CN109679631B - Foam drainage agent composition for ultra-deep gas well, preparation method and application - Google Patents
Foam drainage agent composition for ultra-deep gas well, preparation method and application Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Abstract
The invention relates to a foam drainage agent composition for an ultra-deep gas well, a preparation method and application thereof, and mainly solves the problems that the existing foam drainage agent has poor high-temperature resistance in an acidic environment and cannot solve the problem of production reduction and even spray stoppage of the high-temperature ultra-deep gas well caused by liquid accumulation. The foam water discharging agent composition comprises the following components in parts by mass: (1)1 part of a long-chain polyamine compound; (2) 0-100 parts of cosurfactant; the long-chain polyamine compound has a general molecular formula shown in formula (1): the cosurfactant has the technical scheme that at least one of the zwitter-ion or cationic surfactant with the molecular general formula shown in the formula (2) or the anionic surfactant with the molecular general formula shown in the formula (3) better solves the problem and can be used for drainage and gas production of acidic high-temperature high-salt ultra-deep gas wells.
Description
Technical Field
The invention relates to a foam water discharging agent composition, a preparation method and application thereof, in particular to a foam water discharging agent composition for an ultra-deep gas well, a preparation method and application thereof.
Background
With the enhancement of the exploitation strength of the gas field, the water output of the gas field becomes a key problem restricting the normal production of the gas well. Foam drainage gas production is a drainage gas production technology which is rapidly developed at home and abroad in recent years, and has the advantages of simple equipment, convenience in construction, low cost, wide applicable well depth range, no influence on normal production of gas wells and the like. Foam drainage is to inject foam drainage agent into a well through an oil pipe or an oil casing ring, and foam with certain stability is generated under the stirring of airflow. The liquid phase slipped and deposited in the pipe is changed into foam, the relative density of fluid at the lower part in the pipe is changed, and the continuously produced gas phase displacement foam flows out of the shaft, so that the accumulated liquid in the shaft is discharged, and the purposes of water drainage and gas production are achieved.
The development of foam drainage agent since the sixties of the last century is carried out abroad, and surfactants such as sulfonate, benzene sulfonate, alkylphenol polyoxyethylene and the like are mostly selected. At present, a multi-component compound system is mostly adopted in the foam drainage agent for drainage and gas production, and in order to enhance the stability of single foam, auxiliaries such as alkali, alcohol, polymer, alkanolamide and the like are usually added into a formula to form reinforced foam. US7122509 reports a high temperature foam drainage agent formulation, which adopts a research idea of neutralization of anionic surfactant and amine to improve the temperature resistance of the system, and the drainage effect and use concentration are not referred to in the patent. US20120279715 reports a foam fluid for increasing oil yield by recovering gas in a gas well, which is an amido group-containing quaternary ammonium salt surfactant having both foam drainage and sterilization functions, a hydrophobic chain is a hydrophobic segment in substituted naphthalene ring, benzene ring or natural oil ester, and has strong chlorine resistance and condensate oil resistance, and also has good corrosion inhibition performance, the foam agent with an active matter concentration of 400ppm has a foam drainage rate of 86.8% in tap water and a foam drainage rate of 79.1% in simulated brine with a mineralization degree of 130000mg/L, however, because an amide group sensitive to high temperature is contained in a molecular structure, the foam fluid has poor adaptability to gas wells with a temperature of more than 100 ℃. China is a technology for researching foam drainage and gas production processes from the last 80 years, and a patent CN102212348A discloses a salt-resistant and methanol-resistant foam drainage agent, which comprises the following components in percentage by weight: 20-40% of cocamidopropyl betaine, 45-65% of amine oxide, 5-20% of alpha-olefin sulfonate, 5-15% of triethanolamine, 0.2-2% of fluorocarbon surfactant and 0-5% of methanol, wherein the mineralization resistance can reach 18 ten thousand, and the amount of the foaming agent is 5000ppm, but the agent contains the fluorocarbon surfactant, so that not only the cost is greatly improved, but also the environmental impact is large.
