CN109679616B - Foam drainage agent with pH value response, preparation method and application - Google Patents
Foam drainage agent with pH value response, preparation method and application Download PDFInfo
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Abstract
The invention relates to a pH value response foam water discharging agent, a preparation method and application thereof, and mainly solves the problem that the existing foam water discharging agent contains H2S、CO2The high-temperature and high-salt resistance in an acidic environment is poor, and the problems of production reduction and even blowout stoppage caused by liquid loading of a high-temperature and high-salt ultra-deep gas well cannot be solved. The invention adopts the foam drainage agent comprising the surfactant shown in the formula (1); r1Is selected from C4～C32One of hydrocarbyl or substituted hydrocarbyl, R2、R3、R4Independently selected from H, C1～C5Hydrocarbyl or substituted hydrocarbyl carboxylates, C1～C5Alkyl or substituted alkyl sulfonates, C1～C5Hydrocarbyl or substituted hydrocarbyl phosphates or C1～C5At least one of alkyl or substituted alkyl sulfate, which is not H at the same time; the technical scheme that m is 1-10 solves the problem well, and can be used for drainage and gas production of acidic high-temperature high-salinity ultra-deep gas wells.
Description
Technical Field
The invention relates to a foam water discharging agent, a preparation method and application thereof, in particular to a pH value response foam water discharging agent, 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.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the existing foam drainage agent has poor high-temperature resistance in an acid 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.
The second technical problem to be solved by the present invention is to provide a method for preparing a foam drainage agent responding to the pH value of the foam drainage agent corresponding to the solution of the first technical problem.
The present invention is also directed to a method of using a foam drainage agent having a pH response corresponding to one of the above problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a pH-responsive foam drainage agent, which has a molecular general formula shown in formula (1):
in the formula (1), R1Is selected from C4～C32One of hydrocarbyl or substituted hydrocarbyl, R2、R3、R4Independently selected from H, C1～C5Hydrocarbyl or substituted hydrocarbyl carboxylates, C1～C5Alkyl or substituted alkyl sulfonates, C1～C5Hydrocarbyl or substituted hydrocarbyl phosphates or C1～C5At least one of alkyl sulfate or substituted alkyl sulfate, which is not H at the same time; m is-N (A) CH2CH2-the number of fragments, m ═ 1 to 10; a is a substituent represented by the formula (2); s1, s2 and s3 are the addition number of propoxy groups PO, s1 is 0-30, s2 is 0-30, and s3 is 0-30; r1, r2 and r3 are addition numbers of ethoxy EO, r1 is 0-30, r2 is 0-30 and r3 is0 to 30, and s1+ s2+ m × s3 and r1+ r2+ m × r3 are not zero at the same time.
In the above technical scheme, R1Preferably C8～C24Hydrocarbyl or substituted hydrocarbyl.
In the above technical scheme, R2、R3、R4Preferably H, CH2COOM、(CH2)3SO3M or CH2(CHOH)CH2SO3One of M is not H at the same time.
In the above-mentioned embodiments, M is preferably hydrogen, an alkali metal or a compound represented by the formula NR5(R6(R7)(R8) One of the groups shown.
In the above technical scheme, R5、R6、R7、R8Preferably H, (CH)2)aOH or (CH)2)bCH3In the above-mentioned manner, the first and second substrates are,
in the above technical means, a is preferably 2 to 4, and b is preferably 0 to 5.
In the above-mentioned technical means, m is preferably 1 to 5.
In the above technical solution, s1+ s2+ mxs 3 is preferably 0 to 5, and r1+ r2+ mxr 3 is preferably 0 to 10, and is not zero at the same time; more preferably, s1+ s2+ m × s3 is 1 to 5, and r1+ r2+ m × r3 is 1 to 10.
The key active ingredient of the pH-responsive foam drainage agent of the present invention is (1), and those skilled in the art will appreciate that it can be supplied in various forms, such as a non-aqueous solid form, an aqueous paste form, or an aqueous solution form, for convenience of transportation and storage, or for field use; 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.
