Surfactant and Preparation Method Therefor
20220403225 · 2022-12-22
Inventors
- Yingcheng Li (Shanghai, CN)
- Weidong Zhang (Shanghai, CN)
- Jun Jin (Shanghai, CN)
- Zhiqin Shen (Shanghai, CN)
- Xinning Bao (Shanghai, CN)
- Ou SHA (Shanghai, CN)
Cpc classification
C08G65/2612
CHEMISTRY; METALLURGY
C09K8/584
CHEMISTRY; METALLURGY
International classification
Abstract
A heteroatom-containing alkoxy polyether based anionic-nonionic surfactant has the following molecular formula (I):
R.sub.1—O-(Poly).sub.n-X—Y.sup.a−.a/bM.sup.b+ (I).
In formula (I), R.sub.1 is any one of C.sub.1-C.sub.50 aliphatic group and aromatic group; each occurrence of group Poly, equal to or different from each other, is independently selected from the group represented by formula (Ru—O).sub.m; n is a number from greater than 0 to 300; for each type of group (Ru—O), m is independently a number from greater than 0 to 100; X is any one of alkylene, alkenylene and arylene containing 1-10 carbon atoms; Y is an anionic group; and M is a cation or a cationic group.
Claims
1. A surfactant having a formula (I):
R.sub.1—O-(Poly).sub.n-X—Y.sup.a−.a/bM.sup.b+; (I) wherein: R.sub.1 is any one of C.sub.1-C.sub.50 aliphatic group or aromatic group; each occurrence of group Poly, equal to or different from each other, is independently selected from the group represented by formula (Ru—O).sub.m; in each group Poly, the each occurrence of group Ru, equal to or different from each other, is independently selected from C.sub.2-6 linear or branched alkylene group, with the proviso that: the group Ru in at least a part of the groups Poly is selected from butylene, and there is a spacer group L between at least a part of the groups Poly; wherein the L is a group containing a heteroatom and two free ends having 0 to 30 carbon atoms; n is a number from greater than 0 to 300; for each type of group (Ru—O), m is independently a number from greater than 0 to 100; X is any one of alkylene, alkenylene or arylene containing 1-10 carbon atoms; Y is an anionic group; M is a cation or cationic group maintaining charge balance of the formula; and a is the absolute value of the valence of Y, and b is the absolute value of the valence of M.
2. The surfactant according to claim 1, characterized in that R.sub.1 is any one of C.sub.1-C.sub.50 alkyl, alkenyl, aryl, or polycyclic aromatic hydrocarbon; more preferably any one of C.sub.1-C.sub.30 alkyl, alkenyl, aryl and polycyclic aromatic hydrocarbon; and the heteroatom is N and/or S.
3. The surfactant according to claim 1, characterized in that L is at least one selected from —NR.sub.6—, —S—, and —X.sup.1—R.sub.5—X.sup.2—, wherein X.sup.1 and X.sup.2 are independently selected from NR.sub.6 or S, R.sub.5 is any one selected from C.sub.0-C.sub.10 alkylene, alkenylene and arylene, and R.sub.6 is selected from H or C.sub.1-C.sub.4 alky.
4. The surfactant according to claim 3, characterized in that R.sub.5 is any one selected from the group consisting of C.sub.0-C.sub.6 alkylene, alkenylene and arylene groups, and R.sub.6 is selected from H.
5. The surfactant according to claim 1, characterized in that m is independently any number of 1 to 50.
6. The surfactant according to claim 1, characterized in that X is any one of an alkylene group, an alkenylene group, and an arylene group containing 1 to 6 carbon atoms.
7. The surfactant according to claim 1, characterized in that the anionic group is at least one of carboxylate, sulfonate, sulfate, or phosphate, more preferably at least one of carboxylate or sulfonate; the M is at least one selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, and an ammonium ion; more preferably at least one selected from the group consisting of Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, and NH.sub.4.sup.+.
8. The surfactant according to claim 1, characterized in that two or more identical or different spacer groups L are included in formula (I), and wherein at least one group Poly is positioned between two spacer groups L.