The results show that the poor high-temperature and high-salt resistance is a main factor for restricting the development of the foam drainage technology of the high-temperature ultra-deep gas well. The long-chain polyamine compound containing stable chemical bonds can avoid hydrolysis under acidic high-temperature and high-salt conditions, maintain the stability of a molecular structure and maintain the foam drainage capability of the foam drainage agent to the maximum extent. The invention relates to a foam water discharging agent composition suitable for an ultra-deep gas well, a preparation method and application thereof in water discharging and gas production.
Disclosure of Invention
The invention aims to solve the technical problems that the existing foam discharging agent has poor high-temperature resistance in an acidic environment and cannot solve the problems of yield reduction and even spray stoppage caused by liquid accumulation in a high-temperature ultra-deep gas well, and provides a foam water discharging agent composition for the ultra-deep gas well, which is applied to a high-temperature deep well, has very excellent stability, strong liquid carrying, foaming and foam stabilizing performances under an acidic condition.
The second technical problem to be solved by the present invention is to provide a method for preparing a foam drainage agent composition for ultra-deep gas wells, which corresponds to the solution of the first technical problem.
The third technical problem to be solved by the present invention is to provide an application of the foam drainage agent composition for ultra-deep gas well corresponding to one of the above technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the foam water discharging agent composition for the ultra-deep gas well comprises the following components in parts by weight:
(1)1 part of a long-chain polyamine compound;
(2) 0-100 parts of cosurfactant;
wherein the long-chain polyamine compound has a molecular general formula shown in formula (1):
in the formula (1), R1Is selected from C4～C32One of hydrocarbyl or substituted hydrocarbyl, R2、R3Independently selected from H, C1～C5One of hydrocarbyl or substituted hydrocarbyl; m is-N (A) CH2CH2-the number of fragments, m ═ 1 to 10; a is- [ CH (CH)3)CH2O]s3[CH2CH2O]r3R4，R4Selected from H, C1～C5Hydrocarbyl or substituted hydrocarbyl; s1, s2 and s3 are the addition number of propoxy groups PO, s1 is 0-20, s2 is 0-20, and s3 is 0-20; r1, r2 and r3 are addition numbers of ethoxy EO, r1 is 0-20, r2 is 0-20, and r3 is 0-20;
the zwitterionic or cationic surfactant has a general molecular formula shown in formula (2):
in the formula (2), R5Is selected from C4～C32One of hydrocarbyl or substituted hydrocarbyl, R6、R7Independently selected from (CH)2)aOH or (CH)2)bCH3One of (1), R8Is selected from (CH)2)aOH、(CH2)bCH3、(CH2)cOr (CH)2)c(CHOH)d(CH2)eWherein a is any integer from 2 to 4, b is any integer from 0 to 5, c is any integer from 1 to 4, d is any integer from 0 to 3, and e is any integer from 1 to 4; n is the addition number of propoxy groups PO, and n is 0-15; p is the addition number of an ethoxy group EO, and p is 0-30; x-Is selected from OH-Halogen anion, HCO3 -、NO3 -、CH3OSO3 -、CH3COO-、COO-、SO3 -Or OSO3 -One kind of (1).
The anionic surfactant has a general molecular formula shown in formula (3):
in the formula (3), R9And R10The sum is selected from C3～C31One of hydrocarbyl or substituted hydrocarbyl, M is selected from hydrogen, alkali metal or of the formula NR11(R12)(R13)(R14) At least one of the groups shown, R11、R12、R13、R14Is independently selected from H, (CH)2)aOH or (CH)2)bCH3Wherein a is any integer of 2 to 4, b is any integer of 0 to 5。
In the above technical scheme, R1、R5、R9And R10The sum is preferably C8～C24Hydrocarbyl or substituted hydrocarbyl.
In the above technical scheme, R2、R3、R4Preferably H or CH3More preferably, H.