To solve the second technical problem, the invention adopts the following technical scheme: a method for preparing a pH-responsive foam drainage agent to solve one of the above problems, comprising the steps of:
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 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～C8C is 1-10, and the catalyst is at least one selected from alkali metal hydroxide, alkali metal alkoxide and alkali metal carbonate;
b. reduction reaction:
R0CO(NHCH2CH2)mNH2reducing the lactam by adopting a catalytic hydrogenation method, and carrying out heterogeneous catalytic reaction at high temperature and high pressure to generate corresponding amine; or the following steps are adopted: 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 a metal compound, a metal alkyl compound, a metal amino compound;
c. and (3) polyether esterification:
in the presence of a basic catalyst, the R synthesized in the step b0CH2(NHCH2CH2)cNH2Sequentially reacting with required amount of propylene oxide and ethylene oxide to obtain long-chain polyamine polyether intermediate product R0CH2{N[(CHCH3CH2O)s3(CH2CH2O)r3H][CH2CH2]}mN[(CHCH3CH2O)s1(CH2CH2O)r1H][CHCH3CH2O)s2(CH2CH2O)r2)H]；
d. Carboxylation or sulfonation reaction:
c, mixing the long-chain polyamine polyether intermediate product obtained in the step c with an ionizing agent and a base in a molar ratio of 1: (1-5): (1-10) reacting in a solvent at 50-120 ℃ for 3-20 hours to generate polyamine polyether carboxylate or polyamine polyether sulfonate shown in the structural formula (1); obtaining the foam drainage agent; wherein the ionizing agent is selected from XR9Y1(ii) a The base is selected from alkali metal hydroxide or alkali metal alkoxide; r9Is C1～C6Alkylene or substituted alkylene; y is1Is SO3M1Or COON1，M1And N1Is alkali metal, and X is chlorine, bromine or iodine.
In the above technical scheme, R in the step a1COOR’、H(NHCH2CH2)mNH2The molar ratio of the catalyst is preferably 1 (1-1.3) to 0-0.1.
In the above technical scheme, the catalyst in step a is preferably at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
In the above technical scheme, step b is H-Y+Preferably LiAlH4、LiAlH(OEt)3Or NaBH4One kind of (1).
In the above technical solution, the aprotic solvent in step b is preferably at least one of diethyl ether, tetrahydrofuran, and dioxane.
In the above technical scheme, the long-chain polyamine polyether intermediate in step d: ionizing agent: the molar ratio of the alkali is preferably 1: (1-2): (1-4).
In the above technical scheme, the solvent in the step d is preferably selected from C3～C8Ketone and C6～C9Of aromatic hydrocarbons, e.g. from acetone, butanone, pentanone, mesitylene, toluene or xylene, trimethylbenzene, ethyltolueneBenzene and diethylbenzene.
In the above technical solution, the XR9Y1Examples of (b) include, but are not limited to, alkali metal salts of chloroacetic acid, alkali metal salts of bromoacetic acid, alkali metal salts of 3-chloro-2-hydroxypropanesulfonic acid, alkali metal salts of 2-chloroethanesulfonic acid, and the like.
The foam drainage agent with pH value response 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 application of the foam water-discharging agent with the pH value response in the technical scheme in drainage and gas production of the acidic high-temperature high-salt ultra-deep gas well.
In the above technical scheme, the application of the foam drainage agent is not particularly limited, and those skilled in the art can apply the foam drainage agent according to the existing drainage and gas production process technology, for example, but not limited to, the high-temperature acid gas-containing gas reservoir is preferred, the formation temperature is 150-200 ℃, the total mineralization of formation brine is 5000-200000 mg/L, and H is2S and CO2The content of (A) is 0-35%.
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 with pH value response, a preparation method and application thereof in water discharging and gas production.
The thermal decomposition temperature of the polyamine polyether carboxylate or the polyamine polyether sulfonate prepared by the invention is 200 ℃ or above, and the polyamine polyether carboxylate or the polyamine polyether sulfonate is not hydrolyzed or is hydrolyzed in a trace amount in an acidic aqueous solution, so that the polyamine polyether carboxylate or the polyamine polyether sulfonate has good temperature resistance; secondly, the nonionic fragment and the multi-hydrophilic group in the molecule 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 molecule contains hetero atoms responding to pH, so that the method can be applied to the drainage and gas production process of acidic high-temperature high-salt ultra-deep wells at 180 ℃.
By adopting the technical scheme of the invention, according to a SY/T6465-2000 foamer evaluation method for foam drainage and gas production, foam performance test of the foam drainage agent is carried out, and 0.02-0.15% of the foam drainage agent is in 0-200,000 mg/L salinity saline, before and after high-temperature aging, the foaming height reaches 171mm, the liquid carrying rate reaches 93.3%, and the foam drainage agent has excellent temperature resistance, salt tolerance, foaming and liquid carrying performances in an acidic environment, so that a better technical effect is obtained.