9. The surfactant according to claim 1, characterized in that in each of the groups Poly, at least a part of the group Ru of the groups Poly is selected from ethylene, at least a part of the group Ru of the groups Poly is selected from propylene or isopropylene, and at least a part of the group Ru of the groups Poly is selected from butylene, sec-butylene, isobutylene, or tert-butylene.
10. The surfactant according to claim 1, characterized in that at least two spacer groups L are comprised in formula (I), wherein at least a part of the groups L comprise heteroatom N and at least a part of the groups L comprise heteroatom S.
11. The surfactant according to claim 1, characterized in that in formula (I), the group Poly approaching to the R.sub.1 side has more carbon atoms than the group Poly approaching to the X side.
12. A surfactant having a molecular formula (II):
R.sub.1—O—(R.sub.2O).sub.x-L.sub.1-(R.sub.3O).sub.y-L.sub.2-(R.sub.4O).sub.z—X—Y.sup.a−.a/bM.sup.b+; (II) wherein: R.sub.1 is any one of C.sub.1-C.sub.50 aliphatic group or aromatic group; R.sub.2, R.sub.3 and R.sub.4 are at least one independently selected from the group consisting of ethylene, propylene and butylene, and x, y and z are each independently any number from greater than 0 to 100; L.sub.1 and L.sub.2 are independently a heteroatom-containing group having 0-30 carbon atoms and two free ends. X is any one of alkylene, alkenylene or arylene containing 1-10 carbon atoms; Y is an anionic group; M is a cation or cationic group maintaining charge balance of the formula; and a is the absolute value of the valence of Y, and b is the absolute value of the valence of M.
13. A process of producing the surfactant according to claim 1, comprising the steps of: a) carrying out an alkoxylation reaction on an initiator, ethylene oxide, propylene oxide and butylene oxide in the presence of a catalyst, to provide an alkoxy polyether nonionic surfactant; wherein the initiator is any one of C.sub.1-C.sub.50 alkyl alcohol, alkenyl alcohol, alkylphenol and polycyclic aromatic phenol; b) reacting the alkoxy polyether nonionic surfactant obtained in step a) with an organic amine reagent or a thiol reagent, to provide an alkoxy polyether nonionic surfactant containing N and/or S heteroatoms; and c) carrying out sulfonation or carboxylation reaction on the alkoxy polyether nonionic surfactant containing the heteroatom obtained in step b) and a sulfonation reagent or a carboxylation reagent, and then neutralizing, to provide the alkoxy polyether based anionic-nonionic surfactant.
14. The process of producing the surfactant according to claim 13, wherein the alkoxylation reaction is preferably carried out under conditions of: a reaction temperature of 140 to 200° C. and a reaction pressure of 0 to 5 MPa; a molar ratio of the initiator to the ethylene oxide, the propylene oxide or the butylene oxide of preferably 1:(1-50); and a catalyst of preferably an alkali metal hydroxide, DMC di-metallic polyether catalyst or phosphazene catalyst, preferably in an amount of 0.001 to 2.0% based on the initiator; step b) is carried out at a temperature of preferably 100 to 300° C. and a reaction pressure of preferably 0 to 5 MPa, for preferably 1 to 10 hours; and the sulfonation or carboxylation reaction is preferably carried out at a reaction temperature of 80 to 200° C. and a reaction pressure of 0 to 3 MPa.
15. A process of producing the surfactant according to claim 12, comprising the steps of: a) carrying out an alkoxylation reaction on an initiator, ethylene oxide, propylene oxide and butylene oxide in the presence of a catalyst, to provide an alkoxy polyether nonionic surfactant; wherein the initiator is any one of C.sub.1-C.sub.50 alkyl alcohol, alkenyl alcohol, alkylphenol and polycyclic aromatic phenol; b) reacting the alkoxy polyether nonionic surfactant obtained in step a) with an organic amine reagent or a thiol reagent, to provide an alkoxy polyether nonionic surfactant containing N and/or S heteroatoms; and c) carrying out sulfonation or carboxylation reaction on the alkoxy polyether nonionic surfactant containing the heteroatom obtained in step b) and a sulfonation reagent or a carboxylation reagent, and then neutralizing, to provide the alkoxy polyether based anionic-nonionic surfactant.