In the above technical scheme, R6、R7、R8Preferably CH3、C2H5、(CH2)2OH or C6H5CH2Or R is8X-Preferably CH2COO-、(CH2)3SO3 -、CH2(CHOH)CH2SO3 -One kind of (1).
In the above-mentioned technical means, m is preferably 1 to 5.
In the above technical solutions, s1+ s2+ m is preferable*S3＝0～5，r1+r2+m*r3＝0～10，n＝0～5，p＝0～5。
In the technical scheme, the mass ratio of the long-chain polyamine compound to the cosurfactant in the foam scrubbing agent composition is preferably 1 to (0-10).
The key effective components of the foam drainage agent composition suitable for the ultra-deep gas well are (1) and (2), and the person skilled in the art knows that the foam drainage agent composition can be supplied in various forms for transportation and storage or on-site use, such as a non-aqueous solid form, an aqueous paste form or an aqueous solution form; the aqueous solution form comprises a form of preparing concentrated solution by using water, and is directly prepared into a solution form with the concentration required by site drainage; the water is not particularly required, and can be deionized water or water containing inorganic minerals, and the water containing the inorganic minerals can be tap water or gas field formation water. The foam remover composition of the present invention can be obtained by mixing the long-chain polyamine compound and the co-surfactant at a desired ratio, and is preferably obtained by the following means for solving the second technical problem.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of the foam scrubbing agent composition for solving the technical problems comprises the following steps:
(1) preparation of long-chain polyamine compounds
a. Amidation reaction:
r is to be0COOR' and H (NHCH)2CH2)mNH2Mixing the catalysts according to the molar ratio of 1 (1-2) to 0-0.5, reacting for 3-15 hours at the reaction temperature of 50-200 ℃ under stirring, and evaporating alcohol or water generated in the reaction under normal pressure or reduced pressure to obtain the required amide compound R0CO(NHCH2CH2)mNH2. Wherein R is0Is selected from C3～C31One of hydrocarbyl or substituted hydrocarbyl, R' is selected from H and C1～C8And (b) 1-10, wherein the catalyst is at least one selected from alkali metal hydroxides, alkali metal alkoxides and alkali metal carbonates.
b. Reduction reaction:
R0CO(NHCH2CH2)mNH2the reduction of the lactam can be carried out by catalytic hydrogenation, heterogeneous catalytic reaction at high temperature and high pressure to generate the corresponding amine, or by the following steps: the R synthesized in the step a0CO(NHCH2CH2)mNH2With metal hydrides H-Y+Reduction in an aprotic solvent to give R0CH2(NHCH2CH2)mNH2. Wherein, Y+Is a metal compound, a metal alkyl compound or a metal amino compound.
c. And (3) polyether esterification:
in the presence of a basic catalyst, the R synthesized in the step b0CH2(NHCH2CH2)mNH2Reacting with required amount of propylene oxide and ethylene oxide in sequence to obtain the long-chain polyamine compound shown in the formula (1).
(2) And (2) adding the long-chain polyamine compound synthesized in the step (1) and the cosurfactant according to the required mass part, and uniformly mixing to obtain the required foam drainage agent.
In the above technical scheme, R0COOR’、H(NHCH2CH2)mNH2The molar ratio of the catalyst is preferably 1 (1-1.3) to 0-0.1, and the catalyst is preferably at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
In the above technical scheme, H-Y+Preferably LiAlH4、LiAlH(OEt)3Or NaBH4One kind of (1).
In the above technical solution, the aprotic solvent is preferably at least one of diethyl ether, tetrahydrofuran, and dioxane.
The foam water discharging agent composition for the ultra-deep gas well has good compatibility, and can also contain other treating agents commonly used in the field.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the foam scrubbing agent composition in the technical scheme is applied to drainage and gas production of high-temperature ultra-deep gas wells.
In the technical scheme, the foam scrubbing agent is preferably applied to a high-temperature acid-gas-containing gas reservoir, the stratum temperature is 150-200 ℃, the total salinity of stratum brine is 5000-200000 mg/L, and H2S and CO2The content of (A) is 0-35%.