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 discharging agent F01
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 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. A pressure reactor equipped with a stirring device was charged with 192.8 g (0.4 mol) of C17H33CH2(NHCH2CH2)5NH24.0 g of potassium hydroxide, 469.8 g (8.1 mol) of propylene oxide and 52.8 g (1.2 mol) of ethylene oxide react sequentially at 140-160 ℃ to obtain the long-chain polyamine polyether compound1(R1＝C18H35，m＝5，s1+s2+5s3＝20，r1+r2+5r3＝3，R2＝R3＝R4H), yield 96.2%.
d. Long-chain polyamine polyether compounds1(R1＝C18H35，m＝5，s1+s2+5s3＝20，r1+r2+5r3＝3，R2＝R3＝R4H)177.4 g (0.1 mol) were mixed with 8.0 g (0.2 mol) of sodium hydroxide, 29.5 g (0.15 mol) of sodium 3-chloro-2-hydroxypropanesulfonate and 300 ml of toluene/benzene (v/v ═ 1) in a four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and heated to 90 ℃ for 7 hours. Evaporating to remove solvent, adding water to obtain long-chain polyamine polyether compound1(R1＝C18H35Sodium hydroxypropanesulfonate aqueous solution (R1 + R2+5R3 ═ 3) of m ═ 5, s1+ s2+5s3 ═ 20, and R1+ R2+5R3 ═ 32、R3、R4One of them is CH2CH(OH)CH2SO3Na and the balance of H) is used as a foam discharging agent F01.
(2) F01 was dissolved in deionized water, 100,000mg/L, 200,000mg/L NaCl water, respectively, to make 0.3 wt% foam-expulsion mother liquor.
The performance of the F01 solution, such as foaming power, foam stability, liquid carrying capacity and the like, is 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.
The experiment is carried out by adopting a pressure-resistant and acid-resistant aging device, and the 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 when the F01 performance was measured, the pH was adjusted to 7 and 4 with hydrochloric acid to simulate neutral and acidic gas environments, and the results are shown in table 2.
[ example 3 ]
(1) Preparation of foam discharging agent F02:
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 142.0 g (0.5 mol) of ethyl palmitate 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 C15H31CO(NHCH2CH2)2NH2The yield thereof was found to be 94.5%.
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 34.1 g (0.1 mol) of C is dripped into the mixture at the temperature of minus 5 to 5 DEG C15H31CO(NHCH2CH2)2NH2Adding 50 wt% anhydrous ether solution, slowly heating to about 30 deg.C, and reacting for 5 hr. Carefully pouring the reaction solution into ice water, and carrying out post-treatment to obtain a long-chain polyamine compound C15H31CH2(NHCH2CH2)2NH2The yield thereof was found to be 83.4%.
c. A pressure reactor equipped with a stirring device was charged with 130.8 g (0.4 mol) of C15H31CH2(NHCH2CH2)2NH25.2 g of potassium carbonate, 70.8 g (1.22 mol) of propylene oxide and 35.2 g (0.8 mol) of ethylene oxide are sequentially reacted at 140-160 ℃ to obtain a long-chain polyamine polyether compound 2 (R)1＝C16H33，m＝2，s1+s2+2s3＝3，r1+r2+2r3＝2，R2＝R3＝R4H), yield 97.6%.
d. Long-chain polyamine polyether Compound 2 (R)1＝C16H33，m＝2，s1+s2+2s3＝3，r1+r2+2r3＝2，R2＝R3＝R4H)58.9 g (0.1 mol) were mixed with 5.7 g (0.11 mol) of sodium methoxide, 13.4 g (0.11 mol of 1, 3-propanesultone and 100 ml of cyclopentanone in a four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and after the addition, the temperature was raised to reflux for 5 hours. Steaming to remove solventAdding ammonia water to obtain long-chain polyamine polyether compound 2 (R)1＝C16H33Aqueous ammonium propanesulfonate solutions (R1 + R2+2R3 ═ 2, s1+ s2+2s3 ═ 3, R1+ R2+2R3 ═ 2)2、R3、R4One of them is CH2CH2CH2SO3NH4And the balance being H), is a foam discharging agent F02.