16. The process of producing the surfactant according to claim 15, wherein the alkoxylation reaction is preferably carried out under conditions of: a reaction temperature of 140 to 200° C. and a reaction pressure of 0 to 5 MPa; a molar ratio of the initiator to the ethylene oxide, the propylene oxide or the butylene oxide of preferably 1:(1-50); and a catalyst of preferably an alkali metal hydroxide, DMC di-metallic polyether catalyst or phosphazene catalyst, preferably in an amount of 0.001 to 2.0% based on the initiator; step b) is carried out at a temperature of preferably 100 to 300° C. and a reaction pressure of preferably 0 to 5 MPa, for preferably 1 to 10 hours; and the sulfonation or carboxylation reaction is preferably carried out at a reaction temperature of 80 to 200° C. and a reaction pressure of 0 to 3 MPa.
Description
DESCRIPTION OF DRAWINGS
[0047]
[0048]
[0049]
##STR00001##
[0050]
[0051] Surfactant concentration: 0.3 wt. %
[0052] Blue curve at 90° C.: mineralization degree of 35,000 mg/L, divalent ion content of 1,000 mg/L, and crude oil API=25,
[0053] Red curve at 120° C.: mineralization degree of 300,000 mg/L, divalent ion content of 10,000 mg/L, and crude oil API=18
EMBODIMENTS OF THE INVENTION
[0054] The invention is further illustrated by the following Examples.
Example 1
[0055] Synthesis of Anionic-Nonionic Surfactant of Heteroatom N-Containing Sodium Phenolpolyether Carboxylate
[0056] A certain amount of phenol and KOH in an amount of 1% relative to the weight of phenol as a catalyst were added into a polymerization reactor, the system was heated to 80-90° C. under stirring, a vacuum system was started, dehydrated for 1 hour, then purged with nitrogen for 3-4 times to remove air in the system. The reaction temperature was raised to 200° C., then metered butylene oxide was added slowly, and the reaction pressure was controlled to be <2.0 MPa to carry out etherification reaction. After this step of reaction was finished, a calculated amount of hydrazine hydrate was added, and reacted for 1 hour at a temperature of 100° C. and a pressure of 5 MPa. Then the temperature was raised to 180° C., a calculated amount of propylene oxide was continuously and slowly added, and after the reaction was finished, hydrazine hydrate was added again and reacted at 100° C. for 10 hours. The temperature was raised to 150° C. again, a calculated amount of ethylene oxide was added, for etherification reaction again until the reaction was finished (the reaction pressure being constant). The system was purged with nitrogen, and unreacted ethylene oxide was removed to provide a nonionic surfactant of phenol polyoxybutylene polyoxypropylene polyoxyethylene ether with different polymerization degrees.
[0057] The product obtained above and 2 times of molar amount of potassium hydroxide were added into a reactor, stirred, alkalized at 60° C. for 2 hours, heated to 80° C., sodium chloroacetate was slowly added, reaction was continued for 5 hours after the addition was finished, and post-treatment was carried out to provide an anionic-nonionic surfactant of heteroatom N-containing sodium phenol polyether carboxylate. The structure was shown in Table 1.
Example 2
[0058] Synthesis of Anionic-Nonionic Surfactant of Heteroatom N-Containing Calcium Nonylphenol Polyether Sulfonate
[0059] A certain amount of nonylphenol and KOH in an amount of 0.5% relative to the weight of nonylphenol as a catalyst were added into a polymerization reactor, the system was heated to 80-90° C. under stirring, a vacuum system was started, dehydrated for 1 hour, then purged with nitrogen for 3-4 times to remove air in the system. The reaction temperature was raised to 170° C., then metered propylene oxide was added slowly, and the reaction pressure was controlled to be <0.60 MPa to carry out etherification reaction. After this step of reaction was finished, ethylene diamine was added, and reacted at a temperature of 150° C. and a pressure of 4 MPa for 8 hours. Then a calculated amount of butylene oxide was slowly added, and after the reaction was finished, ethylene diamine was added again and reacted at a temperature of 150° C. and a pressure of 4 MPa for 8 hours. Finally, a calculated amount of ethylene oxide was added, for etherification reaction again until the reaction was finished (the reaction pressure being constant). The system was purged with nitrogen, and unreacted ethylene oxide was removed to provide nonylphenol polyether nonionic surfactant.