The long-chain polyamine compound in the foam drainage agent composition for the ultra-deep gas well has the thermal decomposition temperature of 200 ℃ or above, does not hydrolyze or hydrolyzes in a trace amount in an acidic aqueous solution, and has excellent temperature resistance; secondly, the nonionic fragments and the hydrophilic groups in the composition increase the salt resistance on one hand, and increase the amount of bound water and bound water carried by the foaming agent on the other hand, so that the liquid carrying amount of the foam is increased, and the liquid separation is slowed down; the composition simultaneously has functional groups with opposite electric property of negative and positive, so that the adsorption capacity of the foaming agent on a gas-liquid interface is increased, and the formed composition is more efficient, so that the composition can be applied to the high-temperature ultra-deep well drainage gas recovery process at the temperature of 150 ℃ or above at a lower concentration.
The key effective components (1) and (2) of the foam discharging agent, the solid filler and the adhesive have good compatibility, and the formed solid composition does not influence the foam discharging performance.
In the invention, the content or concentration of the foam scrubbing agent refers to the total content or total concentration of the component (1) and the component (2) in the technical scheme.
By adopting the technical scheme of the invention, 0.02-0.15% of foam discharging agent is in 0-200,000 mg/L salinity saline, the foaming height reaches 165mm before and after high-temperature aging, the liquid carrying rate reaches 92.4%, and the foam discharging agent has excellent temperature resistance, salt tolerance, foaming and liquid carrying performances and achieves better technical effects.
The invention is further illustrated by the following examples.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
[ example 1 ]
(1) Preparation of foam scrubbing agent FM01
a. 127.6 g (0.55 mol) of pentaethylenehexamine and 1.4 g (0.025 mol) of potassium hydroxide solid are added into a reaction bottle provided with a mechanical stirring device, a thermometer, a dropping funnel and an atmospheric distillation device, 148 g (0.5 mol) of methyl oleate is slowly dropped into the reaction bottle under stirring, the reaction is carried out for 6 hours at the reaction temperature of 120-160 ℃, and methanol generated by the reaction is collected at the same time, so that the required amide compound C can be obtained17H33CO(NHCH2CH2)5NH2The yield thereof was found to be 93.8%.
b. Removing water from a three-neck flask device provided with a reflux condenser tube, a dropping funnel and a thermometer, adding 7.6 g (0.2 mol) of lithium aluminum hydride and 90 ml of dry tetrahydrofuran, stirring, dispersing and mixing, and dropwise adding 49.6 g (0.1 mol) of C at-5 DEG C17H33CO(NHCH2CH2)5NH2Then the solution is added dropwise with 40 wt% tetrahydrofuran, and the reaction is carried out for 5 hours by slowly raising the temperature to about 30 ℃. Carefully pouring the reaction solution into ice water, and carrying out post-treatment to obtain a long-chain polyamine compound C17H33CH2(NHCH2CH2)5NH2The yield thereof was found to be 86.5%.
c. C is to be17H33CH2(NHCH2CH2)5NH2100 g, C16H33OC2H4N+(CH3)3Br-10 g of alpha-olefin sulfonate AOS (C)14～18)5 g of water is added and mixed evenly to prepare the foam drainage agent FM01 with the content of 35 percent.
(2) FM01 was dissolved in deionized water, 100,000mg/L, 200,000mg/L NaCl water, respectively, to make 0.3 wt% foam-expulsion mother liquor.
The performances of foaming power, foam stability, liquid carrying capacity and the like of the FM01 solution are measured according to SY/T6465-2000 evaluation method for foam-generating agent for water drainage and gas production, and the results are shown in Table 1.
A temperature resistance experiment is carried out by adopting a pressure-resistant stainless steel aging tank, and performances such as foaming power, foam stability, liquid carrying capacity and the like are measured again after aging is carried out for 24 hours at 180 ℃, and the results are shown in Table 1.