(2) The same as [ example 1 ] except that the aging was carried out at 150 ℃ for 72 hours, the results are shown in Table 3.
[ example 4 ]
The same as [ example 3 ] except that in the measurement of the F02 performance, the pH was adjusted to 7 and 4 with hydrochloric acid to simulate neutral and acidic gas environments, and the aging was carried out at 150 ℃ for 72 hours, the results are shown in Table 4.
[ example 5 ]
(1) Preparation of foam discharging agent F03:
a. adding 36.0 g (0.6 mol) of ethylenediamine and 13.8 g (0.1 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 177.0 g (0.5 mol) of methyl behenate under stirring, reacting for 3 hours at the reaction temperature of 120-160 ℃, and collecting methanol generated by the reaction to obtain the required amide compound C21H43CONHCH2CH2NH2The yield thereof was found to be 91.6%.
b. Removing water from a three-neck flask device provided with a reflux condenser tube, a dropping funnel and a thermometer, adding 15.2 g (0.4 mol) of lithium aluminum hydride and 100 ml of dry dioxane, stirring, dispersing and mixing, and dropping 38.2 g (0.1 mol) of C at-10-5 DEG C21H43CONHCH2CH2NH2The 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 C21H43CH2NHCH2CH2NH2The yield thereof was found to be 87.9%.
c. A pressure reactor equipped with a stirring device was charged with 147.2 g (0.4 mol) of C21H43CH2NHCH2CH2NH25.2 g of potassium carbonate and 280.7 g (4.84 mol) of propylene oxide react at 140-160 ℃ to obtain a long-chain polyamine polyether compound 3 (R)1＝C22H45，m＝1，s1+s2+s3＝12，r1+r2+r3＝0，R2＝R3＝R4H), yield 98.1%.
d. Long-chain polyamine polyether Compound 3 (R)1＝C22H45，m＝1，s1+s2+s3＝12，r1+r2+r3＝0，R2＝R3＝R4H)106.4 g (0.1 mol) were mixed with 16.8 g (0.3 mol) of potassium hydroxide, 15.9 g (0.12 mol) of potassium chloroacetate and 400 ml of acetone in a reaction vessel equipped with a mechanical stirrer, a thermometer and a reflux condenser, and heated to reflux for 10 hours. Evaporating the solvent, and adding water to obtain long-chain polyamine polyether compound 3 (R)1＝C22H45Aqueous potassium acetate solution (R1 + R2+ R3) of 1, s1+ s2+ s 3-12, and R1+ R2+ R3-02、R3、R4One of them is CH2COOK, the remainder being H), a foam discharging agent F03.
(2) The same as [ example 1 ] except that the aging was carried out at 200 ℃ for 24 hours, the results are shown in Table 5.
[ example 6 ]
The same as [ example 5 ] except that in the measurement of the F03 performance, the pH was adjusted to 7 and 4 with hydrochloric acid to simulate neutral and acidic gas environments, and the aging was carried out at 200 ℃ for 24 hours, the results are shown in Table 6.
[ example 7 ]
(1) Preparation of foam discharging agent F04:
a. adding 36.0 g (0.6 mol) of ethylenediamine and 13.8 g (0.1 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 158.3 g (0.5 mol) of methyl abietate (formula 3) while stirring, reacting at the reaction temperature of 120-160 ℃ for 8 hours, and collecting methanol generated by the reaction to obtain the required amide compound C19H29CONHCH2CH2NH2The yield thereof was found to be 85.6%.
b. Removing water from a three-neck flask device provided with a reflux condenser tube, a dropping funnel and a thermometer, adding 13.3 g (0.35 mol) of lithium aluminum hydride and 100 ml of dry dioxane, stirring, dispersing and mixing, and dropping 34.4 g (0.1 mol) of C at-10-5 DEG C19H29CONHCH2CH2NH2The 40 wt% dioxane solution is added dropwise and slowly heated to about 35 ℃ for reaction for 5 hours. Carefully pouring the reaction liquid into ice water, and carrying out post-treatment to obtain a rosin polyamine compound C19H29CH2NHCH2CH2NH2The yield thereof was found to be 73.2%.
c. To a pressure reactor equipped with a stirring device was added 132.0 g (0.4 mol) of C19H29CH2NHCH2CH2NH25.0 g of potassium hydroxide and 160.2 g (3.64 mol) of ethylene oxide react at 140-160 ℃ to obtain the rosin polyamine polyether compound4(R1＝C20H31，m＝1，s1+s2+s3＝0，r1+r2+r3＝9，R2＝R3＝R4H), yield 91.4%.