[0060] The product obtained above and 2 times of molar amount of potassium hydroxide were added into a reactor, stirred, alkalized at 60° C. for 2 hours, heated to 90° C., sodium chlorohexylsulfonate was slowly added in dropwise, reaction was continued for 5 hours after the addition was finished, and then calcium chloride was added for ion exchange, to provide an anionic-nonionic surfactant of heteroatom N-containing calcium nonylphenol polyether sulfonate. The structure was shown in Table 1.
Example 3
[0061] Synthesis of Anionic-Nonionic Surfactant of Heteroatom N-Containing Ammonium Dodecylnaphthalene Polyether Benzenesulfonate
[0062] A certain amount of dodecylnaphthol and KOH in an amount of 2.0% relative to the weight of dodecylnaphthol along with 30 ppm phosphazene as a catalyst were added into a polymerization reactor, the system was heated to 80-90° C. under stirring, a vacuum system was started, dehydrated for 1 hour, then purged with nitrogen for 3-4 times to remove air in the system. The reaction temperature was raised to 180° C., then metered butylene oxide was added slowly, and the reaction pressure was controlled to be <0.60 MPa to carry out etherification reaction. After this step of reaction was finished, propylene diamine was added, and reacted at a temperature of 250° C. and a pressure of 2 MPa for 6 hours. Then a calculated amount of propylene oxide was slowly added, and after the reaction was finished, propylene diamine was added again for an ammoniation reaction. Finally, a calculated amount of ethylene oxide was added again, for etherification reaction at 150° C. again until the reaction was finished (the reaction pressure being constant). The system was purged with nitrogen, and unreacted ethylene oxide was removed to provide dodecyl naphthalene polyether nonionic surfactant.
[0063] The product obtained above and 2 times of molar amount of potassium hydroxide were added into a reactor, stirred, alkalized at 60° C. for 2 hours, heated to 200° C., sodium p-chlorobenzenesulfonate was added, reaction was continued until complete conversion of the raw materials, and a post-treatment of ammonium exchange was carried out, to provide an anionic-nonionic surfactant of heteroatom N-containing ammonium dodecylnaphthalene polyether benzenesulfonate. The structure was shown in Table 1.
Example 4
[0064] Synthesis of Anionic-Nonionic Surfactant of Magnesium Methoxypolyether Carboxylate Containing Heteroatoms of S and N
[0065] A certain amount of methanol and KOH in an amount of 0.5% relative to the weight of the methanol as catalysts were added into a polymerization reactor, the system was heated to 140° C. under stirring, then metered ethylene oxide was added slowly, and the reaction pressure was controlled to be <1.0 MPa to carry out etherification reaction. After this step of reaction was finished, 1,3-propanedithiol was continuously added slowly, and reacted at a temperature of 180° C. and a pressure of 2 MPa for 5 hours. Then a calculated amount of propylene oxide was added and reacted for 4 hours. After the reaction was finished, a calculated amount of para-phenylene diamine was added, and reacted at a temperature of 280° C. and a pressure of 2 MPa for 6 hours. Finally, a calculated amount of butylene oxide was added, and heated to 200° C. for etherification reaction again until the reaction was finished, to provide a nonionic surfactant of heteroatom-containing methoxy polyether.
[0066] The product obtained above and 2 times of molar amount of potassium hydroxide were added into a reactor, stirred, alkalized at 60° C. for 2 hours, heated to 90° C., sodium chloroacetate was slowly added in dropwise, reaction was continued for 5 hours after the addition was finished, and then MgCl.sub.2 was added for ion exchange, to provide an anionic-nonionic surfactant of magnesium methoxypolyether carboxylate containing heteroatoms of S and N. The structure was shown in Table 1.