[ example 2 ]
The same as [ example 1 ] except that in the measurement of FM01 performance, pH was adjusted to 7, 4 and 2 with hydrochloric acid, and the results are shown in Table 2.
[ example 3 ]
(1) Preparation of foam scrubbing agent FM 02:
the same as [ example 1 ], except that C17H33CH2(NHCH2CH2)5NH2100 g, C16H33OC2H4N+(CH3)2CH2COO-10 g, AOS (C)14～18)5 g of water is added and mixed evenly to prepare the foam drainage agent FM02 with the content of 30 percent.
(2) The results are shown in Table 3, as in example 1.
[ example 4 ]
(1) Preparation of foam scrubbing agent FM 03:
the same as [ example 1 ], except that C17H33CH2(NHCH2CH2)5NH2200 g of water is added and mixed evenly to prepare the foam drainage agent FM03 with the content of 30 percent.
(2) The results are shown in Table 4, as in example 1.
[ example 5 ]
(1) Preparation of foam scrubbing agent FM 04:
a. preparation of C in the same manner as [ example 1 ] a17H33CO(NHCH2CH2)5NH2。
b. Removing water from a three-neck flask device provided with a reflux condenser tube, a dropping funnel and a thermometer, adding 11.4 g (0.3 mol) of lithium aluminum hydride and 90 ml of dry dioxane, stirring, dispersing and mixing, and dropping 49.6 g (0.1 mol) of C at-10-5 DEG C17H33CO(NHCH2CH2)5NH2The 40 wt% dioxane solution is added dropwise and slowly heated to about 35 ℃ for reaction for 3 hours. Carefully pouring the reaction solution into ice water, and carrying out post-treatment to obtain a long-chain polyamine compound C17H33CH2(NHCH2CH2)5NH2The yield thereof was found to be 89.0%.
c. To a pressure reactor equipped with a stirring device was added 194.0 g (0.4 mol) of C17H33CH2(NHCH2CH2)5NH24.0 g of potassium hydroxide, 72.5 g (1.25 mol) of propylene oxide and 92.4 g (2.1 mol) of ethylene oxide are sequentially reacted at 140-160 ℃ to obtain a long-chain polyamine compound1 (R1＝C18H35，m＝5，s1+s2+5S3＝3，r1+r2+5r3＝5，R2＝R3＝R4H), yield 95.7%.
d. Long-chain polyamine compounds110 g, C18H37OC2H4N+(CH2CH2OH)2(CH3)CH3COO-90 g internal olefin sulfonate IOS (C)19～23)15 g of water is added and mixed evenly to prepare the foam drainage agent FM04 with the content of 40 percent.
(2) The same as [ example 1 ] except that the aging temperature was 150 ℃ and the results are shown in Table 5.
[ example 6 ]
(1) Preparation of foam scrubbing agent FM 05:
the long-chain polyamine compound obtained in example 5150 g, C18H37O(C2H4O)2C2H4N+(CH3)2CH2COO-50 g, IOS (C)15～19)20 g of water is added and mixed evenly to prepare the foam drainage agent FM05 with the content of 30 percent.
(2) The results are shown in Table 6, as in example 5.
[ example 7 ]
(1) Preparation of foam scrubbing agent FM 06:
a. adding 67.0 g (0.65 mol) of diethylenetriamine and 6.9 g (0.05 mol) of potassium carbonate solid into a reaction bottle provided with a mechanical stirring device, a thermometer, a dropping funnel and a normal pressure distillation device, slowly dropping 114.0 g (0.5 mol) of ethyl laurate while stirring, reacting for 4 hours at the reaction temperature of 120-160 ℃, and collecting ethanol generated by the reaction to obtain the required amide compound C11H23CO(NHCH2CH2)2NH2The yield thereof was found to be 95.2%.