d. Rosin polyamine polyether compounds4(R1＝C20H31，m＝1，s1+s2+s3＝0，r1+r2+r3＝9，R2＝R3＝R4H)72.6 g (0.1 mol) were mixed with 8.0 g (0.2 mol) of sodium hydroxide, 33.3 g (0.2 mol) of sodium 2-chloroethanesulfonate and 100 ml of toluene in a reaction vessel equipped with a mechanical stirrer, a thermometer and a reflux condenser and heated to reflux for 6 hours. Evaporating to remove solvent, adding water to obtain long-chain polyamine polyether compound4(R1＝C20H31Sodium ethanesulfonate aqueous solution (R1 + R2+ R3 ═ 9), where m is 1, s1+ s2+ s3 is 0, and R1+ R2+ R3 is 92、R3、R4One of them is CH2CH2SO3Na and the balance of H) is used as a foam discharging agent F04.
(2) The results are shown in Table 7, as in example 1.
[ example 8 ]
The same as example 7, except that when the performance of F04 was measured, the pH was adjusted to 2 with hydrochloric acid to simulate a high acid-containing gas atmosphere, and the results are shown in table 8.
[ COMPARATIVE EXAMPLE 1 ]
The same as [ example 1 ], except that C is used17H33CO(NHCH2CH2)5NH2(F05) The simulated water was 100,000mg/LNaCl instead of F01, and the results are shown in Table 9.
[ COMPARATIVE EXAMPLE 2 ]
The same as [ example 2 ], except that C is used17H33CO(NHCH2CH2)5NH2(F05) The simulated water was 100,000mg/LNaCl instead of F01, and the results are shown in Table 10.
[ COMPARATIVE EXAMPLE 3 ]
The difference is that C is used as C15H31CO(NHCH2CH2)2NH2(F06) The simulated water was 100,000mg/LNaCl instead of F02, and the results are shown in Table 9.
[ COMPARATIVE EXAMPLE 4 ]
The same as [ example 4 ], except that C is used15H31CO(NHCH2CH2)2NH2(F06) The simulated water was 100,000mg/LNaCl instead of F02, and the results are shown in Table 10.
[ COMPARATIVE EXAMPLE 5 ]
The same as [ example 5 ], except that C is used21H43CONHCH2CH2NH2(F07) The simulated water was 100,000mg/LNaCl instead of F03, and the results are shown in Table 9.
[ COMPARATIVE EXAMPLE 6 ]
The difference is that C is same as [ example 6 ]21H43CONHCH2CH2NH2(F07) The simulated water was 100,000mg/LNaCl instead of F03, and the results are shown in Table 10.
[ COMPARATIVE EXAMPLE 7 ]
The same as [ example 7 ], except that C is used19H29CONHCH2CH2NH2(F08) The simulated water was 100,000mg/LNaCl instead of F04, and the results are shown in Table 9.
[ COMPARATIVE EXAMPLE 8 ]
The same as [ example 8 ], except that C is used19H29CONHCH2CH2NH2(F08) The simulated water was 100,000mg/LNaCl instead of F04, and the results are shown in Table 10.
[ COMPARATIVE EXAMPLE 9 ]
The same as comparative example 1 except that oleyl alcohol polyoxyethylene ether hydroxypropyl sodium sulfonate C was used18H35O(C2H4O)3CH2CH(OH)CH2SO3Na (F09) was substituted for F01 to simulate water at 100,000mg/LNaCl, and the results are shown in Table 9.