Example 5
[0067] Synthesis of Anionic-Nonionic Surfactant of Heteroatom N-Containing Sodium 2-Methyl-Benzyl Polyether Sulfonate
[0068] A certain amount of 2-methyl-benzyl alcohol and KOH in an amount of 0.5% relative to the weight of the 2-methyl-benzyl alcohol as catalysts were added into a polymerization reactor, the system was heated to 170° C. under stirring, then metered propylene oxide was added slowly, and the reaction pressure was controlled to be <1.0 MPa to carry out etherification reaction. After this step of reaction was finished, p-phenylene diamine was added, heated to 200° C. and reacted for 6 hours. Then the temperature was reduced to 150° C., a calculated amount of ethylene oxide was added, and after the reaction was finished, ethylene diamine was added, heated to 180° C. again and reacted for 4 hours. Finally, a calculated amount of butylene oxide was added, for etherification reaction again until the reaction was finished, to provide a nonionic surfactant of heteroatom N-containing 2-methyl-benzyl polyether.
[0069] The product obtained above and 2 times of molar amount of potassium hydroxide were added into a reactor, stirred, alkalized at 60° C. for 2 hours, heated to 80° C., sodium 3-chloro-2-hydroxy-propanesulfonate was slowly added dropwise, reaction was continued for 5 hours after the addition was finished, and post-treatment was carried out to provide an anionic-nonionic surfactant of heteroatom N-containing sodium 2-methyl-benzyl polyether sulfonate. The structure was shown in Table 1.
Example 6
[0070] Synthesis of Anionic-Nonionic Surfactant of Heteroatom N-Containing Sodium Cis-9-Octadecenoloxy Polyether Sulfonate
[0071] A certain amount of oleyl alcohol (cis-9-octadecenol) and KOH in an amount of 0.5% relative to the weight of the oleyl alcohol as catalysts were added into a polymerization reactor, the system was heated to 170° C. under stirring, then metered butylene oxide was added slowly, and the reaction pressure was controlled to be <1.0 MPa to carry out etherification reaction. After this step of reaction was finished, p-phenylene diamine was added, heated to 250° C. and reacted for 6 hours. Then the temperature was reduced to 170° C., a calculated amount of propylene oxide was added, and reacted for 5 hours. After the reaction was finished, ethylene diamine was added, heated to 180° C. again and reacted for 4 hours. Finally, a calculated amount of ethylene oxide was added, for etherification reaction again until the reaction was finished (the reaction pressure being constant). The system was purged with nitrogen, and unreacted ethylene oxide was removed to provide a polyether nonionic surfactant.
[0072] The product obtained above and 2 times of molar amount of potassium hydroxide were added into a reactor, stirred, alkalized at 60° C. for 2 hours, heated to 90° C., sodium 2-chloroethyl sulfonate was slowly added in dropwise, reaction was continued for 5 hours after the addition was finished, and post-treatment was carried out to provide an anionic-nonionic surfactant of heteroatom N-containing sodium cis-9-octadecenoloxy polyether sulfonate. The structure was shown in Table 1.
Example 7
[0073] Synthesis of Anionic-Nonionic Surfactant of Heteroatom N-Containing Sodium Polyether Carboxylate with a Long Carbon Chain
[0074] A certain amount of C.sub.30H.sub.61OH and KOH in an amount of 0.5% relative to the weight of the C.sub.30H.sub.61OH along with 0.01% di-metallic polyether catalyst (DMC) as catalyst were added into a polymerization reactor, the system was heated to 200° C. under stirring, then metered butylene oxide was added slowly, and the reaction pressure was controlled to be <1.0 MPa to carry out etherification reaction. After this step of reaction was finished, p-phenylene diamine was added, and reacted for 6 hours. Then the temperature was reduced to 170° C., a calculated amount of propylene oxide was added, and reacted for 5 hours. After the reaction was finished, ethylene diamine was added, heated to 180° C. again and reacted for 4 hours. Finally, the temperature was reduced to 150° C., and a calculated amount of ethylene oxide was added, for etherification reaction again until the reaction was finished (the reaction pressure being constant). The system was purged with nitrogen, and unreacted ethylene oxide was removed, to provide a nonionic surfactant of polyether with a long carbon chain.