b. After removing water from a three-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer, LiAlH (OEt) was added351 g (0.3 mol) and 120 ml of anhydrous ether are stirred and mixed, and 49.6 g (0.1 mol) of C is dripped into the mixture at the temperature of between 5 ℃ below zero and 5 DEG C11H23CO(NHCH2CH2)2NH2Adding 50 wt% anhydrous ether solution, slowly heating to about 30 deg.C, and reacting for 7 hr. Carefully pouring the reaction solution into ice water, and carrying out post-treatment to obtain a long-chain polyamine compound C11H23CH2(NHCH2CH2)2NH2The yield thereof was found to be 81.9%.
c. C is to be11H23CH2(NHCH2CH2)2NH230 g, C22H45OC2H4N+(CH2CH2OH)2CH2COO-100 g of water is added and mixed evenly to prepare the foam drainage agent FM06 with the content of 35 percent.
(2) The same as [ example 1 ] except that the aging time was 48 hours, the results are shown in Table 7.
[ example 8 ]
(1) Preparation of foam scrubbing agent FM 07:
a. 85.8 g (0.6 mol) of triethylene tetramine and 2.8 g (0.05 mol) of potassium hydroxide solid are added into a reaction bottle provided with a mechanical stirring device, a thermometer, a dropping funnel and an atmospheric distillation device, and 139 g (0.5 mol) of R is slowly dropped into the reaction bottle under stirring0COOCH3(R0The carbon chain distribution of (A) is: c13 5.53％、C15 62.93％、C1731.54 percent. ) Reacting at 120-160 ℃ for 6 hours, and collecting methanol generated by the reaction to obtain the required amide compound R0CO(NHCH2CH2)3NH2The yield thereof was found to be 89.7%.
b. Removing water from a three-neck flask device provided with a reflux condenser tube, a dropping funnel and a thermometer, adding 9.5 g (0.25 mol) of lithium aluminum hydride and 60 ml of dry dioxane, stirring, dispersing and mixing, and dropping R with the content of 39.2 g (0.1 mol) at-10-5 DEG C0CO(NHCH2CH2)3NH2The 40 wt% dioxane solution is added dropwise and slowly heated to about 35 ℃ for reaction for 4 hours. Carefully pouring the reaction solution into ice water, and carrying out post-treatment to obtain a long-chain polyamine compound R0CH2(NHCH2CH2)3NH2The yield thereof was found to be 84.6%.
c. A pressure reactor equipped with a stirring device was charged with 150.4 g (0.4 mol) of R0CH2(NHCH2CH2)3NH24.0 g of potassium hydroxide reacts with 145.2 g (3.3 mol) of ethylene oxide at 140-160 ℃ to obtain a long-chain polyamine compound2(R1＝C16.5H33，m＝3，s1+s2+3S3＝0，r1+r2+3r3＝8，R2＝R3＝R4H), yield 97.2%.
d. Mixing long-chain polyamine-containing compound280 g, C18H37OC2H4N+(CH2CH2OH)2(CH2)3SO3 -80 g, IOS (C)19～23)40 g of water is added and mixed evenly to prepare the foam drainage agent FM07 with the content of 30 percent.
(2) The same as example 1, except that the aging temperature was 160 ℃ and the aging time was 48 hours, the results are shown in the table.
[ example 9 ]
(1) Preparation of foam scrubbing agent FM 08:
the difference is as in [ example 8 ]: long-chain polyamine compounds2200 g of water is added and mixed evenly to prepare the foam drainage agent FM08 with the content of 30 percent.
(2) The results are shown in Table 9, as in example 8.
[ example 10 ]
(1) Preparation of foam scrubbing agent FM 09:
the same as [ example 8 ], except that a long-chain polyamine compound is added2160 g, IOS (C)19～23)40 g of water is added and mixed evenly to prepare the foam drainage agent FM09 with the content of 35 percent.
(2) The results are shown in Table 10, as in example 8.
[ COMPARATIVE EXAMPLE 1 ]
The same as [ example 1 ], except that C16H33OC2H4N+(CH3)3Br-115 g water was added and mixed well to give a 30% strength foam drainage FM10, the results are shown in Table 11.