The same as comparative example 2 except that oleyl alcohol polyoxyethylene ether hydroxypropyl sodium sulfonate C was used18H35O(C2H4O)3CH2CH(OH)CH2SO3Na (F09) was substituted for F01 to simulate water at 100,000mg/LNaCl, and the results are shown in Table 10.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
Watch 10
Claims (9)
1. The foam water discharging agent is characterized in that the molecular general formula of the foam water discharging agent is shown as a formula (1):
in the formula (1), R1Is selected from C8～C24One of hydrocarbyl or substituted hydrocarbyl, R2、R3、R4Independently selected from H, C1～C5Hydrocarbyl or substituted hydrocarbyl carboxylates, C1～C5Alkyl or substituted alkyl sulfonates, C1～C5Hydrocarbyl or substituted hydrocarbyl phosphates or C1～C5At least one of alkyl sulfate or substituted alkyl sulfate, which is not H at the same time; m is-N (A) CH2CH2-the number of fragments, m ═ 1 to 10; a is a substituent represented by the formula (2); s1, s2 and s3 are the addition number of propoxy groups PO, s1 is 0-30, s2 is 0-30, and s3 is 0-30; r1, r2 and r3 are addition numbers of ethoxy groups EO, r1 is 0-30, r2 is 0-30, r3 is 0-30, and s1+ s2+ m × s3 and r1+ r2+ m × r3 are not zero at the same time;
2. the foam drainage agent of claim 1, wherein R is2、R3、R4Independently selected from H, CH2COOM、(CH2)3SO3M or CH2(CHOH)CH2SO3One of M is not H at the same time; m is hydrogen, an alkali metal or a compound of the formula NR5(R6)(R7)(R8) One of the groups shown, R5、R6、R7、R8Is 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 according to claim 1, wherein m is 1-5; s1+ s2+ mxs 3 is 0-5, r1+ r2+ mxr 3 is 0-10, and is not zero at the same time.
4. A method of preparing a foam drainage agent according to any one of claims 1 to 3, comprising the steps of:
a. amidation reaction:
r is to be0COOR' and H (NHCH)2CH2)mNH2Mixing the catalysts in a molar ratio of 1 (1-2) to 0-0.5, stirring at a reaction temperatureReacting at 50-200 ℃ for 3-15 hours, and evaporating alcohol or water generated in the reaction under normal pressure or reduced pressure to obtain an 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～C8M is 1-10, and the catalyst is at least one selected from alkali metal hydroxide, alkali metal alkoxide and alkali metal carbonate;
b. reduction reaction:
R0CO(NHCH2CH2)mNH2reducing the lactam by adopting a catalytic hydrogenation method, and carrying out heterogeneous catalytic reaction at high temperature and high pressure to generate corresponding amine; or the following steps are adopted: the R synthesized in the step a0CO(NHCH2CH2)mNH2And H-Y+Reduction in an aprotic solvent to give R0CH2(NHCH2CH2)mNH2(ii) a Wherein H-Y+Is a metal compound, a metal alkyl compound, a metal amino compound;
c. and (3) polyether esterification:
in the presence of a basic catalyst, the R synthesized in the step b0CH2(NHCH2CH2)mNH2Sequentially reacting with required amount of propylene oxide and ethylene oxide to obtain long-chain polyamine polyether intermediate product R0CH2{N[(CHCH3CH2O)s3(CH2CH2O)r3H][CH2CH2]}mN[(CHCH3CH2O)s1(CH2CH2O)r1H][CHCH3CH2O)s2(CH2CH2O)r2)H]；
d. Carboxylation or sulfonation reaction:
c, mixing the long-chain polyamine polyether intermediate product obtained in the step c with an ionizing agent and a base in a molar ratio of 1: (1-5): (1-10) reacting in a solvent at 50-120 ℃ for 3-20 hours to form the compound of formula(1) Polyamine polyether carboxylate or polyamine polyether sulfonate as shown; obtaining the foam drainage agent; wherein the ionizing agent is selected from XR9Y1At least one of; the base is selected from alkali metal hydroxide or alkali metal alkoxide; y is1Is SO3M1Or COON1，M1And N1Is an alkali metal, and X is chlorine, bromine or iodine; r9Is C1～C6Alkylene or substituted alkylene.
5. The method of claim 4, wherein R is the same as R in step a0COOR’、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.
6. The method of claim 4, wherein the step H is performed in step b-Y+Is LiAlH4、LiAlH(OEt)3Or NaBH4Wherein the aprotic solvent is at least one of diethyl ether, tetrahydrofuran and dioxane.
7. The method for preparing a foam drainage agent according to claim 4, wherein the long-chain polyamine polyether intermediate product of the step d: ionizing agent: the molar ratio of the alkali is 1 to (1-2) to (1-4).
8. The method for preparing a foam drainage agent according to claim 4, wherein the solvent in step d is selected from C3～C8Ketone and C6～C9At least one aromatic hydrocarbon of (1).
9. The application of the foam water-discharging agent as claimed in any one of claims 1 to 3 in drainage and gas production of acidic high-temperature high-salt ultra-deep gas wells.
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