[0075] The product obtained above and 2 times of molar amount of potassium hydroxide were added into a reactor, stirred, alkalized at 60° C. for 2 hours, heated to 90° C., sodium chloroacetate was slowly added in dropwise, reaction was continued for 5 hours after the addition was finished, and post-treatment was carried out to provide an anionic-nonionic surfactant of heteroatom N-containing sodium polyether carboxylate with a long carbon chain. The structure was shown in Table 1.
Example 8
[0076] Synthesis of Heteroatom N-Containing Ammonium Dodecylnaphthalene Polyether Benzenesulfonate
[0077] A certain amount of dodecylnaphthol and KOH in an amount of 2.0% relative to the weight of dodecylnaphthol along with 30 ppm phosphazene as a catalyst were added into a polymerization reactor, the system was heated to 80-90° C. under stirring, a vacuum system was started, dehydrated for 1 hour, then purged with nitrogen for 3-4 times to remove air in the system. The reaction temperature was raised to 160° C., then metered propylene oxide was added slowly, and the reaction pressure was controlled to be <0.60 MPa to carry out etherification reaction. After this step of reaction was finished, propylene diamine was added, and reacted at a temperature of 250° C. and a pressure of 2 MPa for 6 hours. Then a calculated amount of propylene oxide was added, and after the reaction was finished, propylene diamine was added again for an ammoniation reaction. Finally, a calculated amount of ethylene oxide was added again, for etherification reaction at 150° C. again until the reaction was finished (the reaction pressure being constant). The system was purged with nitrogen, and unreacted ethylene oxide was removed to provide dodecyl naphthalene polyether nonionic surfactant.
[0078] The product obtained above and 2 times of molar amount of potassium hydroxide were added into a reactor, stirred, alkalized at 60° C. for 2 hours, heated to 200° C., sodium p-chlorobenzenesulfonate was added, reaction was continued until complete conversion of the raw materials, to provide an anionic-nonionic surfactant of heteroatom N-containing sodium dodecylnaphthalene polyether benzenesulfonate. The structure was shown in Table 1.
Example 9
[0079] Synthesis of Anionic-Nonionic Surfactant of Heteroatom N-Containing Ammonium Cis-9-Octadecenoloxy Polyether Sulfonate
[0080] A certain amount of oleyl alcohol (cis-9-octadecenol) and KOH in an amount of 0.5% relative to the weight of the oleyl alcohol as catalysts were added into a polymerization reactor, the system was heated to 170° C. under stirring, then metered butylene oxide was added slowly, and the reaction pressure was controlled to be <1.0 MPa to carry out etherification reaction. After this step of reaction was finished, p-phenylene diamine was added, heated to 280° C. and reacted for 6 hours. Then, the temperature was reduced to 150° C., and a calculated amount of butylene oxide was added to be reacted for 5 hours, for etherification reaction again until the reaction was finished (the reaction pressure being constant). The system was purged with nitrogen, and unreacted butylene oxide was removed, to provide a polyether nonionic surfactant.
[0081] The product obtained above and 2 times of molar amount of potassium hydroxide were added into a reactor, stirred, alkalized at 60° C. for 2 hours, heated to 90° C., sodium 2-chloroethyl sulfonate was slowly added in dropwise, reaction was continued for 5 hours after the addition was finished, and post-treatment of ammonium exchange was carried out, to provide an anionic-nonionic surfactant of heteroatom N-containing sodium cis-9-octadecenoloxy polyether sulfonate. The structure was shown in Table 1.
