ═ 4) ether palmitate and phenol polyoxypropylene (n ═ 3) ether myristate prepared in step (a) were mixed at a molar ratio of 1: 1.8, and stirring for 3 hours to obtain the chemical agent composition S13 containing the sorbitan polyether carboxylate.
[ EXAMPLES 14 ]
(a) Preparation of sorbitan polyether carboxylate:
adding 183g (1mol) of sorbitol and 2g P to a reaction kettle2O5And removing oxygen in the reaction kettle in vacuum. In N2Heating to 160 ℃ under protection, and reacting for 1.5h to obtain the sorbitan.
② 6.4g of potassium hydroxide is added into the reaction kettle, and the air in the reaction bottle is removed in vacuum. N is a radical of2Under protection, the system is heated to 110 ℃, 132g (3mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.10 MPa. To-be-encircledAfter the reaction of the ethylene oxide is finished, the temperature is raised to 120 ℃, 174g (3mol) of propylene oxide is slowly pumped in, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction of the propylene oxide is finished, 216g (3mol) of butylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.20 MPa. After the reaction was completed, the temperature was reduced to 90 ℃, and the low boiling point substance was removed under reduced pressure, and after cooling, neutralization and dehydration were carried out to obtain 655.4g of sorbitan polyoxyethylene (n ═ 3) polyoxypropylene (n ═ 3) polyoxybutylene (n ═ 3) ether, with a yield of 95.4%.
③ to a dry reactor, 343.5g (0.5mol) of sorbitan polyoxyethylene (n-3) polyoxypropylene (n-3) polyoxybutylene ether, 100g (0.5mol) of lauric acid, and 2.8g of sodium hydrogen carbonate were added, and oxygen was removed in vacuo. In N2Under protection, the system is heated to 215 ℃ and reacted for 2 h. After cooling, dehydration was neutralized to give 419.3g of sorbitan polyoxyethylene (n ═ 3) polyoxypropylene (n ═ 3) polyoxybutylene ether (n ═ 3) lauric acid (m ═ 1.0) ester, 96.5% yield.
(b) Preparation of an auxiliary agent:
the pressure reactor was charged with 158g (1mol) of isomeric dodecanol and 5.6g of potassium hydroxide and the oxygen was removed in vacuo. N is a radical of2Under protection, the system is heated to 120 ℃, 174g (3mol) of propylene oxide is slowly pumped in, and the pressure is controlled to be less than or equal to 0.20 MPa. After completion of the reaction, the temperature was reduced to 90 ℃ and the low boiling point substance was removed under reduced pressure, followed by cooling, neutralization and dehydration to obtain 318.4g of isomeric tridecanol polyoxypropylene (n ═ 3) ether, with a yield of 95.9%.
(c) Preparation of chemical agent composition containing sorbitan polyether carboxylate:
at normal temperature, the sorbitan polyoxyethylene (n ═ 3) polyoxypropylene (n ═ 3) polyoxybutylene (n ═ 3) ether laurate and isomeric decyl alcohol polyoxypropylene (n ═ 3) ether prepared in step (a) are mixed in a molar ratio of 1: 15 and stirring for 3 hours to obtain the chemical agent composition S14 containing the sorbitan polyether carboxylate.
[ COMPARATIVE EXAMPLE 1 ]
Example 1 step (a) preparation of sorbitan polyoxypropylene (n ═ 4) ether lauric acid (m ═ 1.4) ester S15.
[ COMPARATIVE EXAMPLE 2 ]
Example 2 isomeric tridecanol polyoxypropylene (n-3) ether S16 from step (b).
[ example 15 ] measurement of minimum miscible pressure
The invention adopts a thin tube experiment method to research the chemical agent system on CO2Driving the effect of reducing the minimum miscible pressure. With reference to the standard "SY/T6573-. The tubule parameters are shown in Table I. The experimental procedure was as follows: 1. after the thin tube is cleaned, the thin tube is saturated with crude oil at the temperature and pressure required by the experiment. 2. CO injection at experimental temperature, pressure and constant injection rate2Displacing the crude oil, measuring the volume of produced oil once per 0.1 pore volume injection, and recording the upstream and downstream pressures of the tubules and the pump readings. 3. When CO is present2The displacement was stopped after the pump was built up to more than 1.5 pore volumes. 4. Calculation of CO injection at 1.2 pore volumes2The average value of the upstream and downstream pressures of the tubule is recorded as the displacement pressure. 4. And (4) selecting 4-6 pressure points, and repeating the steps 1-3 to perform a thin tube displacement experiment. Firstly, selecting an experiment under the original formation pressure, and determining other displacement pressures by adopting a method of successive approximation to minimum pressure according to the condition of miscibility or not and the degree of miscibility. And then, respectively taking 2-3 pressure points from the miscible section and the immiscible section to carry out a displacement experiment. 5. And drawing a relation curve of the displacement pressure and the displacement efficiency. The intersection of the immiscible and miscible segments is the Minimum Miscible Pressure (MMP).
Table-tubule basic parameters
Crude oil used in the tubule experiment is provided for Jiangsu oil fields, and the experiment temperature is 80 ℃.
First, pure CO was determined by means of a tubule experiment2Minimum miscible pressure of flooding. Then, injecting a certain concentration of chemical agent composition and supercritical CO by using an HPLC pump2Mixing, CO-injecting into a thin tube, and measuring CO by the same method2Minimum miscible pressure of + chemical "flooding. The test results are shown in Table II.
Compositions of epibichemical agents versus CO2Reduction of minimum miscible pressureFruit
[ example 16 ] oil displacement efficiency measurement
According to the standard SY/T6573-2003', the thin tube is adopted to carry out an indoor oil displacement experiment. Respectively developing pure CO at 80 ℃ and 22.0MPa2Drive and CO2+ chemical "flooding experiment, recording injection of 1.2PVCO2And the later oil displacement efficiency. The experimental results are shown in Table III.
Results of oil displacement test in the table three rooms