[ COMPARATIVE EXAMPLE 2 ]
The same as [ example 1 ], except that AOS (C)14～18)115 grams of water were mixed well to produce a 30% strength foam drainage FM11, the results of which are shown in Table 12.
[ COMPARATIVE EXAMPLE 3 ]
The difference is as in [ example 1 ]Is characterized in that C is16H33OC2H4N+(CH3)3Br-And AOS (C)14～18) The mixture was mixed to 115 g at a mass ratio of 2:1, and water was added thereto and mixed uniformly to obtain a 30% content of foam drainage agent FM12, the results of which are shown in Table 13.
[ COMPARATIVE EXAMPLE 4 ]
The same as [ example 6 ], except that C is added18H37O(C2H4O)2C2H4N+(CH3)2CH2COO-120 grams of water was added and mixed well to produce a 30% strength foam drainage FM13, the results are shown in Table 14.
[ COMPARATIVE EXAMPLE 5 ]
The same as [ example 6 ], except that IOS (C)15～19)120 g of water was added and mixed well to obtain a 30% strength foam drainage FM14, the results of which are shown in Table 15.
[ COMPARATIVE EXAMPLE 6 ]
The same as [ example 6 ], except that C is added18H37O(C2H4O)2C2H4N+(CH3)2CH2COO-And IOS (C)15～19)120 g of the mixture was mixed in a mass ratio of 1:1, and water was added thereto and mixed uniformly to obtain a 30% content of foam drainage agent FM15, the results of which are shown in Table 16.
TABLE 1
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TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
Watch 10
TABLE 11
TABLE 12
Watch 13
TABLE 14
Watch 15
TABLE 16
Claims (10)
1. A foam drainage agent composition comprises the following components in parts by weight:
(1)1 part of a long-chain polyamine compound;
(2) 0-100 parts of cosurfactant;
wherein the long-chain polyamine compound has a general molecular formula shown in formula (1):
in the formula (1), R1Is selected from C4～C32One of hydrocarbyl or substituted hydrocarbyl, R2、R3Independently selected from H, C1～C5One of hydrocarbyl or substituted hydrocarbyl; m is-N (A) CH2CH2-the number of fragments, m ═ 1 to 10; a is- [ CH (CH)3)CH2O]s3[CH2CH2O]r3R4，R4Selected from H, C1～C5Hydrocarbyl or substituted hydrocarbyl; s1, s2 and s3 are the addition number of propoxy groups PO, s1 is 0-20, s2 is 0-20, and s3 is 0-20; r1, r2 and r3 are addition numbers of ethoxy EO, r1 is 0-20, r2 is 0-20, and r3 is 0-20;
the cosurfactant is at least one of a zwitterionic surfactant, a cationic surfactant and an anionic surfactant.
2. The foam drainage agent composition according to claim 1, wherein the zwitterionic or cationic surfactant has a general molecular formula represented by formula (2):
in the formula (2), R5Is selected from C4～C32One of hydrocarbyl or substituted hydrocarbyl, R6、R7Independently selected from (CH)2)aOH or (CH)2)bCH3One of (1), R8Is selected from (CH)2)aOH、(CH2)bCH3、(CH2)cOr (CH)2)c(CHOH)d(CH2)eWherein a is any integer from 2 to 4, b is any integer from 0 to 5, c is any integer from 1 to 4, d is any integer from 0 to 3, and e is any integer from 1 to 4; n is the addition number of propoxy groups PO, and n is 0-15; p is the addition number of an ethoxy group EO, and p is 0-30; x-Is selected from OH-Halogen anion, HCO3 -、NO3 -、CH3OSO3 -、CH3COO-、COO-、SO3 -Or OSO3 -One of (1);
the anionic surfactant has a general molecular formula shown in formula (3):
in the formula (3), R9And R10The sum is selected from C3～C31One of hydrocarbyl or substituted hydrocarbyl, M is selected from hydrogen, alkali metal or of the formula NR11(R12)(R13)(R14) At least one of the groups shown, R11、R12、R13、R14Is independently selected from H, (CH)2)aOH or (CH)2)bCH3Wherein a is any integer of 2-4, and b is any integer of 0-5.