Example 10: Evaluation of Emulsifying Property of Surfactant
[0082] The phase evaluation was performed according to SPE 113313 method to calculate the emulsifying capacity. The method mainly comprised the following steps: adding an aqueous solution of surfactant of a desired volume and concentration to a glass tube, and then adding crude oil to the solution, at a water-oil ratio in volume (WOR) of about 1.0. Sealing was followed by mixing. The mixture obtained was then placed in a metal bath, heated to a set temperature, and periodically sampled to mix, so as to enhance mass transfer between the phases. Equilibrium was considered to be reached until the visual interface position did not change. The emulsifying capacity was expressed in terms of the solubilization parameter SP, i.e., the volume or weight of water solubilized by unit volume or weight of surfactant in an oil, or the volume or weight of an oil solubilized by unit volume or weight of surfactant in water. The results were shown in Tables 2 and 3.
Example 11: Evaluation of Interfacial Properties of Surfactant
[0083] The interfacial tension change between the 0.3 wt % surfactant and a crude oil was measured with a TX-500C Spinning Drop Interface Tensiometer or a Dataphysics SVT20 under the conditions of oil reservoir temperature and a rotation speed of 5000 r/min, until oil drops were balanced. The results were shown in Tables 2 and 3.
Example 12: Evaluation of Oil-Washing Properties of Surfactant
[0084] A certain amount of oil-sand, with oil:sand=1:4 (weight ratio), was aged at the reservoir temperature for 10 days, during which stirring was carried out for 5 minutes every 2 hours. 5 g of the aged oil-sand was then mixed uniformly with a 0.3 wt % surfactant solution with a weight ratio of the oil-sand:the solution=1:10, and aged for 48 hours at the oil reservoir temperature. Crude oil in the solution was extracted with petroleum ether, adjusted with a 50 ml colorimetric tube to a metered volume, colorimetric analyzed with a spectrophotometer at a wavelength of 430 nm. The concentration of crude oil in the surfactant solution was calculated by referring to the standard curve. The results were shown in Tables 2 and 3.
Example 13: Evaluation of Oil Displacement Property of Surfactant
[0085] The oil displacement effect was physically simulated using the complex oil displacement system according to the SY/T6424-2000 complex oil displacement system performance test method, where a simulated oil displacement experiment was carried out at the oil reservoir temperature. Firstly, the core was injected with water till no crude oil was found in the effluent, then with a 0.3PV (pore volume of the core) of the surfactant composition, then with water till no crude oil was found in the effluent, so that the crude oil recovery improved was calculated. The results were shown in Tables 2 and 3.
Comparative Example 1
[0086] C.sub.30H.sub.61O(CH.sub.2CH.sub.2).sub.10CH.sub.2CH.sub.2COONa was prepared according to the process of CN201210188897.6, and property evaluations were performed, and the results were shown in Tables 2 and 3.
Comparative Example 2
[0087] The surfactant C.sub.30H.sub.61O—(BO).sub.8—(PO).sub.12-(EO).sub.30—SO.sub.3Na was prepared according to the process of US20110281779A1, and the properties were evaluated, and the results were shown in Tables 2 and 3.
TABLE-US-00001 TABLE 1 Surfactant compositions and structures of Examples 1-7 Surfactant Examples R.sub.1 —O— (R.sub.2O).sub.x - L.sub.1 - (R.sub.3O).sub.y - L.sub.2 - (R.sub.4O).sub.z - X-Y.sup.a−.sub.a/bM.sup.b+ 1 R.sub.1 = phenyl, R.sub.2 = C.sub.4H.sub.8, R.sub.3 = C.sub.3H.sub.6, R.sub.4 = C.sub.2H.sub.4, L.sub.1 = L.sub.2 = HNNH, x = 28, y = 20, z = 40, X = CH.sub.2, Y = COO.sup.−, a = b = 1, M = Na.sup.+ 2 R.sub.1 = nonylphenyl, R.sub.2 = C.sub.3H.sub.6, R.sub.3 = C.sub.4H.sub.8, R.sub.4 = C.sub.2H.sub.4, L.sub.1 = L.sub.2 = HNCH.sub.2CH.sub.2NH, x = 50, y = 12, z = 50, X = C.sub.6H.sub.12, Y = SO.sub.3.sup.−.sub., a = 1, b = 2, M = Ca.sup.2+ 3 R.sub.1 = dodecylnaphthalene, R.sub.2 = C.sub.4H.sub.8, R.sub.3 = C.sub.3H.sub.6, R.sub.4 = C.sub.2H.sub.4, L.sub.1 = L.sub.2 = HNCH.sub.2CH.sub.2CH.sub.2NH, x = 1, y = 50, z = 42, X = C.sub.6H.sub.4, Y = SO.sub.3.sup.−.sub., a = 1, b = 1, M = NH.sub.4.sup.+ 4 R.sub.1 = CH.sub.3, R.sub.2 = C.sub.2H.sub.4, R.sub.3 = C.sub.3H.sub.6, R.sub.4 = C.sub.4H.sub.8, L.sub.1 = SCH.sub.2CH.sub.2CH.sub.2S, L.sub.2 = HNC.sub.6H.sub.4NH, x = 22, y = 50, z = 1, X = CH.sub.2, Y = COO.sup.−, a = 1, b = 2, M = Mg.sup.2+ 5 R.sub.1 = 2—CH.sub.3—C.sub.6H.sub.4.sub.
TABLE-US-00002 TABLE 2 High temperature property of surfactants of Examples 1-7 Test conditions: 90° C., TDS of 35,000 mg/L, divalent ion content of 1,000 mg/L, crude oil API = 25, core permeability of 220 mD Interfacial Oil washing Improved Solubilization tension property recovery Examples parameters (mN/m) (%) (%) 1 12.5 0.00178 63 8.9 2 13.3 0.000997 68 9.2 3 17.2 0.000501 79 14.3 4 12.8 0.00160 62 9.3 5 14.1 0.00103 65 11.1 6 16.0 0.000611 73 13.3 7 13.3 0.000965 69 12.2 8 17.0 0.000521 78 14.1 9 15.8 0.000631 72.5 13.2 C. Ex. 1 6.8 0.0135 35 4.6 C. Ex. 2 8.0 0.00446 51 7.0
[0088] The surfactant composition produced by Example 3 was formulated into different concentrations, each was tested for the oil-water interfacial tension with the crude oil above. The results were listed in Table 3.
TABLE-US-00003 TABLE 3 oil-water interfacial tension between the surfactants (at different concentrations) and the crude oil Amount of the surfactant (wt %) 0.05 0.1 0.2 0.3 Interfacial tension (mN/m) 0.00526 0.000999 0.000688 0.000501
[0089] The results showed that the surfactant according to the invention had high oil-water interfacial activity for the tested thickened oil.
[0090] The surfactant of the invention was used for high-temperature and high-salinity thickened oil reservoirs, and the oil-water interfacial tension of the surfactant was tested, and the result was shown in Table 4.
TABLE-US-00004 TABLE 4 High temperature property of surfactants of Examples 1-7 Test conditions: 120° C., TDS of 300,000 mg/L, divalent ion content of 10,000 mg/L, crude oil API = 18, and core permeability of 500 mD Interfacial Oil washing Improved oil Solubilization tension property recovery Examples parameters (mN/m) (%) (%) 1 14.1 0.00100 65 8.8 2 13.3 0.00203 67 9.3 3 18.0 0.000379 82 15.1 4 12.7 0.00343 66 8.4 5 16.4 0.00266 72 12.2 6 18.1 0.000421 74 14.9 7 15.2 0.00388 64 9.3 8 17.9 0.000399 81 14.9 9 18.0 0.000429 74 14.8 C. Ex. 1 5.6 0.0422 34 3.7 C. Ex. 2 9.1 0.00518 52 7.3
[0091] As seen from the results in Tables 2, 3 and 4, the surfactants prepared by the present invention were superior in performances. The present inventors surprisingly found that both the emulsifying ability and the oil-washing ability were significantly improved, and an unexpected effect of improving the recovery ratio was obtained, as compared with Comparative Examples 1 and 2.