3. The foam drainage agent composition according to claim 2, wherein R is1、R5、R9And R10The sum of C11～C23Hydrocarbyl or substituted hydrocarbyl; r2、R3、R4Is H or CH3One of (1); r6、R7Is CH3、C2H5、(CH2)2One of OH; r8X-Is CH2COO-、(CH2)3SO3 -、CH2(CHOH)CH2SO3 -One kind of (1).
4. The foam drainage agent composition according to claim 2, wherein m is 1 to 5, s1+ s2+ m s3 is 0 to 5, r1+ r2+ m r3 is 0 to 10, n is 0 to 5, and p is 0 to 5.
5. The foam drainage agent composition according to claim 1, wherein the mass ratio of the long-chain polyamine compound to the cosurfactant in the foam drainage agent composition is 1: 0-10.
6. The foam drainage agent composition according to any one of claims 1 to 5, wherein the co-surfactant is selected from at least one of a zwitterionic or cationic surfactant and at least one of an anionic surfactant.
7. A method of making the foamed drainage agent composition of any of claims 1 to 6 comprising the steps of:
(1) preparation of long-chain polyamine compounds
a. Amidation reaction:
r is to be0COOR' and H (NHCH)2CH2)mNH2Mixing the catalysts according to the molar ratio of 1 (1-2) to 0-0.5, reacting for 3-15 hours at the reaction temperature of 50-200 ℃ under stirring, and evaporating alcohol or water generated in the reaction under normal pressure or reduced pressure to obtain the required amide compound R0CO(NHCH2CH2)mNH2(ii) a Wherein R is0Is selected from C3～C31One of hydrocarbyl or substituted hydrocarbyl, R' is selected from H and C1～C8The catalyst is at least one selected from alkali metal hydroxide, alkali metal alkoxide and alkali metal carbonate;
b. reduction reaction:
R0CO(NHCH2CH2)mNH2the reduction of the lactam adopts a catalytic hydrogenation method, and generates heterogeneous catalytic reaction at high temperature and high pressure to generate corresponding amine, or adopts the following steps: the R synthesized in the step a0CO(NHCH2CH2)mNH2With metal hydrides H-Y+Reduction in an aprotic solvent to give R0CH2(NHCH2CH2)mNH2(ii) a Wherein, Y+Is metal ion, metal alkyl ion, metal amino ion;
c. and (3) polyether esterification:
in the presence of a basic catalyst, the R synthesized in the step b0CH2(NHCH2CH2)mNH2Reacting with required amount of propylene oxide and ethylene oxide in sequence to obtain long-chain polyamine compound shown in formula (1);
(2) and (2) uniformly mixing the long-chain polyamine compound synthesized in the step (1) and the cosurfactant according to the required mass part to prepare the foam drainage agent composition.
8. The method of making the foam drainage agent composition of claim 7, wherein R is0COOR’、H(NHCH2CH2)mNH2The molar ratio of the catalyst is (1-1.3) to (0-0.1), and the catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
9. The method of making the foam drainage agent composition of claim 7, wherein the H is-Y+Is LiAlH4Or NaBH4The aprotic solvent is at least one of diethyl ether, tetrahydrofuran and dioxane.
10. The use of the foam water drainage agent composition as claimed in any one of claims 1 to 6 in drainage and gas production of high-temperature ultra-deep gas wells.
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| CN117343714A (en) * | 2022-06-27 | 2024-01-05 | 中国石油化工股份有限公司 | Foaming agent composition, acid gas switch viscoelastic foam system, method for improving recovery ratio by using foaming agent composition and acid gas switch viscoelastic foam system and application of acid gas switch viscoelastic foam system |
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